Use of iron-based compounds for the synthesis of boron compounds, and the corresponding processes

Abstract

The present invention relates to the use of iron-based compounds for the synthesis of boron compounds, and the corresponding processes. (no figures)

Description

Title of the invention: Use of iron-based compounds for the synthesis of boron compounds, and the corresponding processes. Technical field

[0001] The present invention relates to the use of iron-based compounds for the synthesis of boron compounds, and the corresponding processes. State of the art

[0002] The carbon-boron bond is one of the most versatile bonds in synthetic organic chemistry, serving as a pivot for the preparation, under mild conditions, of a wide variety of major chemical functionalities (often from boronic esters). Although pioneering work on organoboranes is often associated with Nobel Laureate in Chemistry H.C. Brown, it was their applications in the Suzuki-Miyaura coupling that highlighted the full potential of boron derivatives in synthesis. Indeed, this coupling, recognized by the award of the Nobel Prize in Chemistry in 2010, is one of the most commonly applied strategies in the pharmaceutical and agrochemical industries (fine chemicals sector) for the formation of carbon-carbon bonds.For example, in the pharmaceutical industry, the Suzuki-Miyaura coupling is used in nearly 25% of small molecule drug syntheses and accounts for 40% of carbon-carbon bond formation reactions.

[0003] Alkylboronic esters are most often prepared by hydroboration reactions of olefins or by transmetallation reactions of electrophilic boron derivatives with highly reactive compounds such as organolithium or organomagnesium compounds. However, significant limitations are associated with these methods, such as problems controlling regioselectivity during the hydroboration reactions of internal olefins and functional compatibility issues related to the use of highly reactive organolithium or organomagnesium compounds. These limitations considerably reduce the range of applications of these methods.

[0004] The Miyaura borylation coupling reaction is currently dominated by palladium-based catalysts, a precious metal, but this palladium-catalyzed coupling has major drawbacks:

[0005] 1) It is mainly limited to the coupling between a borylation reagent and a halogenated or pseudo-halogenated partners bearing an sp2 (or even sp) hybridized carbon lead to the formation of arylboronic esters. Indeed, the ease with which Pd(II)-alkyl intermediates formed during the coupling reaction are eliminated limits its application to halogenated or pseudo-halogenated partners bearing sp3 hybridized carbons. Therefore, this method cannot be used to prepare... Alkylated boron compounds are preferred partners for extensions of the Suzuki-Miyaura reaction with C(sp3) partners, which are currently very rarely reported.

[0006] 2) It uses an expensive and relatively toxic metal, which generates, by An example of the additional costs involved in meeting strict regulations for palladium content in active pharmaceutical ingredients (typically < 5 ppm) is the need to consider the following. In the context of sustainable development, it has also been estimated that the global warming potential (GWP) for the production of 1 kg of palladium is 3880 kg of CO2 equivalent (e-CO2). By comparison, the production of 1 kg of iron has a GWP of only 1.5 kg of e-CO2.

[0007] Iron is one of the few base metals that has been successfully tested as a catalyst in industrial cross-coupling processes on a kilogram scale. Although a few examples of iron-based catalysts for the Miyaura borylation reaction have been described in the prior art, few have been reported as being effective for coupling halogenated partners bearing sp3-hybridized carbons. Moreover, they often rely on the use of activated boronic derivatives (using an organolithium or organomagnesium compound), which represent significant limitations in terms of functional compatibility and / or are limited in terms of their range of applications.

[0008] The invention aims to remedy the problem mentioned above and to catalyze the borylation reaction of Miyaura.

[0009] An object of the invention is the use of iron imino-anilidide complexes to catalyze the Miyaura borylation reaction, in particular for the creation of C(sp3)-B bonds.

[0010] Another object of the invention is to provide preparation methods in which iron iminoanilidide complexes are advantageous for preparing organoboron compounds. Description of the invention.

[0011] The present invention relates to the use of at least one of the compounds of the following general formula (I):

[0012]

[0013] (I)

[0014] in which: • A is chosen from: • a group -X in which X is chosen from - a chlorine atom - a bromine atom • a group

[0015] [Chem.2]

[0016] in which: - M is a coordinating solvent - p is chosen from 1, 2, 3, 4 or a decimal number that can vary from a value greater than 0 but less than 4 • a group

[0017] [Chem.3] • B, C, D, and E, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms • Rb, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s)

[0018] as catalysts for the Miyaura borylation reaction, in particular for the creation of C(sp3)-B bonds.

[0019] It was unexpectedly found that iron iminoanilidide complexes could catalyze the Miyaura borylation reaction.

[0020] A can represent X, this group X being chosen from a chlorine or bromine atom, X(Li-X)-(M)p and (Acac)2. In case of steric hindrance due to the groups B, C, D, E, Rb R2, R3, R4, R5, R6, R7, R8, R9 and Rio, A advantageously represents X.

[0021] When there is little or no steric hindrance due to the groups B, C, D, E, Rb R2, R3, R4, R5, R6, R7, R8, R9 and R10, A advantageously represents XX(Li-X)-(M)p.

[0022] The term "coordinating solvent" means any solvent capable of stabilizing the electron deficiency of a metal cation by donating a portion of its electron density using a lone pair. The coordinating solvent is selected from the group consisting of diethyl ether, dimethoxymethane, dimethoxyethane, diethoxymethane, tetrahydrofuran, tert-butylmethyl ether, tert-butylethyl ether, methyl tetrahydrofuran, 1,4-dioxane, tert-amyl methyl ether, or anisole, preferably tetrahydrofuran. The value of p can be 1, 2, 3, 4, or a decimal number greater than 0 but less than 4, preferably 1.

[0023] When A represents two acetyloacetonate groups, the compounds do not degrade or lose their properties under the action of ambient air.

[0024] The expression "ambient air" refers to the surrounding air naturally present in the atmosphere, and whose composition can vary depending on the location or altitude.

[0025] By "linear", we mean the carbon atoms of the alkyl chain, with the exception of those at the ends of the chain, are all linked one to one through a carbon-carbon bond, in such a way that each carbon atom has only two carbon-carbon bonds, that the carbon atom at the beginning of the chain has only one carbon-carbon bond with the rest of the chain and that the carbon atom at the end of the chain has only one carbon-carbon bond.

[0026] The term “branched” means that each carbon atom in the alkyl chain can include 3 to 4 carbon-carbon bonds.

[0027] By “catalyst” is meant a chemical substance which, directly or after transformation by another chemical substance, enables or makes possible a chemical reaction.

[0028] The expression "Miyaura borylation reaction" refers to the creation of a carbon-boron bond by cross coupling between a halogenated or pseudo-halogenated derivative and a borylation reagent with a metallic catalyst.

[0029] In a particular embodiment, the invention relates to the use as defined above, using a diborated compound, in particular a diboronic acid ester.

[0030] The term "diborated compound" means a compound bearing a boron-boron bond. By way of example and without limitation, diborated compounds may be diboronic acid esters, diborinic acid esters, or diboranes.

[0031] In a particular embodiment, the invention relates to the use, as defined above, of at least one of the compounds of the following general formula (la):

[0032] [Chem.4]

[0033] (the)

[0034] in which: • X is chosen from - a chlorine atom - a bromine atom • B, C, D, and E, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 10 carbon atoms • Ri, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s)

[0035] as catalysts for the Miyaura borylation reaction, in particular for the creation of C(sp3)-B bonds.

[0036] This structure corresponds to the presence of steric hindrance around the iron atom due to the B, C, D, E, Rb, R2, R3, R4, R5, R6, R7, Rs, R9 and Rio groups

[0037] To facilitate understanding of what follows, we arbitrarily consider 3 axes of symmetry (I), (II) and (III) as represented in the diagram below

[0038] [Chem.5]

[0039] Axis (I) creates a symmetry between C and D, and between B and E. Axis (II) includes the carbon bearing R3 and the carbon bearing the nitrogen of the same phenyl group, and creates a symmetry between Ri and R5, and between R2 and R4. Axis (III) includes the carbon bearing R8 and the carbon bearing the nitrogen of the same phenyl group, and creates a symmetry between R6 and R10, and between R7 and R9.

[0040] In a particular embodiment, the invention relates to the use, as defined above, of at least one of the compounds with the following general formula (Ib):

[0041] [Chem.6]

[0042] (Ib)

[0043] in which: • X is chosen from - a chlorine atom - a bromine atom • M is a coordinating solvent • p is chosen from 1, 2, 3, 4 or a decimal number that can vary from a value greater than 0 but less than 4 • B, C, D, and E, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms • Ri, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s),

[0044] as catalysts for the Miyaura borylation reaction, in particular for the creation of C(sp3)-B bonds.

[0045] This structure corresponds to the absence of steric hindrance, or to the presence of low steric hindrance around the iron atom due to the B, C, D, E, Rb, R2, R3, R4, R5, Rg, R7, Rg, R9 and Rio groups

[0046] Advantageously, the compound of formula (Ib) has the following formula:

[0048] To facilitate understanding of what follows, we arbitrarily consider 3 axes of symmetry (I), (II) and (III) as represented in the diagram below

[0049] [Chem. 8] 0)

[0050] Axis (I) creates a symmetry between C and D, and between B and E. Axis (II) includes the carbon bearing R3 and the carbon bearing the nitrogen of the same phenyl group, and creates a symmetry between Ri and R5, and between R2 and R4. Axis (III) includes the carbon bearing R8 and the carbon bearing the nitrogen of the same phenyl group, and creates a symmetry between R6 and Rio, and between R7 and R9.

[0051] In a particular embodiment, the invention relates to the use, as defined above, of at least one of the compounds of the following general formula (the):

[0052] [Chem.9]

[0053] (the)

[0054] in which: • B, C, D, and E, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms • Ri, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s)

[0055] as catalysts for the Miyaura borylation reaction, in particular for the creation of C(sp3)-B bonds.

[0056] To facilitate understanding of what follows, we arbitrarily consider 3 axes of symmetry (I), (II) and (III) as represented in the diagram below

[0057] [Chem. 10]

[0058] Axis (I) creates a symmetry between C and D, and between B and E. Axis (II) includes the carbon bearing R3 and the carbon bearing the nitrogen of the same phenyl group, and creates a symmetry between Ri and R5, and between R2 and R4. Axis (III) includes the carbon bearing R8 and the carbon bearing the nitrogen of the same phenyl group, and creates a symmetry between R6 and R10, and between R7 and R9.

[0059] In a particular embodiment, the invention relates to the use, as defined above, of at least one of the compounds, • of the following general formula:

[0060] [Chem. 11]

[0061] (the)

[0062] in which: • X is chosen from - a chlorine atom - a bromine atom • B, C, D and E are chosen from: a hydrogen atom, a halogen, in in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atom(s), in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxy group of 1 to 10 carbon atom(s) or a linear or branched dialkylamino group of 2 to 20 carbon atoms, at least one of the groups B, C, D or E being different from the others. • Ri, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms, provided that: - Ri is different from R5 and / or R2 is different from R4

[0063] and R6 must be different from R10 and / or R7 must be different from R9 G is chosen from a hydrogen atom a linear or branched alkyl group of 1 to 5 carbon atom(s)

[0064] This particular embodiment corresponds to an absence of symmetry with respect to axis (I), axis (II) and axis (III). • or the following general formula:

[0065] [Chem. 12]

[0066] (the)

[0067] in which: • X is chosen from - a chlorine atom - a bromine atom • B, C, D and E are chosen from: a hydrogen atom, a halogen, in in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms, at least one of the groups B, C, D, or E being different from the others • Ri, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms, provided that: • Ri is different from R5 and / or R2 is different from R4

[0068] and • R6 must be identical to R10 and R7 must be identical to R9

[0069] or • R6 is different from Rio and / or R7 is different from R9

[0070] and • Ri is identical to R5 and R2 is identical to R4 • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s)

[0071] This particular embodiment corresponds to the absence of symmetry with respect to the axis (I) and the axis (II), and the presence of symmetry with respect to the axis (III). • or the following general formula:

[0072] [Chem. 13]

[0073] (the)

[0074] in which: • X is chosen from - a chlorine atom - a bromine atom • B, C, D and E are chosen from: a hydrogen atom, a halogen, in in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms, at least one of the groups B, C, D, or E being different from the others • Ri, R2, R3, R4, R5, R6, R7, Rs, R9 and Rio are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atom(s) or a linear or branched dialkylamino group of 2 to 20 carbon atoms, provided that: - Ri is identical to R5 - R2 is identical to R4 - R6 is identical to R10 - R7 is identical to R9 • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s)

[0075] This particular embodiment corresponds to the absence of symmetry with respect to axis (I). It also corresponds to the presence of symmetry with respect to axis (II) and axis (III). • or the following general formula:

[0076] [Chem. 14]

[0077] (the)

[0078] in which: • X is chosen from - a chlorine atom - a bromine atom B, C, D and E are chosen from: a hydrogen atom, a halogen, in specific F or Cl, a trifluoromethyl group CF3, a group linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms, provided that B is identical to E and D is identical to C Rb, R2, R3, R4, R5, R6, R7, Rs, R9 and Rio are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms, provided that: Ri must be different from R5 and / or R2 must be different from R4

[0079] R6 is different from Rio and / or R7 is different from R9 G is chosen from a hydrogen atom a linear or branched alkyl group of 1 to 5 carbon atom(s)

[0080] This particular embodiment corresponds to the presence of a symmetry by relation to axis (I). It also corresponds to the absence of symmetry with respect to axis (II) and axis (III). or the following general formula:

[0081] [Chem. 15]

[0082]

[0083] (there) in which: X is chosen from a chlorine atom a bromine atom B, C, D, and E are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms, provided that B is identical to E and D is identical to C • Ri, R2, R3, R4, R5, R6, R7, Rs, R9 and Rio are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms, provided that: - Ri is different from R5 and / or R2 is different from R4

[0084] and - R6 is identical to Rio and R7 is identical to R9

[0085] or - R6 is different from R10 and / or R7 is different from R9

[0086] and - Ri is identical to R5 and R2 is identical to R4 • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s)

[0087] This particular embodiment corresponds to the presence of symmetry with respect to axis (I) and axis (III). It also corresponds to the absence of symmetry with respect to axis (II). • or the following general formula:

[0088] [Chem. 16]

[0089] (the)

[0090] in which: • X is chosen from - a chlorine atom - a bromine atom • B, C, D and E are chosen from: a hydrogen atom, a halogen, in in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms, provided that B is identical to E and D is identical to C • Ri, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms, provided that: - Ri is identical to R5 - R2 is identical to R4 - R6 is identical to R10 - R7 is identical to R9 • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s)

[0091] as catalysts for the Miyaura borylation reaction, in particular for the creation of C(sp3)-B bonds.

[0092] This particular embodiment corresponds to the presence of symmetry with respect to axis (I), axis (II) and axis (III).

[0093] In a particular embodiment, the invention relates to the use, as defined above, of at least one of the compounds, • of the following general formula (Ib):

[0094] [Chem. 17]

[0095] (Ib)

[0096] in which: • X is chosen from - a chlorine atom - a bromine atom • M is a coordinating solvent • p is chosen from 1, 2, 3, 4 or a decimal number that can vary from a value greater than 0 but less than 4 • B, C, D and E are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atom(s), in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxy group of 1 to 10 carbon atom(s) or a linear or branched dialkylamino group of 2 to 20 carbon atoms, at least one of the groups B, C, D or E being different from the others. • Ri, R2, R3, R4, R5, R6, R7, Rs, R9 and Rio are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atom(s) or a linear or branched dialkylamino group of 2 to 20 carbon atoms, provided that: - Ri is different from R5 and / or R2 is different from R4

[0097] and - R6 is different from Rio and / or R7 is different from R9 • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s)

[0098] This particular embodiment corresponds to an absence of symmetry with respect to axis (I), axis (II) and axis (III). • or the following general formula (Ib):

[0099] (Ib)

[0100] in which: • X is chosen from - a chlorine atom - a bromine atom • M is a coordinating solvent • p is chosen from 1, 2, 3, 4 or a decimal number that can vary from a value greater than 0 but less than 4 • B, C, D, and E are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms, with at least one of the groups B, C, D, or E being different from the others • Ri, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms, provided that: • Ri is different from R5 and / or R2 is different from R4

[0101] and • R6 is identical to Rio and R7 is identical to R9

[0102] or • R6 is different from Rio and / or R7 is different from R9

[0103] and • Ri is identical to R5 and R2 is identical to R4 • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s)

[0104] This particular embodiment corresponds to the absence of symmetry with respect to the axis (I) and the axis (II), and the presence of symmetry with respect to the axis (III). • or the following general formula (Ib):

[0105] [Chem. 19]

[0106] (Ib)

[0107] in which: • X is chosen from - a chlorine atom - a bromine atom • M is a coordinating solvent • p is chosen from 1, 2, 3, 4 or a decimal number that can vary from a value greater than 0 but less than 4 • B, C, D, and E are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms, at least one of the groups B, C, DouE being different from the others Rb, R2, R3, R4, R5, R6, R7, Rs, R9 and Rio are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms, provided that: Ri is identical to R5 R2 is identical to R4 R6 is identical to R10 R7 is identical to R9 G is chosen from a hydrogen atom a linear or branched alkyl group of 1 to 5 carbon atom(s)

[0108] This particular embodiment corresponds to the absence of symmetry with respect to axis (I). It also corresponds to the presence of symmetry with respect to axis (II) and axis (III). or the following general formula (Ib):

[0109] [Chem.20]

[0110] (Ib)

[0111] in which: • X is chosen from - a chlorine atom - a bromine atom • M is a coordinating solvent • p is chosen from 1, 2, 3, 4 or a decimal number that can vary from a value greater than 0 but less than 4 • B, C, D, and E are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms, provided that B is identical to E and D is identical to C • Ri, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms, provided that: - Ri is different from R5 and / or R2 is different from R4

[0112] and - R6 must be different from R10 and / or R7 must be different from R9 • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s)

[0113] This particular embodiment corresponds to the presence of symmetry with respect to axis (I). It also corresponds to the absence of symmetry with respect to axis (II) and axis (III). • or the following general formula (Ib):

[0114] [Chem.21]

[0115]

[0116] (Ib) in which: • X is chosen from - a chlorine atom - a bromine atom • M is a coordinating solvent • p is chosen from 1, 2, 3, 4 or a decimal number that can vary from a value greater than 0 but less than 4 • B, C, D, and E are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms, provided that B is identical to E and D is identical to C • Ri, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atom(s) or a linear or branched dialkylamino group of 2 to 20 carbon atoms, provided that: - Ri is different from R5 and / or R2 is different from R4

[0117] and - R6 is identical to Rio and R7 is identical to R9

[0118] or - R6 must be different from R10 and / or R7 must be different from R9

[0119] and - Ri is identical to R5 and R2 is identical to R4 • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s)

[0120] This particular embodiment corresponds to the presence of symmetry with respect to axis (I) and axis (III). It also corresponds to the absence of symmetry with respect to axis (II). • or the following general formula (Ib):

[0121] [Chem.22]

[0122] (Ib)

[0123] in which: • X is chosen from - a chlorine atom - a bromine atom • M is a coordinating solvent • p is chosen from 1, 2, 3, 4 or a decimal number that can vary from a value greater than 0 but less than 4 • B, C, D, and E are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms, provided that B is identical to E and D is identical to C • Ri, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms, provided that: - Ri is identical to R5 - R2 is identical to R4 - R6 is identical to R10 - R7 is identical to R9 • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s)

[0124] as catalysts for the Miyaura borylation reaction, in particular for the creation of C(sp3)-B bonds.

[0125] This particular embodiment corresponds to the presence of symmetry with respect to axis (I), axis (II) and axis (HD

[0126] In a particular embodiment, the invention relates to the use, as defined above, of at least one of the compounds • of the following general formula:

[0127] [Chem.23]

[0128] (the)

[0129] in which: • B, C, D, and E are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms, with at least one of the groups B, C, D, or E being different from the others • Ri, R2, R3, R4, R5, R6, R7, Rs, R9 and Rio are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms, provided that: - Ri is different from R5 and / or R2 is different from R4

[0130] and - R6 must be different from R10 and / or R7 must be different from R9 • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s)

[0131] This particular embodiment corresponds to an absence of symmetry with respect to axis (I), axis (II) and axis (III). • or the following general formula:

[0132] [Chem.24]

[0133] (the)

[0134] in which: • B, C, D, and E are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms, with at least one of the groups B, C, D, or E being different from the others • Ri, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms, provided that: - Ri is different from R5 and / or R2 is different from R4 - R6 is identical to Rio and R7 is identical to R9

[0136] or - R6 is different from Rio and / or R7 is different from R9

[0137] and - Ri is identical to R5 and R2 is identical to R4 • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s)

[0138] This particular embodiment corresponds to the absence of symmetry with respect to the axis (I) and the axis (II), and the presence of symmetry with respect to the axis (III). • or the following general formula:

[0139] [Chem.25]

[0140] (the)

[0141] in which: • B, C, D, and E are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms, with at least one of the groups B, C, D, or E being different from the others • Ri, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a group trifluoromethyl CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms, provided that: - Ri is identical to R5 - R2 is identical to R4 - R6 is identical to Rio - R7 is identical to R9 • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s)

[0142] This particular embodiment corresponds to the absence of symmetry with respect to axis (I). It also corresponds to the presence of symmetry with respect to axis (II) and axis (III). or the following general formula:

[0144] (the)

[0145] in which: • B, C, D, and E are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms, provided that B is identical to E and D is identical to C • Ri, R2, R3, R4, R5, R6, R7, Rs, R9 and Rio are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms, provided that: - Ri is different from R5 and / or R2 is different from R4

[0146] and - R6 is different from Rio and / or R7 is different from R9 • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s)

[0147] This particular embodiment corresponds to the presence of symmetry with respect to axis (I). It also corresponds to the absence of symmetry with respect to axis (II) and axis (III). • or the following general formula:

[0148] [Chem.27]

[0150] in which: • B, C, D, and E are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms, provided that B is identical to E and D is identical to C • Ri, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms, provided that: - Ri is different from R5 and / or R2 is different from R4

[0151] and - R6 is identical to R10 and R7 is identical to R9

[0152] or - R6 is different from R10 and / or R7 is different from R9

[0153] and - Ri is identical to R5 and R2 is identical to R4 • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s)

[0154] This particular embodiment corresponds to the presence of symmetry with respect to axis (I) and axis (III). It also corresponds to the absence of symmetry with respect to axis (II). • or the following general formula:

[0155]

[0156] (the)

[0157] in which: • B, C, D, and E are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms, provided that B is identical to E and D is identical to C • Ri, R2, R3, R4, R5, R6, R7, Rs, R9 and Rio are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms, provided that: - Ri is identical to R5 - R2 is identical to R4 - R6 is identical to R10 - R7 is identical to R9 • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s)

[0158] as catalysts for the Miyaura borylation reaction, in particular for the creation of C(sp3)-B bonds.

[0159] This particular embodiment corresponds to the presence of symmetry with respect to axis (I), axis (II) and axis (III).

[0160] In a particular embodiment, the invention relates to the use, as defined above, of at least one of the compounds • of the following general formula:

[0161] [Chem.29]

[0162] (the)

[0163] in which: • X is chosen from - a chlorine atom - a bromine atom • B, C, D and E are fluorine atoms • Ri, R2, R3, R4, R5, R6, R7, Rs, R9 and Rio, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s) • or the following general formula (Ib):

[0165] (Ib)

[0166] in which: • X is chosen from - a chlorine atom - a bromine atom • M is a coordinating solvent • p is chosen from 1, 2, 3, 4 or a decimal number that can vary from a value greater than 0 but less than 4 • B, C, D and E are fluorine atoms • Ri, R2, R3, R4, R5, R6, R7, Rs, R9 and Rio, identical or different, are chosen among: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s) • or the following general formula:

[0167]

[0168]

[0169]

[0170]

[0171]

[0172] (THE) in which: • B, C, D and E are fluoride atony • Ri, R2, R3, R4, R5, R6, R7, Rs, R9 and Rio, identical or different, are chosen among: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s) as catalysts for the Miyaura borylation reaction, in particular for the creation of C(sp3)-B bonds. This particular embodiment corresponds to the presence of 4 fluorine atoms on the phenyl group bearing groups B, C, D and E. This has the effect of modifying the electronic properties of the iron atom of the catalyst. In a particular embodiment, the invention relates to the use of compounds of formula (I), as defined above, selected from:

[0174] In a particular embodiment, the invention relates to the use of at least one of the compounds of formulas (la), (Ib) or (le) as defined above, for the synthesis of one of the compounds of the following formula:

[0176]

[0177] In a particular embodiment, the invention relates to the use of at least one of the compounds of formulas (la), (Ib) or (le) as defined above for carrying out a Miyaura borylation reaction from a compound (SI) [Chem. 34]

[0178]

[0179]

[0180] (IF) in which Rn is chosen from: - a grouping [Chem.35]

[0181] in which q is equal to 0, 1 or 2 and Rn represents a linear or branched alkyl group of 1 to 10 carbon atom(s), in particular 1, - a group [Chem.36]

[0182]

[0183]

[0184] in which q and Rn have the meaning defined above, - a grouping [Chem.37] with a compound of formula (S2): Z-Hal in which Z is chosen from: - a linear or branched alkyl group of 1 to 20 carbon atoms or a cyclic group of 3 to 12 carbon atoms, in particular an octyl, hexyl, cycloheptyl or cyclopentyl group - an 1-adamantyl group with the formula

[0186]

[0187]

[0188]

[0189]

[0190]

[0185] - a grouping: [Chem. 39] possibly substituted by one or two methyl groups, - a group [Chem.40] - a grouping [Chem.41] ..O1BS - a grouping [Chem.42] a group

[0191]

[0192]

[0193]

[0194]

[0195]

[0196]

[0197]

[0198]

[0199]

[0200] [Chem.43] - a grouping [Chem. 44] and Hal is chosen from among: - a chlorine atom - a bromine atom - an iodine atom - a group of OTs. In the compound (SI), there are 4 boron-oxygen bonds such that the Ru groups are linked in pairs to form a ring. The Hal group can represent a halogen (chlorine, bromine and iodine) or a pseudo-halogen (-OTs). The advantage of using a pseudo-halogen compared to a halogen is the possibility of observing better reactivity compared to that obtained with a halogen due to the release of different anions in the medium. Another object of the invention relates to a method for preparing a compound of formula (X): [Chem. 45] (X) in which Rn is chosen from: - a group

[0201] [Chem.46]

[0202] in which q is equal to 0, 1 or 2 and Rn represents a linear or branched alkyl group of 1 to 10 carbon atom(s), in particular 1, - a group [Chem.47]

[0203] in which q and R[2] have the meaning defined above, - a grouping [Chem.48]

[0204] and in which T2 and T3 are, identical or different, chosen from: - a hydrogen atom, - a linear or branched alkyl group of 1 to 20 carbon atoms or a cyclic group of 3 to 12 carbon atoms, possibly substituted by one or more phenyl groups or tert-butyldimethylsil ether group, - a linear ether group of 1 to 20 carbon atom(s), - a linear alkylamine group of 1 to 20 carbon atom(s), possibly protected, in particular by a tert-butoxycarbonyl group or a carboxybenzyl group - a benzocyclopentane group,

[0205] possibly Ti, T2 and T3 are linked together so as to form a polycycloalkane, in particular an adamantyl group, and possibly fused with a phenyl group,

[0206] possibly two of Ti, T2 and T3 are linked so as to form a cyclic ether group,

[0207] possibly two of T2 and T3 are linked so as to form a cyclic amine,

[0208] provided that Tb, T2 and T3 do not simultaneously represent a hydrogen atom,

[0209] comprising a step of contacting a compound of Formula (XI):

[0210] [Chem.49]

[0211] (XI)

[0212] with a compound of Formula (XII):

[0213] [Chem.50]

[0214] in which Hal is chosen from: - a chlorine atom - a bromine atom - an iodine atom - a group of OTs,

[0215] in the presence of a compound of formula (I):

[0216]

[0217]

[0218]

[0219]

[0220] (I) in which: • A is chosen from: • a grouping -X in which X is chosen from - a chlorine atom - a bromine atom • a group [Chem. 52] (M) U 4. x in which: - M is a coordinating solvent - p is chosen from 1, 2, 3, 4 or a decimal number that can vary from a value greater than 0 but less than 4 • a group

[0221] [Chem.53] • B, C, D, and E, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms • Ri, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s) [O222] and a base.

[0223] By way of non-limiting example, the Miyaura borylation reaction is carried out in the presence of a halogenated derivative (1 equivalent), a diboronic acid ester (2 equivalents), a base (1.2 equivalents) and the catalyst under stirring at 25°C for 48h.

[0224] In a particular embodiment, the invention relates to a method for preparing, as defined above, a compound of formula (X):

[0225] [Chem.54]

[0226]

[0227] (X) in which Ru is chosen from among: - a group

[0228] [Chem.55] in which q is equal to 0, 1 or 2 and Rn represents a linear or branched alkyl group of 1 to 10 carbon atom(s), in particular 1, - a group

[0229] [Chem.56] in which q and R[2] have the meaning defined above, - a grouping

[0230] [Chem.57]

[0231] and wherein T2 and T3 are, identical or different, chosen from: - a hydrogen atom, - a linear or branched alkyl group of 1 to 20 carbon atoms or a cyclic group of 3 to 12 carbon atoms, possibly substituted by one or more phenyl groups or tert-butyldimethylsil ether group, - a linear ether group of 1 to 20 carbon atom(s), - a linear alkylamine group of 1 to 20 carbon atom(s), possibly protected, in particular by a tert-butoxycarbonyl group or a carboxybenzyl group - a benzocyclopentane group,

[0232]

[0233]

[0234]

[0235]

[0236]

[0237]

[0238]

[0239]

[0240]

[0241]

[0242] possibly Ti, T2 and T3 are linked together to form a polycycloalkane, in particular an adamantyl group, and possibly fused with a phenyl group, possibly two of Ti, T2 and T3 are linked in such a way as to form a cyclic ether group, possibly two of Tb, T2 and T3, are linked in such a way as to form a cyclic amine. provided that Tb, T2 and T3 do not simultaneously represent a hydrogen atom, including a step of contacting a compound of Formula (XI): [Chem. 5 8] ii (XI) with a compound of Formula (XII): [Chem.59] T3 in which Hal is chosen from among: - a chlorine atom - a bromine atom - an iodine atom - a group of OTs, in the presence of a compound with formula (la): [Chem. 60]

[0244]

[0245] (there) in which: X is chosen from a chlorine atom a bromine atom B, C, D, and E, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 10 carbon atoms. Ri, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms G is chosen from a hydrogen atom a linear or branched alkyl group of 1 to 5 carbon atom(s)

[0246] and a base.

[0247] In a particular embodiment, the invention relates to a preparation process, as defined above, of a compound of formula (X):

[0248]

[0249]

[0250]

[0251] [Chem.61] Ru Ï2 t3 (X) in which Ru is chosen from among: - a group [Chem. 62]

[0252] in which q is equal to 0, 1 or 2 and Rn represents a linear or branched alkyl group of 1 to 10 carbon atom(s), in particular 1, - a group [Chem.63]

[0253]

[0254] in which q and Rn have the meaning defined above, - a grouping [Chem. 64] and in which T2 and T3 are, identical or different, chosen from: - a hydrogen atom,

[0255]

[0256]

[0257]

[0258]

[0259]

[0260]

[0261]

[0262]

[0263] - a linear or branched alkyl group of 1 to 20 carbon atoms or a cyclic group of 3 to 12 carbon atoms, possibly substituted by one or more phenyl groups or tert-butyldimethylsil ether group, - a linear ether group of 1 to 20 carbon atom(s), - a linear alkylamine group of 1 to 20 carbon atom(s), possibly protected, in particular by a tert-butoxycarbonyl group or a carboxybenzyl group - a benzocyclopentane group, possibly Ti, T2 and T3 are linked together to form a polycycloalkane, in particular an adamantyl group, and possibly fused with a phenyl group, possibly two of Ti, T2 and T3 are linked in such a way as to form a cyclic ether group, possibly two of Tb, T2 and T3, are linked in such a way as to form a cyclic amine. provided that Tb, T2 and T3 do not simultaneously represent a hydrogen atom, including a step of bringing into contact a compound of Formula (XI): [Chem.65] : \ / \ 7 ^11 7 (XI) with a compound of Formula (XII): [Chem. 66]

[0264] in which Hal is chosen from among: - a chlorine atom - a bromine atom - an iodine atom - a group of -OTs,

[0265] in the presence of a compound of formula (Ib):

[0266] [Chem.67]

[0267] (Ib)

[0268] in which: • X is chosen from - a chlorine atom - a bromine atom • M is a coordinating solvent • p is chosen from 1, 2, 3, 4 or a decimal number that can vary from a value greater than 0 but less than 4 • B, C, D, and E, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms • Ri, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atom(s), in particular a linear alkyl group or branched with 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s),

[0269] and a base.

[0270] In a particular embodiment, the invention relates to a method for preparing, as defined above, a compound of formula (X):

[0271] [Chem.68] B---C _ ' R "T3

[0272] (X)

[0273] in which Ru is chosen from: - a grouping

[0274] [Chem.69] in which q is equal to 0, 1 or 2 and Rn represents a linear or branched alkyl group of 1 to 10 carbon atom(s), in particular 1, - a group

[0275] [Chem.70] in which q and Rn have the meaning defined above, - a grouping

[0276]

[0277]

[0278]

[0279]

[0280]

[0281]

[0282]

[0283]

[0284]

[0285] [Chem.71] and in which Ti, T2 and T3 are, identical or different, chosen from: - a hydrogen atom, - a linear or branched alkyl group of 1 to 20 carbon atoms or a cyclic group of 3 to 12 carbon atoms, possibly substituted by one or more phenyl groups or tert-butyldimethylsil ether group, - a linear ether group of 1 to 20 carbon atom(s), - a linear alkylamine group of 1 to 20 carbon atom(s), possibly protected, in particular by a tert-butoxycarbonyl group or a carboxybenzyl group - a benzocyclopentane group, possibly Ti, T2 and T3 are linked together to form a polycycloalkane, in particular an adamantyl group, and possibly fused with a phenyl group, possibly two of Tb, T2 and T3, are linked in such a way as to form a cyclic ether group, possibly two of Tb, T2 and T3, are linked in such a way as to form a cyclic amine. provided that Tb, T2 and T3 do not simultaneously represent a hydrogen atom, including a step of bringing into contact a compound of Formula (XI): [Chem.72] 7 Ru Rii 7 (XI) with a compound of Formula (XII):

[0286] [Chem.73]

[0287] in which Hal is chosen from: - a chlorine atom - a bromine atom - an iodine atom - a group of OTs,

[0288] in the presence of a compound of formula (the):

[0289] [Chem.74]

[0290] (the)

[0291] in which: • B, C, D, and E, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms • Ri, R2, R3, R4, R5, R6, R7, Rs, R9 and Rio, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s),

[0292] and a base.

[0293] In a particular embodiment, the invention relates to a preparation process, as defined above, in which said process is carried out under an inert atmosphere.

[0294] In a particular embodiment, the invention relates to a preparation process, as defined above, in which said base is a lithium amide, in particular selected from LiNMeEt, LiNMe2, LiNEt2, LiN(iPr)2, LiNTMS2, LiNPhMe, in particular LiNMeEt or LiNMe2, in particular LiNMeEt.

[0295] In this embodiment, the base is the conjugate base of an amine, for which the counter-ion is a lithium cation.

[0296] In a particular embodiment, the invention relates to a preparation process, as defined above, in which said process is carried out in solution in a non-coordinating nonpolar solvent, in particular chosen from benzene, hexane, toluene, cyclohexane or methylcyclohexane.

[0297] In a particular embodiment, the invention relates to a preparation process, as defined above, in which said process is carried out in solution in a coordinating solvent selected from diethyl ether, dimethoxymethane, dimethoxyethane, diethoxymethane, tetrahydrofuran, tert-butylmethyl ether, tert-butylethyl ether, methyl tetrahydrofuran, tert-amylmethyl ether or 1,4-dioxane, in particular selected from tetrahydrofuran, tert-butylmethyl ether or 1,4-tert-amylmethyl ether.

[0298] The advantage of using a coordinating solvent is that the electron deficiency of the iron atom is stabilized by the lone pairs of solvent molecules

[0299] In a particular embodiment, the invention relates to a preparation process, as defined above, in which said base is LiNMeEt and said process is carried out in solution in tert-amymethyl ether.

[0300] In a particular embodiment, the invention relates to a preparation process, as defined above, in which said base is LiNMeEt and said process is carried out in solution in tetrahydrofuran.

[0301] In a particular embodiment, the invention relates to a preparation process, as defined above, in which said compound of formula (I), (la), (Ib) or (le) is present at a molar concentration of 5 to 35% relative to the compound of formula (XII), in particular at a molar concentration of 10 to 20%.

[0302] By "5 to 35% molar concentration", we mean: 5 to 10% molar concentration, 10 to 15% molar concentration, 15 to 20% molar concentration, 20 to 25% molar concentration, 25 to 30% molar concentration and 30 to 35% molar concentration.

[0303] The expression "in molar concentration relative to compound of formula (XII)" means that compound of formula (I), (la), (Ib) or (le) is present at a concentration of 5 to 35 mol% depending on the number of moles of compound of formula (XII). By way of example and without limitation, if compound of formula (XII) is present at a concentration of one mole, then compound of formula (I), (la), (Ib) or (le) is present at a concentration of 0.05 to 0.35 moles.

[0304] The catalysts of the Invention can be prepared as follows.

[0305] This description relates to a process for preparing a compound of formula (la) as defined above:

[0306] [Chem.75]

[0307] (the)

[0308] in which: • X is chosen from - a chlorine atom - a bromine atom B, C, D, and E, identical or different, are chosen from: an atom of hydrogen, a halogen, in particular F or Cl, a group

[0309]

[0310]

[0311]

[0312]

[0313] trifluoromethyl CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms • Ri, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s) comprising a sequential addition step of n-butyllithium followed by halide of iron (II) FeX2 on a compound of formula (II) in which B, C, D, E, G, Rb R2, R3, R4, R5, R6, R7, R8, R9 and R10 have the meanings indicated above. In this embodiment, the addition reaction consists of the deprotonation of the secondary amine group of compound (II) located between two phenyl groups to create the N-Fe bond. Lithium does not coordinate to compound (la) due to steric hindrance around the iron atom caused by the B, C, D, E, Rb, R2, R3, R4, R5, R6, R7, R8, R9, and R10 groups. The resulting compound (la) is sensitive to oxygen and must be stored under inert atmospheric conditions.

[0314] In another embodiment, the present description relates to a preparation process, as defined above, in which the aforementioned addition step is carried out in a cyclic or non-cyclic ether solvent, in particular chosen from tetrahydrofuran, diethyl ether, dimethoxymethane, dimethoxyethane, diethoxymethane, tetrahydrofuran, tert-butylmethyl ether, tert-butylethyl ether, methyl tetrahydrofuran, 1,4-dioxane, methoxycyclopentane, tert-amyl methyl ether or anisole, preferably tetrahydrofuran, from -78°C to 25°C, preferably at -78°C, for 30 minutes, then 2h at 25°C, then 15h under stirring.

[0315] The expression "ethereal solvent" designates a solvent in which there is at least one ether function.

[0316] This sequential addition can be carried out either in a single solvent, or in a first solvent for the addition of n-butyllithium, then after evaporation of this solvent, in a second solvent for the addition of FeX2.

[0317] By way of non-limiting example, this step of sequential addition of n-butyllithium and FeX2 (1 / 1) can be carried out for the addition of n-butyllithium into hexane, then for the addition of FeX2 into a cyclic or non-cyclic ether solvent, in particular chosen from tetrahydrofuran, diethyl ether, dimethoxymethane, dimethoxyethane, diethoxymethane, tetrahydrofuran, tert-butylmethyl ether, tert-butylethyl ether, methyl tetrahydrofuran, 1,4-dioxane, methoxycyclopentane, tert-amyl methyl ether or anisole.

[0318] By way of non-limiting example, this step of sequential addition of n-butyllithium and FeX2 (1 / 1) can be carried out for the addition of n-butyllithium in a non-coordinating nonpolar solvent in particular chosen from benzene, hexane, toluene, cyclohexane, methylcyclohexane, and then for the addition of FeX2 in tetrahydrofuran.

[0319] By "non-coordinating nonpolar solvent" is meant a solvent in which the center of gravity of the sums of the differences in electronegativity coincide,

[0320] By way of non-limiting example, this step of adding n-butyllithium and Fe2 chloride (1 / 1) can be carried out in tetrahydrofuran at temperatures of -78°C to 25°C, preferably -78°C to -30°C for 30 minutes, then 2h from -78°C to 25°C, preferably from 0°C to 25°C, then 15h from -78°C to 25°C, preferably from 0°C to 25°C under stirring.

[0321] In another embodiment, the present description relates to a preparation process, as defined above, comprising a step of preparing a compound of formula (II):

[0323]

[0324]

[0325]

[0326]

[0327]

[0328]

[0329]

[0322] in which B, C, D, E, G, Rb R2, R3, R4, R5, R6, R7, Rs, R9 and R10 have the meanings indicated above, said step, comprising an aromatic nucleophilic substitution step of a compound of formula (III) [Chem.78] in which B, C, D, E, G, Rb, R2, R3, R4, and R5 have the meanings indicated above, and F is a fluorine atom on a compound of formula (IV): [Chem.79]

[0330] (IV)

[0331] in which R6, R7, R8, R9, and R10 have the meanings indicated above

[0332] to obtain said compound of formula (II)

[0333] In this embodiment, the aromatic nucleophilic substitution occurs via the lithium amide of compound (IV) which substitutes for the fluorine of compound (III).

[0334] In another embodiment, the present description relates to a preparation process, as defined above, in which the aforementioned aromatic nucleophilic substitution step is carried out in a cyclic or non-cyclic ether solvent, in particular selected from diethyl ether, dimethoxymethane, dimethoxyethane, diethoxymethane, tetrahydrofuran, tert-butylmethyl ether, tert-butylethyl ether, methyl tetrahydrofuran, 1,4-dioxane, methoxycyclopentane, tert-amyl methyl ether or anisole, preferably tetrahydrofuran and at a temperature of 25°C to 125°C, preferably at 25°C.

[0335] By way of non-limiting example, this aromatic nucleophilic substitution of compound (IV) on compound (III) (1 / 1) is carried out in tetrahydrofuran at temperatures from 25 °C to 125 °C, preferably from 25 °C to 75 °C.

[0336] In another embodiment, the present description relates to a preparation process, as defined above, in which the aforementioned aromatic nucleophilic substitution step is carried out in a non-coordinating nonpolar solvent, in particular selected from benzene, hexane, toluene, cyclohexane, methylcyclohexane, preferably in toluene and at a temperature of 25°C to 125°C, preferably at 25°C or 90°C.

[0337] By way of non-limiting example, this aromatic nucleophilic substitution of compound (IV) on compound (III) (2,5 / 1) is carried out in toluene at temperatures from 25°C to 125°C, preferably from 25°C to 75°C.

[0338] In another embodiment, the present description relates to a preparation process, as defined above, comprising a step of preparing a compound of formula (III)

[0339] [Chem. 80]

[0340] (III)

[0341] wherein B, C, D, E, G, Rb, R2, R3, R4, and R5 have the meanings indicated above, and F is a fluorine atom

[0342] said step comprising a condensation reaction of a compound of formula (V)

[0343] [Chem.81]

[0344] (V)

[0345] in which B, C, D, and E have the meanings indicated above, and F is a fluorine atom

[0346] on a compound of formula (VI):

[0347] [Chem. 82]

[0348] (VI)

[0349] in which Rb R2, R3, R4, and R5 have the meanings indicated above

[0350] to obtain said compound of formula (III)

[0351] In this embodiment, the condensation step forming compound (III) is carried out from an aldehyde, compound (V) and an amine, compound (IV).

[0352] In another embodiment, the present description relates to a preparation process, as defined above, in which the aforementioned condensation step is carried out, at a temperature of 0°C to 150°C, in a non-coordinating nonpolar or alcoholic solvent, in particular selected from hexane, toluene, benzene, cyclohexane, methylcyclohexane, butan-1-ol, butan-2-ol, isobutanol, tert-butanol, propan-2-ol, isopropanol, methanol, or ethanol, preferably hexane at 25°C, or preferably toluene at 150°C, or preferably ethanol at 90°C.

[0353] The expression "alcoholic solvent" refers to a solvent which contains a hydroxyl function.

[0354] By way of non-limiting example, this condensation of an aldehyde and an amine (1 / 1) is carried out in the presence of MgSO4 (0.08 mol%) in hexane at temperatures from 25°C to 75°C, preferably at 25°C.

[0355] By way of non-limiting example, this condensation of an aldehyde and an amine is carried out in the presence of para-toluenesulfonic acid (1 / 1,1 / 0.01) in toluene at temperatures from 25°C to 150°C, preferably at 150°C.

[0356] By way of non-limiting example, this condensation of an aldehyde and an amine (1 / 1,1) takes place in ethanol at temperatures from 25°C to 90°C, preferably at 25°C

[0357] In another embodiment, the present description relates to a process for preparing, as defined above, a compound of formula (la)

[0358] [Chem. 83]

[0359] (the)

[0360] in which: • X is chosen from - a chlorine atom - a bromine atom • B, C, D, and E, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms • Ri, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s)

[0361] comprising: a) a condensation step of a compound of formula (V)

[0362] [Chem. 84]

[0363] (V)

[0364] in which B, C, D, and E have the meanings indicated above and F is a fluorine atom

[0365] on a compound of formula (VI):

[0366] [Chem. 85]

[0368] in which Rb R2, R3, R4, and R5 have the meanings indicated above

[0369] to obtain the compound of formula (III)

[0370] [Chem. 86]

[0371] (III)

[0372] wherein B, C, D, E, G, Rb, R2, R3, R4, and R5 have the meanings indicated above, and F is a fluorine atom

[0373] b) an aromatic nucleophilic substitution step of said compound of formula (III) on a compound of formula (IV):

[0374] [Chem. 87] ^9 R

[0375] (IV)

[0376] in which R6, R7, R8, R9, and Rio have the meanings indicated above

[0377] to obtain the compound of formula (II)

[0378] [Chem.88]

[0379] (II)

[0380] in which B, C, D, E, G, Rb, R2, R3, R4, R5, R6, R7, Rs, R9 and R10 have the meanings indicated above

[0381] c) a step of sequential addition of n-butyl lithium and then of iron (II) halide FeX2 to said compound of formula (II) to obtain the compound of formula (la).

[0382] In another embodiment, the present description relates to a process for preparing, as defined above, a compound of formula (Ib):

[0383] [Chem.89]

[0384] (Ib)

[0385] in which: X is chosen from - a chlorine atom - a bromine atom • M is a coordinating solvent • p is chosen from 1, 2, 3, 4 or a decimal number that can vary from a value greater than 0 but less than 4 • B, C, D, and E, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms • Ri, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 1 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s)

[0386] comprising a sequential addition step of n-butyl-lithium followed by iron (II) halide FeX2 on a compound of formula (II)

[0387] [Chem.90]

[0389] in which B, C, D, E, G, Rb R2, R3, R4, R5, R6, R7, Rs, R9 and R10 have the meanings indicated above.

[0390] In this embodiment, the addition reaction consists of the deprotonation of the secondary amine function of compound (II) located between two phenyl groups in order to create the N-Fe bond. A first X atom bonded to iron coordinates to a lithium atom, itself already coordinated by another X atom. This coordination can occur in the absence or presence of slight steric hindrance around the iron atom due to the B, C, D, E, Rb, R2, R3, R4, R5, Re, R7, Rs, R9, and Rio groups. The resulting compound is sensitive to ambient air and must be stored under inert atmospheric conditions.

[0391] In another embodiment, the present description relates to a preparation process, as defined above, in which the aforementioned addition step is carried out in a cyclic or non-cyclic ether solvent, in particular selected from tetrahydrofuran, diethyl ether, dimethoxymethane, dimethoxyethane, diethoxymethane, tetrahydrofuran, tert-butylmethyl ether, tert-butylethyl ether, methyl tetrahydrofuran, 1,4-dioxane, methoxycyclopentane, tert-amyl methyl ether or anisole, preferably tetrahydrofuran, from -78°C to 25°C, preferably at -78°C, for 30 minutes, then 2h at 25°C, then 15h at 25°C under stirring.

[0392] This sequential addition can be carried out either in a single solvent, or in a first solvent for the addition of n-butyllithium, then after evaporation of this solvent, in a second solvent for the addition of FeCX2.

[0393] By way of non-limiting example, this step of sequential addition of n-butyllithium and FeX2 (1 / 1) can be carried out for the addition of n-butyllithium into hexane, then for the addition of FeX2 into a cyclic or non-cyclic ether solvent, in particular chosen from tetrahydrofuran, diethyl ether, dimethoxymethane, dimethoxyethane, diethoxymethane, tetrahydrofuran, tert-butylmethyl ether, tert-butylethyl ether, methyl tetrahydrofuran, 1,4-dioxane, methoxycyclopentane, tert-amyl methyl ether or anisole.

[0394] By way of non-limiting example, this step of sequential addition of n-butyllithium and FeX2 (1 / 1) can be carried out for the addition of n-butyllithium in a non-coordinating nonpolar solvent in particular chosen from benzene, hexane, toluene, cyclohexane, methylcyclohexane, and then for the addition of FeX2 in tetrahydrofuran.

[0395] By way of non-limiting example, this step of adding n-butyllithium and FeCl2 (1 / 1) can be carried out in tetrahydrofuran at temperatures from -78°C to 25°C, preferably -78°C to -30°C for 30 minutes, then for 2 hours from -78°C to 25°C, of preferably from 0°C to 25°C, then 15h from -78°C to 25°C, preferably from 0°C to 25°C with stirring.

[0396] In another embodiment, the present description relates to a preparation process, as defined above, comprising a step of preparing a compound of formula (II):

[0397] [Chem.91]

[0398] (II)

[0399] in which B, C, D, E, G, Rb R2, R2, R4, R5, Re, R7, Rs, Rç and Rio have the meanings indicated above, said step, comprising an aromatic nucleophilic substitution step of a compound of formula (III)

[0400] [Chem.92]

[0401] (III)

[0402] wherein B, C, D, E, G, Rb, R2, R2, R4, and R5 have the meanings indicated above, and F is a fluorine atom

[0403] on a compound of formula (IV):

[0404] [Chem.93]

[0405] (IV)

[0406] in which R6, R7, R8, R9, and R10 have the meanings indicated above

[0407] to obtain said compound of formula (II).

[0408] In this embodiment, the aromatic nucleophilic substitution occurs via the lithium amide of compound (IV) which substitutes for the fluorine of compound (III).

[0409] In another embodiment, the present description relates to a preparation process, as defined above, in which the aforementioned aromatic nucleophilic substitution step is carried out in a cyclic or non-cyclic ether solvent, in particular selected from diethyl ether, dimethoxymethane, dimethoxyethane, diethoxymethane, tetrahydrofuran, tert-butylmethyl ether, tert-butylethyl ether, methyl tetrahydrofuran, 1,4-dioxane, methoxycyclopentane, tert-amyl methyl ether or anisole, preferably tetrahydrofuran and at a temperature of 25°C to 125°C, preferably at 25°C.

[0410] By way of non-limiting example, this aromatic nucleophilic substitution of compound (IV) on compound (III) (1 / 1) is carried out in tetrahydrofuran at temperatures from 25 °C to 125 °C, preferably from 25 °C to 75 °C.

[0411] In another embodiment, the present description relates to a preparation process, as defined above, in which the aforementioned aromatic nucleophilic substitution step is carried out in a non-coordinating nonpolar solvent, in particular selected from benzene, hexane, toluene, cyclohexane, methylcyclohexane, preferably in toluene and at a temperature of 25°C to 125°C, preferably at 25°C or 90°C.

[0412] By way of non-limiting example, this aromatic nucleophilic substitution of compound (IV) on compound (III) (2,5 / 1) is carried out in toluene at temperatures from 25°C to 125°C, preferably from 25°C to 75°C.

[0413] In another embodiment, the present description relates to a preparation process, as defined above, comprising a step of preparing a compound of formula (III)

[0414] [Chem.94]

[0416] in which B, C, D, E, G, Rb, R2, R3, R4, and R5 have the meanings indicated above, and F is a fluorine atom

[0417] said step comprising a condensation reaction of a compound of formula (V)

[0418] [Chem.95]

[0419] (V)

[0420] in which B, C, D, and E have the meanings indicated above, and F is a fluorine atom

[0421] on a compound of formula (VI):

[0422] [Chem.96] _2 H R5

[0423] (VI)

[0424] in which Rh R2, R3, R4, and R5 have the meanings indicated above

[0425] to obtain said compound of formula (III).

[0426] In this embodiment, the condensation step forming the imine of compound (III) is carried out from an aldehyde, compound (V) and an amine, compound (IV).

[0427] In another embodiment, the present description relates to a preparation process, as defined above, in which the aforementioned condensation step is carried out, at a temperature of 0°C to 150°C, in a non-coordinating nonpolar or alcoholic solvent, in particular selected from hexane, toluene, benzene, cyclohexane, methylcyclohexane, butan-1-ol, butan-2-ol, isobutanol, tert-butanol, propan-2-ol, isopropanol, methanol, or ethanol, preferably hexane at 25°C, or preferably toluene at 150°C, or preferably ethanol at 90°C.

[0428] By way of non-limiting example, this condensation of an aldehyde and an amine (1 / 1) is carried out in the presence of MgSO4 (0.08 mol%) in hexane at temperatures from 25°C to 75°C, preferably at 25°C.

[0429] By way of non-limiting example, this condensation of an aldehyde and an amine is carried out in the presence of para-toluenesulfonic acid (1 / 1,1 / 0.01) in toluene at temperatures from 25°C to 150°C, preferably at 150°C

[0430] By way of non-limiting example, this condensation of an aldehyde and an amine (1 / 1,1) takes place in ethanol at temperatures from 25°C to 90°C, preferably at 25°C

[0431] In another embodiment, the present description relates to a process for preparing, as defined above, a compound of formula (Ib)

[0432] [Chem.97]

[0434]

[0435]

[0436]

[0437]

[0438] in which: • X is chosen from - a chlorine atom - a bromine atom • M is a coordinating solvent • p is chosen from 1, 2, 3, 4 or a decimal number that can vary from a value greater than 0 but less than 4 • B, C, D, and E, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 10 carbon atoms • Ri, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 1 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s) comprising: a) a condensation step of a compound of formula (V) [Chem.98] in which B, C, D, and E have the meanings indicated previously and F is a fluorine atom on a compound of formula (VI):

[0440] [Chem.99]

[0442] in which Rb R2, R3, R4, and R5 have the meanings indicated above

[0443] to obtain the compound of formula (III)

[0444] [Chem. 100]

[0445] (III)

[0446] in which B, C, D, E, G, Rb, R2, R3, R4, and R5 have the meanings indicated above, and F is a fluorine atom

[0447] b) an aromatic nucleophilic substitution step of said compound of formula (III) on a compound of formula (IV):

[0448] [Chem. 101]

[0449] (IV)

[0450] in which R6, R7, R8, R9, and R10 have the meanings indicated above

[0451] to obtain the compound of formula (II)

[0453]

[0454]

[0455]

[0456]

[0457]

[0458]

[0459]

[0452] in which B, C, D, E, G, Rb, R2, R2, R4, R5, Re, R7, Rs, R9 and Rio have the meanings indicated above c) a step of sequential addition of n-butyl lithium and then of iron (II) halide FeX2 to said compound of formula (II) to obtain the compound of formula (Ib). In a particular embodiment, the present description relates to a process for preparing, as defined above, a compound of formula (the): in which: • B, C, D, and E, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a group

[0460]

[0461]

[0462]

[0463]

[0464]

[0465] trifluoromethyl CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms • Ri, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 1 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s) comprising a sequential addition step of n-butyl lithium, then of iron (III) tris-acetylacetonate on a compound of formula (II) [Chem. 104] in which B, C, D, E, G, Rb, R2, R3, R4, R5, R6, R7, Rs, R9 and R10 have the meanings indicated above to obtain said compound of formula (the). In this embodiment, the addition reaction consists of the deprotonation of the secondary amine function of compound (II) located between two phenyl groups in order to create the N-Fe bond. The compounds of formula (le) thus obtained are stable in ambient air.

[0466] In another embodiment, the present description relates to a preparation process, as defined above, in which the aforementioned addition step is carried out in a cyclic or non-cyclic ether solvent, in particular selected from tetrahydrofuran, diethyl ether, dimethoxymethane, dimethoxyethane, diethoxymethane, tetrahydrofuran, tert-butylmethyl ether, tert-butylethyl ether, methyl tetrahydrofuran, 1,4-dioxane, methoxycyclopentane, tert-amyl methyl ether or anisole, preferably tetrahydrofuran, from -78°C to 25°C, preferably at 25°C, then for 16 hours at 25°C with stirring.

[0467] This sequential addition can be carried out either in a single solvent, or in a first solvent for the addition of n-butyllithium, then after evaporation of this solvent, in a second solvent for the addition of Fe(acac)3.

[0468] By way of non-limiting example, this step of sequential addition of n-butyllithium and Fe(acac)3 (1 / 1) can be carried out for the addition of n-butyllithium into hexane, then for the addition of Fe(acac)3 into a cyclic or non-cyclic ether solvent, in particular chosen from tetrahydrofuran, diethyl ether, dimethoxymethane, dimethoxyethane, diethoxymethane, tetrahydrofuran, tert-butylmethyl ether, tert-butylethyl ether, methyl tetrahydrofuran, 1,4-dioxane, methoxycyclopentane, tert-amyl methyl ether or anisole.

[0469] By way of non-limiting example, this step of sequential addition of n-butyllithium and Fe(acac)3 (1 / 1) can be carried out for the addition of n-butyllithium in a non-coordinating nonpolar solvent in particular chosen from benzene, hexane, toluene, cyclohexane, methylcyclohexane, and then for the addition of Fe(acac)3 in tetrahydrofuran.

[0470] By way of non-limiting example, this step of adding n-butyllithium and Fe(acac)3 (1 / 1) can be carried out in tetrahydrofuran at temperatures from -78°C to 25°C, preferably -78°C to -30°C for 30 minutes, then 2 hours from -78°C to 25°C, preferably from 0°C to 25°C, then 16 hours from -78°C to 25°C, preferably at 25°C.

[0471] In another embodiment, the present description relates to a preparation process, as defined above, comprising a step of preparing a compound of formula (II):

[0473] (II)

[0474] in which B, C, D, E, G, Rb R2, R3, R4, R5, R6, R7, Rs, R9 and R10 have the meanings indicated above, said step, comprising an aromatic nucleophilic substitution step of a compound of formula (III)

[0475] [Chem. 106]

[0476] (III)

[0477] wherein B, C, D, E, G, Rb, R2, R3, R4, and R5 have the meanings indicated above, and F is a fluorine atom

[0478] on a compound of formula (IV):

[0479] [Chem. 107]

[0480] (IV)

[0481] in which R6, R7, R8, R9, and Rio have the meanings indicated above

[0482] to obtain said compound of formula (II).

[0483] In this embodiment, the aromatic nucleophilic substitution occurs via the lithium amide of compound (IV) which substitutes for the fluorine of compound (III).

[0484] In another embodiment, the present description relates to a preparation process, as defined above, in which the aforementioned aromatic substitution step is carried out in a cyclic or non-cyclic ether solvent, in particular selected from diethyl ether, dimethoxymethane, dimethoxyethane, diethoxymethane, tetrahydrofuran, tert-butylmethyl ether, tert-butylethyl ether, methyl tetrahydrofuran, 1,4-dioxane, methoxycyclopentane, tert-amyl methyl ether or anisole, preferably tetrahydrofuran and at a temperature of 25°C to 125°C, preferably at 25°C.

[0485] By way of non-limiting example, this aromatic nucleophilic substitution of compound (IV) on compound (III) (1 / 1) is carried out in tetrahydrofuran at temperatures from 25 °C to 125 °C, preferably from 25 °C to 75 °C.

[0486] In another embodiment, the present description relates to a preparation process, as defined above, in which the aforementioned addition step is carried out in a non-coordinating nonpolar solvent, in particular selected from benzene, hexane, toluene, cyclohexane, methylcyclohexane, preferably in toluene and at a temperature of 25 °C to 125 °C, preferably at 25 °C or 90 °C.

[0487] By way of non-limiting example, this aromatic nucleophilic substitution of compound (IV) on compound (III) (2.5 / 1) is carried out in toluene at temperatures from 25°C to 125°C, preferably from 90°C to 125°C. By way of non-limiting example, this aromatic nucleophilic substitution of compound (IV) on compound (III) (2.5 / 1) is carried out in toluene at temperatures from 25°C to 125°C, preferably from 25°C to 75°C.

[0488] In another embodiment, the present description relates to a preparation process, as defined above, comprising a step of preparing a compound of formula (III) [Chem. 108]

[0490] (III)

[0491] in which B, C, D, E, G, Rb, R2, R3, R4, and R5 have the meanings indicated above, and F is a fluorine atom

[0492] said step, comprising a condensation step of a compound of formula (V)

[0493] [Chem. 109]

[0494] (V)

[0495] wherein B, C, D, E, G, Rb, R2, R3, R4, and R5 have the meanings indicated above, and F is a fluorine atom

[0496] on a compound of formula (VI):

[0497] [Chem. 110] HN

[0498] (VI)

[0499] in which Rb R2, R3, R4, and R5 have the meanings indicated above, for to obtain said compound of formula (III).

[0500] In this embodiment, the imine formation step of compound (III) is carried out from an aldehyde, compound (V) and an amine, compound (IV).

[0501] In another embodiment, the present description relates to a preparation process, as defined above, in which the aforementioned condensation step is carried out, at a temperature of 0°C to 150°C, in a non-coordinating nonpolar or alcoholic solvent, in particular selected from hexane, toluene, benzene, cyclohexane, methylcyclohexane, butan-1-ol, butan-2-ol, isobutanol, tert-butanol, propan-2-ol, isopropanol, methanol or ethanol, preferably hexane at 25°C, or preferably in toluene at 150°C or preferably in ethanol at 90°C.

[0502] By way of non-limiting example, this condensation of an aldehyde and an amine (1 / 1) is carried out in the presence of MgSO4 (0.08 mol%) in hexane at temperatures from 25°C to 75°C, preferably at 25°C.

[0503] By way of non-limiting example, this condensation of an aldehyde and an amine is carried out in the presence of para-toluenesulfonic acid (1 / 1,1 / 0.01) in toluene at temperatures from 25°C to 150°C, preferably at 150°C

[0504] By way of non-limiting example, this condensation of an aldehyde and an amine (1 / 1,1) takes place in ethanol at temperatures from 25°C to 90°C, preferably at 25°C

[0505] In another embodiment, the present description relates to a process for preparing, as defined above, a compound of formula (the)

[0506] [Chem. 111]

[0507]

[0508] (THE) in which:

[0509]

[0510] • B, C, D, and E, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms • Ri, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 1 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s) comprising: a) a condensation step of a compound of formula (V) [Chem. 112]

[0511]

[0512]

[0513]

[0514] in which B, C, D, and E have the meanings indicated above, and F is a fluorine atom on a compound of formula (VI): [Chem. 113]

[0515]

[0516] wherein Rb R2, R3, R4, and R5 have the meanings indicated above

[0517] to obtain the compound of formula (III)

[0518] [Chem. 114]

[0519] (III)

[0520] in which B, C, D, E, G, Rb, R2, R3, R4, and R5 have the meanings indicated above, and F is a fluorine atom

[0521] b) an aromatic nucleophilic substitution step of said compound of formula (III) on a compound of formula (IV):

[0522] [Chem. 115]

[0524] wherein R6, R7, R8, R9, and R10 have the meanings indicated above

[0525] to obtain the compound of formula (II)

[0528] in which B, C, D, E, G, Rb, R2, R3, R4, R5, R6, R7, Rs, R9 and R10 have the meanings indicated above,

[0529] c) a step of sequential addition of n-butyl lithium and then of iron(III) tris-acetylacetonate to said compound of formula (II) to obtain said compound of formula (le). Examples Materials and methods

[0530] The ¹H and ¹³C NMR spectra were acquired at 298 K on a Bruker AM250, AV300, or AV360 MHz spectrometer. The ¹⁷Li and ¹⁹F NMR spectra were acquired at 295 K on a Bruker 300 and 250 spectrometer, respectively. The chemical shifts of the ¹H spectra were measured using an internal reference of residual protonated CHC¹³ in CDC¹³ (7.24 ppm) or residual protonated benzene in benzene-d⁶ (7.16 ppm).

[0531] Elemental analyses were carried out at Analytische Laboratorien GMBH in Lindlar, Germany.

[0532] High-resolution mass spectra were measured by electrospray ionization (ESI) with a Bruker MicrOTOFq time-of-flight mass spectrometer or a Waters LCT spectrometer using electrospray ionization-time-of-flight mass spectrometry (ESLTOF)

[0533] The general procedures for the preparation of compounds of formula (la), (II) and (III) are presented below.

[0534] [Chem. 117]

[0535] (la) (II) (III)

[0536] wherein the groups R2, R4, R7 and R9 represent a hydrogen atom, and the Rh groups R3, R5, R6, R8 and Rio have the meanings set forth in the following table [Table B c DEGX RVRS R^R1® RS R3 Rdt i%] (IH) Rdt [%] (II) Rdt Procedure [^] (ïa)^ H Illll HH lilllii Cl Me Me Me Me 60^ iiiiiiii H .....H...... H h.......... Cl iPr Me H 66^ H 66^ I lll Clll ill H lll H 66^ iiiiiii H OMe 5^ H H.......... Ci iPr iPr HH 87 U ■Il FH lilllll Cl iPr iPf 1® H 6114 IBIIII H .....H...... H .....H Me Cl iPr iPr HH - 26^ 28 H Illll i HP l Ill HP l Ixl IPIII FF ''''f "ï"" .............. Cl îPr iPr HH 66 K °c. Procedure Al [f] Procedure [b] Pt B2 23 jcedure A2. [g] Procedure A3. [d] Procedure 81. 'C. [gj Procedure B3. [h] Procedure B3: Procedure B3'. Al: The appropriate aniline derivative (1 eq) is added with stirring to a solution of the appropriate 2-fluorobenzaldehyde derivative (1 eq) and MgSO4 in hexane (c = 1.6 M) at 25 °C. The solution is stirred for 2 h at this temperature, then filtered, concentrated under reduced pressure, and cooled to -20 °C to give the corresponding compound (III) as yellow crystals.

[0537] Procedure A2: In a Dean-Stark apparatus, para-toluenesulfonic acid (0.01 eq) is added with stirring to a solution of the appropriate 2-fluorobenzaldehyde derivative (1 eq) and the appropriate aniline derivative (1.1 eq) in toluene (c = 0.40 M). The solution is heated to 150°C for 15 h. Then, the solution is cooled to 25°C before the addition of a saturated aqueous solution of Na₂CO₃. The aqueous phase is separated and extracted with Et₂O. The organic phases are combined, dried over MgSO₄, filtered, and concentrated under reduced pressure to give a slightly yellow oil. Recrystallization in hexane at -20°C gives the corresponding compound (III) in the form of yellow colored crystals.

[0538] Procedure A3: 2,6-Diisopropylamine (1.1 eq) is added to a solution of perfluorobenzaldehyde (1 eq) in EtOH (c = 1.5 M) at 25 °C, and the solution is stirred at this temperature for 2 h. The solution is concentrated under reduced pressure and then cooled to -20 °C; the corresponding compound (III) is obtained as yellow crystals.

[0539] Procedure B1: A solution of n-butyllithium (n-Buli) (1 eq) is added with stirring to a solution of the appropriate aniline derivative (1 eq) in tetrahydrofuran (THF) (c = 1 M) at -78 °C. The solution is stirred for 15 h and then cannulated into a solution of the appropriate compound (III) (1 eq) in THF (c = 1 M) at 25 °C. The solution is stirred for 2 h at this temperature and then water is added. The aqueous phase is separated and extracted with hexane. The organic phases are combined, dried over MgSO4, filtered, and concentrated under reduced pressure to give a brown-colored oil. Recrystallization in hot ethanol or at -20 °C gives the corresponding compound (II) as yellow-colored crystals.

[0540] Procedure B2: The appropriate compound (III) (1 eq) is added to a suspension of lithium (2,6-diisopropylphenyl)amide (2.5 eq) in toluene (10 mL) at 25 °C. The solution is heated to 90 °C with stirring for 72 h or to 25 °C for 48 h. The solution is then cooled to 25 °C before the addition of a saturated aqueous solution of Na₂CO₃. The aqueous phase is separated and extracted with Et₂O. The organic phases are combined, dried over MgSO₄, filtered, and concentrated under reduced pressure to give a slightly brown oil. Recrystallization in hot EtOH gives the corresponding compound (II) as pale yellow crystals.

[0541] Procedure B3: TiCl4 (0.5 eq) was added to a solution of 2,6-diisopropylaniline (3 eq) in hexane (c = 1 M) under stirring at 0 °C. The solution was stirred at 25 °C for 24 h. The solution was then heated under reflux and a solution of 2-fluoroacetophenone (1 eq) in hexane (c = 2.6 M) was added. The solution was heated under reflux for 16 h. A brown solid appeared in the solution. The solution was filtered and the solid was washed with hexane. The organic phases were collected and washed with water. The aqueous phase was separated and then extracted with hexane. The organic phases were collected and dried with MgSO4, filtered, and concentrated under vacuum until a yellow oil appeared. n-BuLi (1 eq) was added to a stirred solution of 2,6-diisopropylaniline (1 eq) in THF (c = 1 M) at -78 °C.The solution is stirred for 18 hours, then deposited using a cannula into the previously prepared yellow oil solution. Synthesized in THF at 25°C, the solution is stirred for 2 hours at 25°C. Water is then added. The aqueous phase is separated and extracted with Et2O. The organic phases are combined, dried with MgSO4, filtered, and the solvent is evaporated under vacuum to obtain a slightly brown oil. The slightly brown oil is recrystallized from hot ethanol to obtain the corresponding compound (II) as a pale white powder.

[0542] Procedure Cl: n-BuLi (1.6 eq) is added with stirring to a solution of the appropriate compound (III) (1 eq) in THF (c = 0.4 M) at -78 °C. The cooling bath is removed 30 minutes after the addition. The solution is stirred for 2 h at 25 °C. Then, FeCl2 (1 eq) is added. The solution is stirred for 15 h at 25 °C, and then the solvent is evaporated under reduced pressure. The residual solid is washed with hexane and then extracted with Et2O. The dark red solution is concentrated and cooled to -20 °C to give a dark red powder of the corresponding compound (la).

[0543] EXAMPLE 1: Synthesis of (E)-N-mesityl-l-(perfluorophenyl)methanimine

[0544] [Chem. 118]

[0545] 2,4,6-Trimethylaniline (2.3 mL, 16.05 mmol) was added to a solution of perfluorobenzaldehyde (1.8 mL, 15 mmol) in EtOH (10 mL) at 25 °C, and the solution was then refluxed (90 °C) for 16 h. After evaporation of the solvent and recrystallization in Et2O at -20 °C, (E)-A-mesityl-l-(perfluorophenyl)methanimine (4.4 g, 14 mmol, 94%) was obtained as yellow crystals. *H NMR (360 MHz, CDC13, 25 °C) 0 ppm 8.36 (s, 1H, NH), 6.91 (s, 2H, H Ar), 2.30 (s, 3H, p-Me), 2.15 (s, 6H, o-Me). 13 C NMR (90 MHz, CDC13, 25°C) ô 151.6, 148.4, 134.2, 129.0, 126.5, 20.8, 18.1. MS-HR (ESI) m / z calculated for C16H13F5N [M+H]+ 314.0963, found: 314.0957.

[0546] EXAMPLE 2: Synthesis of (-(2-ethylphenyl)-1-(pentafluorophenol Dmethanimine)

[0547] [Chem. 119] w

[0548] 2-Ethylaniline (2.0 mL, 16.5 mmol) was added to a solution of perfluorobenzaldehyde (1.8 mL, 15 mmol) in EtOH (10 mL) at 25 °C and the solution was then refluxed (90 °C) for 16 h. After evaporation of the solvent and recrystallization in ether at -20 °C, (£)-A-(2-ethylphenyl)-l-(pentafluorophenyl)methanimine (3.7 g, 13.3 mmol, 82%) was obtained as yellow crystals. *H NMR (360 MHz, CDC13, 25 °C) ô ppm 8.59 (s, 1H, NH), 7.34-7.26 (m, 3H, H Ar), 7.03-6.98 (m, 1H, H Ar), 2.84 (q, 2H, J = 7.5 Hz, CH2CH3), 1.26 (t, 3H, J = 7.5 Hz, CH2CH3). 13C NMR (90 MHz, CDC13, 25°C) ô 149.8, 147.3, 138.8, 129.0, 127.4, 126.9, 116.9, 24.8, 14.9. MS-HR (ESI) m / z calculated for Ci5HnF5N [M+H]+ 300.0806, found: 300.0799.

[0549] EXAMPLE 3: Synthesis of (E)-2,3,4,5-tetrafluoro-N-mesityl-6-((mesi tyliminojmethyDaniline)

[0550] [Chem. 120] \

[0551] (£)-A-mesityl-l-(perfluorophenyl)methanimine (2.5 g, 8 mmol) was added to a solution of lithium (2,4,6-trimethylphenyl)amide (2.8 g, 20 mmol) in toluene (16 mL) and then stirred for 48 h at 25°C. After the addition of a saturated NaHCO3 solution (50 mL), the aqueous phase was extracted with EtOAc (50 mL). The organic phases were collected, dried over MgSO4, filtered, and concentrated under reduced pressure. Recrystallization in MeOH at -20°C was performed, yielding pale yellow crystals of the product (£)-2,3,4,5-tetrafluoro-A-mesityl-6-((mesitylimino)methyl)aniline (3.3 g, 7.7 mmol, 96%). ¹³C {19F} NMR (360 MHz, CDC13, 25°C) µp ppm 10.94 (s, 1H, NH3), 8.66 (s, 1H, ArCHN), 6.92-6.90 (m, 4H, HAr), 2.30 (s, 6H, p-Me), 2.22 (s, 6H, o-Me), 2.15 (s, 6H, o-Me). ¹³C {19F} NMR (100 MHz, CDC1 3, 25°C) ô ppm 157.8, 147.5, 137.6, 135.9, 135.8, 135.4, 135.3, 135.1, 134.1, 131.9, 129.5, 129.0, 128.5, 127.3, 102.5, 20.9, 20.7, 18.4. MS-HR (ESI) m / z calculated for C25 H25F4N [M+H]+ 429.1948, found: 429.1934.

[0552] EXAMPLE 4: Synthesis of (E^N -(2-ethylphenyl)-2-(((2-ethylpheny) l)imino)methyl)-3.4.5.6-tetrafluoroaniline

[0553] [Chem. 121]

[0554] (E)-N-(2-ethylphenyl)-l-(pentafluorophenyl)methanimine (2.4 g, 8 mmol) was added to a solution of lithium 2-(ethylphenyl)amide (2.5 mL, 20 mmol) in toluene (16 mL) and then stirred for 48 h at 25°C. After the addition of a saturated NaHCO3 solution (50 mL), the aqueous phase was extracted with EtOAc (50 mL). The organic phases were collected, dried over MgSO4, filtered, and concentrated under reduced pressure. Recrystallization in MeOH at -20°C gave pale yellow crystals of the product (£')-A-(2-ethylphenyl)-2-(((2-ethylpheny l)imino)methyl)-3,4,5,6-tetrafluoroaniline (2.7 g, 6.75 mmol, 84%). *H NMR (360 MHz, CDC13, 25 °C) ô ppm 10.91 (s, 1H, NH), 8.84 (s, 1H, ArCHN), 7.32-7.23 (m, 4H, H Ar), 7.21-7.12 (m, 2H, H Ar), 7.04-7.00 (m, 2H, H Ar), 2.81-2.70 (m, 4H, CH2CH3), 1.26 (t, 3H, J = 7.5 Hz, CH2CH3), 1.13 (t, 3H, J = 7.5 Hz, CH2CH3). 13C {19 F] NMR (100 MHz, CDC13, 25°C) ô ppm 153.9, 149.1, 139.3, 137.7, 137.0, 133.7, 132.9, 131.3, 128.9, 128.6, 127.1, 127.0, 126.1, 124.8, 122.2, 118.2, 106.0, 24.9, 24.7, 14.8, 14.2. MS-HR (ESI) m / z calculated for C23H21F4N2 [M+H]+ 401.1635, found: 401.1621. . EXAMPLE 5#: Summary of P5

[0555] [Chem. 122]

[0556] n-BuLi (2.5 M in hexane) (2 mL, 5 mmol) was added with stirring to a solution of (E)-2,3,4,5-tetrafluoro-A-mesityl-6-((mesitylimino)methyl)aniline (2.1 g, 5 mmol) in THF (10 mL) at -78 °C. The cooling bath was removed 30 minutes after the addition. The solution was stirred for 4 h at 25 °C. Then, FeCl2 (0.63 g, 5 mmol) was added. The solution was stirred overnight, and then the solvent was evaporated under reduced pressure. The residual solid was washed with hexane or pentane (10 mL) and then extracted with Et2O (25 mL). The ether solution was filtered, then concentrated and replaced with hexane (20 mL). After adding a few drops of THF and cooling to -20°C, red-colored crystals of product P5 (2.09 g, 3.0 mmol 60%) were obtained. Elemental analysis calculated for C25H23Cl2F4FeLiN2(C4H8O)2: C, 56.19; H, 5.57; N, 3.97, found: C, 54.53; H 5.92; N 4.15. 'H NMR (360 MHz, C6D6-50 pL THF-d8, 25 °C) 0 ppm 71.05 (s, 3H, p-Me), 33.95 (s, 3H, p-Me), 25.51 (s, 2H, mH Ar), 24.01 (br s, 6H, o-Me), 14.16 (s, 2H, mH Ar), 4.37 (br s, 12H, THF), 2.15 (br s, 6H, o-Me), 1.69 (br s, 12H, THF). 7Li NMR (117 MHz, C6D6-50pL THF-d8, 25 °C) ô ppm 239.6 (br s). . EXAMPLE 6#: Summary of P6

[0557] [Chem. 123]

[0558] n-BuLi (2.5 M in hexane) (2 mL, 5 mmol) was added with stirring to a solution of (£')-A-(2-ethylphenyl)-2-(((2-ethylphenyl)imino)methyl)-3,4,5,6-tetrafluor oaniline (2 g, 5 mmol) in THF (10 mL) at -78 °C. The cooling bath was removed 30 minutes after the addition. The solution was stirred for 4 h at 25 °C. Then, FeCl2 (0.63 g, 5 mmol) was added. The solution was stirred overnight and then the The solvent was evaporated under reduced pressure. The residual solid was washed with hexane or pentane (10 mL) and then extracted with Et2O (25 mL). The ether solution was filtered, concentrated, and replaced with hexane (20 mL). After adding a few drops of THF and cooling to -20°C, red crystals of product P6 (1.1 g, 1.6 mmol, 35%) were obtained. Elemental analysis calculated for C23HigC12F4FeLiN2(C4H8O)2: C, 54.97; H, 5.21; N, 4.14; found: C, 51.13; H, 4.90; N, 4.40. 1H NMR (250 MHz, C6D6-50 pL THF-d8, 25 °C) ô ppm 34.58 (br s, 1H, H Ar), 26.05 (s, 1H, H Ar), 23.66 (s, 1H, H Ar), 14.94 (s, 2H, H Ar), 12.90 (s, 1H, H Ar), 4.94 (br s, 10H, THF), 1.91 (br s, 10H, THF), -7.84 (br s, 4H, CH2), -10.46 (br s, 6H, CH3), -37.60 (s, 1H, H Ar), -71.64 (s, 1H, H Ar), -87.68 (br s, 1H, ArCHN). EXAMPLE 7#: Summary of P7

[0559] [Chem. 124]

[0560] n-BuLi (2.5 M in hexane) (2.8 mL, 7 mmol) is added with stirring to a solution of (E)-2,3,4,5-tetrafluoro-N-mesityl-6-((mesitylimino)methyl)aniline (3 g, 7 mmol) in THF (15 mL) at -78 °C. The cooling bath is removed 30 minutes after the addition. The solution is stirred for 4 h at 25 °C and concentrated under reduced pressure to give the lithium amide of (E)-2,3,4,5-tetrafluoro-N-mesityl-6-((mesitylimino)methyl)aniline. To a solution of Fe(acac)3 (2.1 g, 6 mmol) in THF (12 mL), lithium amide of (£)-2,3,4,5-tetrafluoro-A-mesityl-6-((mesitylimino)methyl)aniline (2.6 g, 6 mmol) in THF (6 mL) is added while stirring at 25 °C. The solution is then stirred for 16 hours at the same temperature. The red-colored solution turns dark green. After cooling to -20 °C, filtration through Celite and evaporation are performed. The solid is washed with cold pentane to yield a dark green powder, product P7 (2 g, 2.9 mmol, 50%).Calculated elemental analysis for C35H37F4FeN2O4: C, 61.68; H, 5.47; N, 4.11, found: C, 59.9; H 5.39; N 3.92. 'H NMR (250 MHz, C6D6-50 pL THF-d8 25 °C) 62.91 (br s, 3H, p-Me), 50.93 (br s, 3H, p-Me), 28.92 (br s, 14H, o-Me and mH Ar), 20.99 (br s, . 14H, Me and mH Ar), -25.10 (br s, 2H, CH) (deviations in integration values ​​may be observed due to signal width) EXAMPLE 8#: Summary of P8

[0561] [Chem. 125]

[0562] n-BuLi (2.5 M in hexane) (0.8 mL, 2.0 mmol) was added with stirring to a solution of (£')-2,3,4,5-tetrafluoro-A-mesityl-6-((mesitylimino)methyl)aniline (0.77 g, 1.8 mmol) in THF (3.6 mL) at -78 °C. The cooling bath was removed 30 minutes after the addition. The solution was stirred for 4 h at 25 °C. Then, FeBr2 (0.389 g, 1.8 mmol) was added. The solution was stirred overnight, and then the solvent was evaporated under reduced pressure. The residual solid was washed with hexane or pentane and then extracted with Et2O. The ether solution was filtered, then concentrated and replaced with hexane. After adding a few drops of THF and cooling to -20°C, red-colored crystals of product P8 (0.63 g, 0.8 mmol, 44%) were obtained. 'H NMR (250 MHz, C6D6-50 pL THF-d8, 25 °C) 0 ppm 71.09 (s, 3H, p-Me), 33.98 (s, 3H, p-Me), 27.42 (br s, 8H, mH Ar and o-Me), 15.91 (s, 2H, mH Ar), 4.43 (br s, 14H, THF), 2.13 (br s, 6H, o-Me), 1.75 (br s, 14H, THF).7Li NMR (117 MHz, C6D6 -50pL THF-d8, 25 °C) ô ppm 162.66 (br s). . EXAMPLE 9#: Summary of P9

[0563] [Chem. 126]

[0564] n-BuLi (2.5 M in hexane) (1.2 mL, 3.0 mmol) was added with stirring to a solution of (E)-A-(2-(mesitylamino)benzylidene)-2,4,6-trimethylaniline (LO g,

[0565] 2.8 mmol) in THF (7 mL) at -78 °C. The cooling bath was removed 30 minutes after the addition. The solution was stirred for 2 h at 25 °C. Then, FeCl2 (0.356 g, 2.8 mmol) was added. The solution was stirred overnight, and then the solvent was evaporated under reduced pressure. The residual solid was washed with hexane and then extracted with Et2O. The ether solution was filtered, concentrated, and cooled to -20 °C to give dark red crystals of product P9 (1.12 g, 1.77 mmol, 75%). Calculated elemental analysis for C33H4iCl2FeLiN2O2: C, 62.78; H, 6.55; N, 4.44; found: C, 62.54; H, 6.68; N, 4.47. IR (cm1): 2953, 2925, 1622, 1605, 1570, 1521, 1461, 1433, 1377, 1333, 1260, 1207, 1224, 1182, 1162, 1143, 1041, 922, 873, 854, 793, 748, 672. 'H NMR (250MHz, C6D6-50 pL THF-d8, 25 °C) ô ppm 95.8 (br s, 1H, mH Ar), 85.7 (br s, 1H, mH Ar), 58.4 (s, 3H, p-Me), 34.6 (s, 3H, p-Me), 24.5 (s, 2H, mH Ar), 15.2 (br s, 8H, mH Ar overlap with o-Me), 4.6 (s, 8H, THF), 1.8 (s, 8H, THF), 0.5 (br s, 6H, o-Me), -39.9 (s, 1H, ArCHN), -44.8 (br s, 1H, p-H Ar). 7Li NMR (117 MHz, C6D6-50pL THF-d8, 25 °C) ô 238.2 (br s). . EXEMPLE 10#: Synthèse de P10 [Chem. 127]

[0566] n-BuLi (2.5 M in hexane) (1.0 mL, 2.5 mmol) was added with stirring to a solution of (£jA-(2-(((2,6-diisopropylphenyl)imino)methyl)phenyl)-2,4,6-trimethylaniline (1.0 g, 2.5 mmol) in THF (10 mL) at -78 °C. The cooling bath was removed 30 minutes after the addition. The solution was stirred for 2 h at 25 °C. Then, FeCl2 (0.318 g, 2.5 mmol) was added. The solution was stirred overnight, and then the solvent was evaporated under reduced pressure. The residual solid was washed with hexane and then extracted with Et2O. The ether solution was filtered, concentrated, and cooled to -20 °C to give dark red crystals of product P10 (0.96 g, 1.42 mmol, 57%). Calculated elemental analysis for C36H47Cl2FeLiN2O2: C, 64.20; H, 7.03; N, 4.16, found: C, 63.83; H, 7.16; N, 4.22. IR (cm1): 2957, 2961, 2925, 2876, 1659, 1605, 1517, 1461, 1431, 1375, 1364, 1335, 1300, 1257, 1204, 1168, 1157, 1125, 1108, 1096, 1043, 924, 888, 873, 856, 837, 810, 797, 751, 735, 678.‘H NMR (250MHz, C6D6-50 pL THF-d8, 25 °C) ô ppm 93.6 (br s, 1H, m-H Ar), 84.0 (br s, 1H, m-H Ar), 56.6 (s, 3H, p-Me), 23.8 (s, 2H, m-H Ar), 15.2 (s, 2H, m-H Ar), 14.2 (br s, 6H, o-Me), 6.9 (s, 8H, THF), 2.5 (s, 8H, THF), 1.0 (br s, 6H, CHMeMe), -16.4 . (br s, 6H, CHMeMe), -35.6 (s, 1H, ArCHN), -39.0 (br s, 1H, p-H Ar), -43.9 (br s, 1H, p-H Ar), -49.0 (br s, 2H, CHMeMe). 7Li NMR (117 MHz, C6D6-50pL THF-d8, 25 °C) ô ppm 258.2 (br s). EXEMPLE 11#: Synthèse de Pli

[0567] [Chem. 128]

[0568] n-BuLi (2.5 M in hexane) (1.4 mL, 3.5 mmol) was added with stirring to a solution of (£jA-(2-((2,6-diisopropylphenyl)amino)benzylidene)-2,6-diisopropylaniline (1.5 g, 3.4 mmol) in THF (15 mL) at -78 °C. The cooling bath was removed 30 minutes after the addition. The solution was stirred for 2 h at 25 °C. Then, FeCl2 (0.431 g, 3.4 mmol) was added. The solution was stirred overnight, and then the solvent was evaporated under reduced pressure. The residual solid was washed with hexane and then extracted with Et2O. The ether solution was filtered, concentrated, and cooled to -20 °C to give red-colored crystals of the Pli product (1.91 g, 2.66 mmol, 78%). Elemental analysis calculated for C3çH53Cl2FeLiN2O2: C, 65.46; H, 7.47; N, 3.91, found: C, 64.91; H 7.37; No. 3.95. 'H NMR (250MHz, C6D6-50 pL THF-d8, 25 °C) ô ppm 91.4 (s, 1H, mH Ar), 83.3 (s, 1H, mH Ar), 23.3 (s, 2H, mH Ar), 14.5 (s, 2H, mH Ar), 4.5 (br s, 8H, THF), 4.3 (br s, 6H, CHMeMe), 1.8 (br s, 8H, THF), 1.4 (br s, 6H, CHMeMe), -8.6 (s, 1H, oH Ar), -16.4 (br s, 6H, CHMeMe), -19.1 (br s, 6H, CHMeMe), -29.5 (br s, 2H, CHMeMe), -34.5 (s, 1H, pH Ar), -39.5 (s, 1H, pH Ar), -42.1 (br s, 1H, ArCHN), -51.6 (br s, 2H, CHMeMe), -56.5 (s, 1H, pH Ar). 7Li NMR (117 MHz, C6D6-50pL THF-d8, 25 °C) ô ppm 269.8 (br s). . EXAMPLE 12#: Summary of P12

[0569] [Chem. 129]

[0570] n-BuLi (1.6 M in hexane) (1.2 mL, 1.91 mmol) was added with stirring to a solution of (£jA-(2,6-diisopropylphenyl)-2-(((2,6-diisopropylphenyl) (imino)methyl)-4-methoxyaniline (0.9 g, 1.91 mmol) in THF (9 mL) at -78 °C. The cooling bath was removed 30 minutes after the addition. The solution was stirred for 2 h at 25 °C. Then, FeCl2 (0.242 g, 1.91 mmol) was added. The solution was stirred overnight, and then the solvent was evaporated under reduced pressure. The residual solid was washed with hexane and then extracted with Et2O. The ether solution was filtered, concentrated, and cooled to -20 °C to give dark red crystals of product P12 (1.24 g, 1.65 mmol, 87%). Calculated elemental analysis for C40H55Cl2FeLiN2O3: C, 64.44; H, 7.44; N, 3.76, found: C, 63.00; H 7.47; N 4.25. 'H NMR (250MHz, C6D6-50 pL THF-d8, 25 °C) ô ppm 91.1 (s, 1H, mH Ar), 91.9 (s, 1H, mH Ar), 24.9 (s, 2H, mH Ar), 17.0 (s, 3H, OMe), 15.5 (s, 2H, mH Ar), 4.6 (s, 6H, CHMeMe), 4.3 (br s, 8H, THF), 1.7 (br s, 8H, THF), 1.2 (br s, 6H, CHMeMe), -15.2 (br s, 6H, CHMeMe), -17.8 (br s, 6H, CHMeMe), -33.4 (s, 1H, ArCHN), -42.4 (br s, 1H, pH Ar), -54.9(s, 1H, pH Ar). 7Li NMR (117 MHz, C6D6-50pL THF-d8, 25 °C) at ppm 277.4 (br s) . EXAMPLE 13#: Synthesis of P13

[0571] [Chem. 130]

[0572] n-BuLi (2.5 M in hexane) (0.75 mL, 1.85 mmol) was added with stirring to a solution of (£jA-(2,6-diisopropylphenyl)-2-(((2,6-diisopropylphenyl)imino)methyl)-5-fluoroaniline (0.84 g, 1.84 mmol) in THF (8.5 mL) at -78 °C. The cooling bath was removed 30 minutes after the addition. The solution was stirred for 2 h at 25 °C. Then, FeCl2 (0.233 g, 1.84 mmol) was added. The solution was stirred overnight, and then the solvent was evaporated under reduced pressure. The residual solid was washed with hexane and then extracted with Et2O. The ether solution was filtered, concentrated, and cooled to -20 °C to give colored crystals red of product P13 (0.347 g, 0.473 mmol, 26%). Elemental analysis calculated for C39H52Cl2FFeLiN2O2: C, 63.86; H, 7.15; N, 3.82, found: C, 63.47; H 7.18; N 3.89.IR (cm1): 2958, 2927, 2871, 1614, 1575, 1522, 1463, 1435, 1422, 1386, 1322, 1311, 1254, 1209, 1181, 1165, 1105, 1095, 1059, 1041, 1001, 935, 910, 888, 848, 798, 782, 770, 736, 721. *H NMR (250MHz, C6D6, 25 °C) ô ppm 93.8 (br s, 1H, m-H Ar), 92.2 (br s, 1H, m-H Ar), 20.6 (s, 2H, m-H Ar), 13.1 (s, 2H, m-H Ar), 4.9 (br s, 8H, THF), 3.8 (s, 6H, CHMeMe), 1.9 (br s, 14H, CHMeMe; THF), -17.2 (br s, 6H, CHMeMe), . -19.7 (br s, 6H, CHMeMe), -34.5 (s, 1H, ArCHN), -36.7 (br s, 1H, p-H Ar), -37.1 (s, 1H, p-H Ar), -54.5 (s, 1H, p-H Ar). 7Li NMR (117 MHz, C6D6-50[iL THF-d8, 25 °C) ô ppm 273.5 (br s). EXEMPLE 14#: Synthèse de P14

[0573] [Chem. 131]

[0574] n-BuLi (2.5 M in hexane) (0.9 mL, 2.2 mmol) was added with stirring to a solution of (E)-N-(1-(2-((2,6-diisopropylphenyl)amino)phenyl)ethylidene)-2,6-diisopropylaniline (1.0 g, 2.2 mmol) in THF (10 mL) at -78 °C. The cooling bath was removed 30 minutes after the addition. The solution was stirred for 2 h at 25 °C. Then, FeCl2 (0.28 g, 2.2 mmol) was added. The solution was stirred overnight, and then the solvent was evaporated under reduced pressure. The residual solid was washed with hexane and then extracted with Et2O. The ethereal solution is filtered, concentrated, and cooled to -20°C to give red-colored crystals of product P14 (0.445 g, 0.61 mmol, 28%). Calculated elemental analysis for C4OH55Cl2FeLiN2O2: C, 65.85; H, 7.60; N, 3.84; found: C, 66.02; H, 7.68; N, 3.96. 'H NMR (250MHz, C6D6, 25 °C) ô ppm 79.3 (br s, 1H, mH Ar), 22.4 (s, 2H, mH Ar), 14.3 (s, 2H, mH Ar), 5.4 (br s, 6H, CHMeMe), 4.7 (s, 8H, THF), 1.8 (br s, 8H, THF), -0.3 (br s, 6H, CHMeMe), -19.0 (br s, 6H, CHMeMe), -20.4 (br s, 6H, CHMeMe), -41.3 (br s, 1H, pH Ar), -41.7 (br s, 1H, pH Ar), -49.3 (s, 1H, oH Ar), -60.2(s, 1H, pH Ar), -95.4 (s, 3H, Me(C(N))). 7Li NMR (117 MHz, C6D6-50[iL THF-d8, 25 °C) ô ppm 309.3 (br s). EXAMPLE 15#: Synthesis of P15.

[0575] [Chem. 132]

[0576] n-BuLi (2.5 M in hexane) (1.2 mL, 1.9 mmol) was added with stirring to a solution of (£jA-(2,6-diisopropylphenyl)-2-(((2,6-diisopropylphenyl )imino)methyl)-3-methoxyaniline (0.9 g, 1.9 mmol) in THF (9 mL) at -78 °C. The cooling bath was removed 30 minutes after the addition. The solution was stirred for 2 hours at 25 °C. Then, FeCl₂ (0.242 g, 1.91 mmol) was added. The solution was stirred overnight, and then the solvent was evaporated under reduced pressure. The residual solid was washed with hexane and then extracted with Et₂O. The ethereal solution was filtered, concentrated, and cooled to -20 °C to give red-colored crystals of product P15 (1.18 g, 1.58 mmol, 83%). Calculated elemental analysis for C₄₀H₅₅Cl₂FeLiN₂O₃: C, 64.44; H, 7.44; N, 3.7; found: C, 64.03; H, 7.52; N, 3.83. IR (cm'): 3068, 2960, 2927, 2869, 1621, 1608, 1574, 1511, 1462, 1437, 1323, 1248, 1221, 1206, 1171, 1159, 1120, 1098, 1058, 1042, 989, 935, 913, 861, 794. (250MHz, C6D6 -50 pL THF-d8, 25 °C) ô ppm 76.8 (s, 1H, mH Ar), 21.3 (s, 2H, mH Ar), 13.4 (s, 2H, mH Ar), 4.9 (br s, 8H, THF), 4.5 (s, 3H, OMe), 3.7 (s, 6H, CHMeMe), 1.9 (br s, 14H, THF, CHMeMe), -17.5 (br s, 6H, CHMeMe), -20.2 (br s, 6H, CHMeMe), -31.6 (br s, 1H, ArCHN), -34.6 (s, 1H, pH Ar), -34.9 (s, 1H, pH Ar), -34.6 (br s, 2H, CHMeMe), -55.8 (s, 1H, pH Ar). 7Li NMR (117 MHz, C6D6-50pL THF-d8, 25 °C) ô ppm 277.7 (br s). .

[0577] EXEMPLE 16 : Synthèse A de l'ester pinacolique de l'acide 1-nonylboronique

[0578] [Chem. 133]

[0579] The reaction was carried out under an inert atmosphere in a glove box. A solution of bis(pinacolato)dibore (2 eq) in benzene (c = 0.5 M) was added to catalyst P5 (10 mol%) and EtNMeLi (1.2 eq). A solution of bromononane (1 eq) in benzene (c = 0.25 M) was added to the solution, which was then made up to a total bromononane concentration of 0.08 M. The reaction mixture was stirred at 25 °C for 48 h (not optimized time), and then a saturated aqueous solution of NH4Cl was added. After extraction with EtOAc, the combined organic phases were dried over MgSO4, filtered, and evaporated under reduced pressure. Silica gel column chromatography was performed and gave the pinacolic ester of 1-nonylboronic acid with a 25% yield. 'H NMR (300 MHz, CDC13, 22 °C) 0 ppm 1.43-1.33 (m, 2H), 1.25-1.24 (m, 22H), 0.87 (t, J = 6.4 Hz, 3H), 0.76 (t, J = 7.6 Hz, 2H).13C{ 'H] NMR (75 MHz, CDC13, 22 °C) ô ppm 83.0, 32.6, 32.0, 29.5, 29.4, 25.0, 24.2, 22.8, 14.3. .

[0580] EXAMPLE 17; Synthesis B of the pinacolic ester of 1-nonylboronic acid

[0581] [Chem. 134]

[0582] The reaction was carried out under an inert atmosphere in a glove box. A solution of bis(pinacolato)dibore (2 eq) in tert-amylmethyl ether (c = 0.5 M) was added to catalyst P5 (10 mol%) and EtNMeLi (1.2 eq). A solution of bromononane (1 eq) in tert-amylmethyl ether (c = 0.25 M) was added to the solution, which was then made up to a total bromononane concentration of 0.08 M. The reaction mixture was stirred at 25 °C for 48 h (not optimized time), and then a saturated aqueous solution of NH4Cl was added. After extraction with EtOAc, the combined organic phases were dried over MgSO4, filtered, and evaporated under reduced pressure. An analysis by *H NMR using 1,3,5-trimethoxybenzene as an internal standard gave the pinacolic ester of 1-nonylboronic acid with a 44% yield.

[0583] EXAMPLE 18: C synthesis of the pinacolic ester of 1-nonylboronic acid

[0584] [Chem. 135]

[0585] The reaction was carried out under an inert atmosphere in a glove box. A solution of bis(pinacolato)dibore (2 eq) in methyl tert-L-butyl ether (c = 0.5 M) was added to catalyst P5 (10 mol%) and EtNMeLi (1.2 eq). A solution of bromononane (1 eq) in methyl tert-L-butyl ether (c = 0.25 M) was added to the solution, which was then brought to a total bromononane concentration of 0.08 M. The reaction mixture was stirred at 25 °C for 44 h (not optimized time), and then a saturated aqueous solution of NH4Cl was added. After extraction with EtOAc, the combined organic phases were dried over MgSO4, filtered, and evaporated under reduced pressure. An analysis by ¹H NMR using 1,3,5-trimethoxybenzene as an internal standard gave the pinacolic ester of 1-nonylboronic acid with a 37% yield. Analysis by NMR spectroscopy gives the same result as in Example 16.

[0586] EXAMPLE 19: C synthesis of the pinacolic ester of 1-nonylboronic acid

[0587] [Chem. 136]

[0588] The reaction was carried out under an inert atmosphere in a glove box. Bis(pinacolato)dibore (2 eq) was added to catalyst P5 (10 mol%) and EtNMeLi (1.2 eq). A solution of bromononane (1 eq) in THF (c = 0.25 M) was added to the mixture, which was then made up to a total bromononane concentration of 0.16 M. The reaction mixture was stirred at 25 °C for 36 h (not optimized time), and then a saturated aqueous solution of NH4Cl was added. After extraction with EtOAc, the combined organic phases were dried over MgSO4, filtered, and evaporated under reduced pressure. A 1H NMR analysis using 1,3,5-trimethoxybenzene as an internal standard yielded the pinacolic ester of 1-nonylboronic acid in 49% yield. Silica gel column chromatography was performed and yielded the pinacolic ester of 1-nonylboronic acid in 35% yield.Analysis by NMR spectroscopy gives the same result as example 16.

[0589] EXAMPLE 20: Synthesis D of the pinacolic ester of 1-nonylboronic acid

[0590] [Chem. 137]

[0591] The reaction was carried out under an inert atmosphere in a glove box. Bis(pinacolato)dibore (2 eq) was added to catalyst P8 (10 mol%) and EtNMeLi (1.2 eq). A solution of bromononane (1 eq) in THF (c = 0.25 M) was added to the mixture, which was then made up to a total bromononane concentration of 0.16 M. The reaction mixture was stirred at 25 °C for 36 h (non-optimized time), and then a saturated aqueous solution of NH4Cl was added. After extraction with EtOAc, the combined organic phases were dried over MgSO4, filtered, and evaporated under reduced pressure. An analysis by ¹H NMR using 1,3,5-trimethoxybenzene as an internal standard gave the pinacolic ester of 1-nonylboronic acid with a 42% yield. Analysis by NMR spectroscopy gave the same result as Example 16.

[0592] EXAMPLE 21: Synthesis E of the pinacolic ester of 1-nonylboronic acid

[0593] [Chem. 138]

[0594] The reaction was carried out under an inert atmosphere in a glove box. Bis(pinacolato)dibore (2 eq) was added to catalyst P7 (10 mol%) and EtNMeLi (2 eq). A solution of bromononane (1 eq) in THF (c = 0.25 M) was added to the mixture, which was then made up to a total bromononane concentration of 0.16 M. The reaction mixture was stirred at 25 °C for 36 h (not optimized time), and then a saturated aqueous solution of NH4Cl was added. After extraction with EtOAc, the combined organic phases were dried over MgSO4, filtered, and evaporated under reduced pressure. 1H NMR analysis using 1,3,5-trimethoxybenzene as an internal standard gave the pinacolic ester of 1-nonylboronic acid with a 45% yield. Analysis by NMR spectroscopy gives the same result as example 16.

[0595] EXAMPLE 22: Synthesis A of the pinacolic ester of acid cycloheptylboronic

[0596] [Chem. 139]

[0597] The reaction was carried out under an inert atmosphere in a glove box. A solution of bis(pinacolato)dibore (2 eq) in benzene (c = 0.5 M) was added to catalyst P5 (10 mol%) and EtNMeLi (1.2 eq). A solution of bromocycloheptane (1 eq) in benzene (c = 0.25 M) was added to the solution, which was then made up to a total bromocycloheptane concentration of 0.08 M. The reaction mixture was stirred at 80 °C for 48 h (not optimized time), and then a saturated aqueous solution of NH4Cl was added. After extraction with EtOAc, the combined organic phases were dried over MgSO4, filtered, and evaporated under reduced pressure. Silica gel column chromatography was performed, yielding the pinacolic ester of cycloheptylboronic acid in 39% yield. 1H NMR (300 MHz, CDC13, 22 °C) ô ppm 1.78-1.68 (m, 4H), 1.57-1.54 (m, 2H), 1.49-1.43 (m, 6H), 1.23 (s, 12H). 13C{ 'H] NMR (75 MHz, CDC13, 22 °C) ô ppm 82.9, 29.8, 29.1, 28.5, 24.9.

[0598] EXAMPLE 23: Synthesis B of the pinacolic ester of cycloheptylboronic acid

[0600] The reaction is carried out under an inert atmosphere in a glove box. Bis(pinacolato)dibore (2 eq) is added to catalyst P5 (10 mol%) and EtNMeLi (1.2 eq). A solution of bromocycloheptane (1 eq) in THF (c = 0.25 M) is added to the mixture, which is then brought up to a total bromocycloheptane concentration of 0.16 M. The reaction mixture is stirred at 25 °C for 36 h (non-optimized time), and then a saturated aqueous solution of NH4Cl is added. After extraction with EtOAc, the combined organic phases are dried over MgSO4, filtered, and evaporated under reduced pressure.

[0601] EXAMPLE 24: Synthesis of the pinacolic ester of 2-(4-phenylbutyD- Boronica

[0602] [Chem. 141]

[0603] The reaction was carried out under an inert atmosphere in a glove box. Bis(pinacolato)dibore (2 eq) was added to catalyst P5 (10 mol%) and EtNMeLi (1.2 eq). A solution of (3-bromobutyl)benzene (1 eq) in THF (c = 0.25 M) was added to the mixture, which was then made up by adding THF to obtain a total (3-bromobutyl)benzene concentration of 0.16 M. The reaction mixture was stirred at 25 °C for 36 h (non-optimized time), and then a saturated aqueous solution of NH4Cl was added. After extraction with EtOAc, the combined organic phases were dried over MgSO4, filtered, and evaporated under reduced pressure. An analysis by 'H NMR using 1,3,5-trimethoxybenzene as an internal standard gave the pinacolic ester of 2-(4-phenylbutyl)-boronic acid with 31% yield.

[0604] EXAMPLE 25: Synthesis A of the pinacolic ester of l-(3-phenylpropyl)-boronic acid

[0605] [Chem. 142]

[0606] The reaction was carried out under an inert atmosphere in a glove box. Bis(pinacolato)dibore (2 eq) was added to catalyst P5 (10 mol%) and EtNMeLi (1.2 eq). A solution of (3-bromopropyl)benzene (1 eq) in THF (c = 0.25 M) was added to the mixture, which was then made up by adding THF to obtain a total (3-bromopropyl)benzene concentration of 0.16 M. The reaction mixture was stirred at 25 °C for 36 h (non-optimized time), and then a saturated aqueous solution of NH4Cl was added. After extraction with EtOAc, the combined organic phases were dried over MgSO4, filtered, and evaporated under reduced pressure. An H-NMR analysis using 1,3,5-trimethoxybenzene as an internal standard gave the pinacolic ester of l-(3-phenylpropyl)boronic acid with a 57% yield. Silica gel column chromatography was performed and gave the pinacolic ester of l-(3-phenylpropyl)boronic acid with a 44% yield.1 H NMR (300 MHz, CDC13, 22 °C) ô ppm 7.29-7.24 (m, 2H), 7.19-7.13 (m, 3H), 2.61 (t, J = 7.6 Hz, 2H), 1.79-1.68 (m, 2H), 1.24 (s, 12 H ), 0.83 (t, J = 8.0 Hz, 2H). 13C{1 H] NMR (75 MHz, CDC13, 22 °C) ô ppm 142.9, 128.7, 128.3, 125.7, 83.1, 38.7, 26.2, 25.0. .

[0607] EXEMPLE 26 : Synthèse B de l'ester pinacolique de l'acid l-(3-phénylpropyl)- boronique

[0608] [Chem. 143]

[0609] The reaction was carried out under an inert atmosphere in a glove box. Bis(pinacolato)dibore (2 eq) was added to catalyst P5 (10 mol%) and EtNMeLi (1.2 eq). A solution of (3-chloropropyl)benzene (1 eq) in THF (c = 0.25 M) was added to the mixture, which was then made up by adding THF to obtain a total (3-chloropropyl)benzene concentration of 0.16 M. The reaction mixture was stirred at 25 °C for 36 h (non-optimized time), and then a saturated aqueous solution of NH4Cl was added. After extraction with EtOAc, the organic phases The combined mixtures were dried over MgSO4, filtered, and evaporated under reduced pressure. ¹H NMR analysis using 1,3,5-trimethoxybenzene as an internal standard gave the pinacolic ester of 1-(3-phenylpropyl)boronic acid with a 55% yield. NMR spectroscopy analysis gave the same result as in Example 25.

[0610] EXAMPLE 27: Synthesis A of the pinacolic ester of 2-(2-methyl-4-phenylbutyD-boronic acid

[0611] [Chem. 144]

[0612] The reaction was carried out under an inert atmosphere in a glove box. Bis(pinacolato)dibore (2 eq) was added to catalyst P5 (10 mol%) and EtNMeLi (1.2 eq). A solution of (3-methyl-3-chlorobutyl)benzene (1 eq) in THF (c = 0.25 M) was added to the mixture, which was then made up to a total (3-methyl-3-chlorobutyl)benzene concentration of 0.16 M. The reaction mixture was stirred at 25 °C for 36 h (not optimized time), and then a saturated aqueous solution of NH4Cl was added. After extraction with EtOAc, the combined organic phases were dried over MgSO4, filtered, and evaporated under reduced pressure. An analysis by 'H NMR using 1,3,5-trimethoxybenzene as an internal standard gave the pinacolic ester of 2-(2-methyl-4-phenylbutyl)-boronic acid with 23% yield.

[0613] EXAMPLE 28: Synthesis B of the pinacolic ester of 2-(2-methyl-4-phenylbutyD-boronic acid

[0614] [Chem. 145]

[0615] The reaction is carried out under an inert atmosphere in a glove box. Bis(pinacolato)dibore (2 eq) is added to catalyst P5 (10 mol%) and EtNMeLi (1.2 eq). A solution of (3-methyl-3-chlorobutyl)benzene (1 eq) in tert-amylmethyl ether (c = 0.25 M) is added to the mixture, which is then made up to the required concentration by adding terLamylmethyl ether to obtain a total (3-methyl-3-chlorobutyl)benzene concentration of 0.16 M. The reaction mixture is stirred at 25 °C. for 36 hours (not optimized time), then a saturated aqueous solution of NH4Cl is added. After extraction with EtOAc, the combined organic phases are dried over MgSO4, filtered, and evaporated under reduced pressure.

[0616] EXAMPLE 29: Synthesis of the pinacolic ester of 1-adamantylboronic acid

[0617] [Chem. 146]

[0618] The reaction is carried out under an inert atmosphere in a glove box. Bis(pinacolato)dibore (2 eq) is added to catalyst P5 (10 mol%) and EtNMeLi (1.2 eq). A solution of 1-bromoadamantane (1 eq) in THF (c = 0.25 M) is added to the mixture, which is then brought up to a total concentration of 0.16 M of THF. The reaction mixture is stirred at 25 °C for 36 h (non-optimized time), and then a saturated aqueous solution of NH4Cl is added. After extraction with EtOAc, the combined organic phases are dried over MgSO4, filtered, and evaporated under reduced pressure.

[0619] EXAMPLE 30: Synthesis of the pinacolic ester of 4-(l-(benzyloxycarbonylDpiperidinylD-boronic acid)

[0620] [Chem. 147]

[0621] The reaction is carried out under an inert atmosphere in a glove box. Bis(pinacolato)dibore (2 eq) is added to catalyst P5 (10 mol%) and EtNMeLi (1.2 eq). A solution of benzyl 4-bromopiperidine-l-carboxylate (1 eq) in THF (c = 0.25 M) is added to the mixture, which is then brought up to a total concentration of benzyl 4-bromopiperidine-l-carboxylate of 0.16 M. The reaction mixture is stirred at 25 °C for 36 h (non-optimized time), and then a saturated aqueous solution of NH4Cl is added. After extraction with EtOAc, the combined organic phases are dried over MgSO4, filtered, and evaporated under reduced pressure.

[0622] EXAMPLE 31: Synthesis of the pinacolic ester of 3-oxetanylboronic acid

[0623] [Chem. 148]

[0624] The reaction is carried out under an inert atmosphere in a glove box. Bis(pinacolato)dibore (2 eq) is added to catalyst P5 (10 mol%) and EtNMeLi (1.2 eq). A solution of 3-bromooxetane (1 eq) in THF (c = 0.25 M) is added to the mixture, which is then brought up to a total concentration of 3-bromooxetane of 0.16 M. The reaction mixture is stirred at 25 °C for 36 h (non-optimized time), and then a saturated aqueous solution of NH4Cl is added. After extraction with EtOAc, the combined organic phases are dried over MgSO4, filtered, and evaporated under reduced pressure.

[0625] EXAMPLE 32: Synthesis of the pinacolic ester of 3-(l-(tert-) acid butoxycarbonyDazetidinyD-boronic

[0626] [Chem. 149]

[0627] The reaction is carried out under an inert atmosphere in a glove box. Bis(pinacolato)dibore (2 eq) is added to catalyst P5 (10 mol%) and EtNMeLi (1.2 eq). A solution of 3-tert-butyl 3-bromoazetidine-l-carboxylate (1 eq) in THF (c = 0.25 M) is added to the mixture, which is then brought up to a total concentration of 0.16 M tert-butyl 3-bromoazetidine-l-carboxylate. The reaction mixture is stirred at 25 °C for 36 h (non-optimized time), and then a saturated aqueous solution of NH4Cl is added. After extraction with EtOAc, the combined organic phases are dried over MgSO4, filtered, and evaporated under reduced pressure.

[0628] EXAMPLE 33: Synthesis of the pinacolic ester of 3-(( tert-butyldimethylsilydoxypropylboronic acid)

[0629] [Chem. 150]

[0630] The reaction is carried out under an inert atmosphere in a glove box. Bis(pinacolato)dibore (2 eq) is added to catalyst P5 (10 mol%) and to EtNMeLi (1,2 (eq). A solution of (4-bromobutoxy)(terLbutyl)dimethylsilane (1 eq) in THF (c = 0.25 M) is added to the mixture, which is then brought to a total concentration of (4-bromobutoxy)(terLbutyl)dimethylsilane of 0.16 M. The reaction mixture is stirred at 25 °C for 36 h (not optimized time), and then a saturated aqueous solution of NH4Cl is added. After extraction with EtOAc, the combined organic phases are dried over MgSO4, filtered, and evaporated under reduced pressure.

[0631] EXAMPLE 34: Synthesis of the pinacolic ester of cyclopentylboronic acid

[0632] [Chem. 151]

[0633] The reaction is carried out under an inert atmosphere in a glove box. Bis(pinacolato)dibore (2 eq) is added to catalyst P5 (10 mol%) and EtNMeLi (1.2 eq). A solution of bromocyclopentane (1 eq) in THF (c = 0.25 M) is added to the mixture, which is then brought up to a total bromocyclopentane concentration of 0.16 M. The reaction mixture is stirred at 25 °C for 36 h (non-optimized time), and then a saturated aqueous solution of NH4Cl is added. After extraction with EtOAc, the combined organic phases are dried over MgSO4, filtered, and evaporated under reduced pressure.

[0634] EXAMPLE 35: Synthesis of the pinacolic ester of 1-hexylboronic acid

[0635] [Chem. 152]

[0636] The reaction is carried out under an inert atmosphere in a glove box. Bis(pinacolato)dibore (2 eq) is added to catalyst P5 (10 mol%) and EtNMeLi (1.2 eq). A solution of 1-bromohexane (1 eq) in THF (c = 0.25 M) is added to the mixture, which is then brought up to a total concentration of 0.16 M. The reaction mixture is stirred at 25 °C for 36 h (non-optimized time), and then a saturated aqueous solution of NH4Cl is added. After extraction with EtOAc, the combined organic phases are dried over MgSO4, filtered, and evaporated under reduced pressure.

[0637] EXAMPLE 36: Synthesis of the pinacolic ester of 2-(2.3-dihydro-1H-indenylboronic acid

[0638] [Chem. 153]

[0639] The reaction is carried out under an inert atmosphere in a glove box. Bis(pinacolato)dibore (2 eq) is added to catalyst P5 (10 mol%) and EtNMeLi (1.2 eq). A solution of 2-bromo-2,3-dihydro-1H-indene (1 eq) in THF (c = 0.25 M) is added to the mixture, which is then brought up to a total concentration of 0.16 M of 2-bromo-2,3-dihydro-1H-indene. The reaction mixture is stirred at 25 °C for 36 h (non-optimized time), and then a saturated aqueous solution of NH4Cl is added. After extraction with EtOAc, the combined organic phases are dried over MgSO4, filtered, and evaporated under reduced pressure.

Claims

1. Demands Use of at least one of the compounds with the following general formula (I): [Chem. 154] (I) in which: • A is chosen from: • a grouping -X in which X is chosen from - a chlorine atom - a bromine atom • a group [Chem. 155] in which: M is a coordinating solvent p is chosen from 1, 2, 3, 4 or a decimal number that can vary from a value greater than 0 but less than 4 a group [Chem. 156]

2. • B, C, D, and E, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atom(s), in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atom(s), or a linear or branched dialkylamino group of 2 to 20 carbon atoms • Ri, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group C F3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s) as catalysts for the Miyaura borylation reaction, in particular for the creation of C(sp3)-B bonds, in particular, using a diborated compound, in particular a diboronic acid ester. Use, according to claim 1, □ of at least one of the compounds with the following general formula: (there) in which: • X is chosen from - a chlorine atom - a bromine atom • B, C, D, and E, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 10 carbon atoms • Ri, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group C F3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms • G is chosen from - a hydrogen atom a linear or branched alkyl group of 1 to 5 carbon atom(s) Or □ of at least one of the compounds with the following general formula (Ib): [Chem. 158] (Ib) in which: X is chosen from a chlorine atom a bromine atom M is a coordinating solvent p is chosen from 1, 2, 3, 4 or a decimal number that can vary from a value greater than 0 but less than 4 B, C, D, and E, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms. Rb, R2, R3, R4, R5, R6, R7, Rs, R9, and Rio, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms. G is chosen from a hydrogen atom a linear or branched alkyl group of 1 to 5 carbon atom(s), Or □ of at least one of the compounds with the following general formula: [Chem. 159] (THE) in which: B, C, D, and E, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, partly

3. a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms • Rb, R2, R3, R4, R5, R6, R7, Rs, R9 and Rio, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group C F3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s) as catalysts for the Miyaura borylation reaction, in particular for the creation of C(sp3)-B bonds. Use, according to claim 1 or 2, of at least one of the compounds, • of the following general formula: (there) in which: X is chosen from a chlorine atom a bromine atom B, C, D and E are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atom(s), in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxy group of 1 to 10 carbon atom(s) or a linear or branched dialkylamino group of 2 to 20 carbon atoms, at least one of the groups B, C, D or E being different from the others. Rb, R2, R3, R4, R5, R6, R7, Rs, R9 and Rio are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylmino group of 2 to 20 carbon atoms, provided that: Ri must be different from R5 and / or R2 must be different from R4 R6 is different from Rio and / or R7 is different from R9 G is chosen from a hydrogen atom a linear or branched alkyl group of 1 to 5 carbon atom(s) or the following general formula: (there) in which: • X is chosen from - a chlorine atom - a bromine atom • B, C, D and E are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxy group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms, at least one of the groups B, C, D, or E being different from the others • Ri, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylmino group of 2 to 20 carbon atoms, provided that: • Ri is different from R5 and / or R2 is different from R4 • R6 is identical to Rio and R7 is identical to R9 Or • R6 must be different from R10 and / or R7 must be different from R9 And • Ri is identical to R5 and R2 is identical to R4 • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s) • or the following general formula: [Chem. 162] (there) in which: • X is chosen from - a chlorine atom - a bromine atom • B, C, D and E are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atom(s), in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxy group of 1 to 10 carbon atom(s), or a linear or branched dialkylamino group of 2 with 20 carbon atoms, at least one of the groups B, C, D or E being different from the others Rb, R2, R3, R4, R5, R6, R7, Rs, R9 and Rio are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylmino group of 2 to 20 carbon atoms, provided that: Ri is identical to R5 R2 is identical to R4 R6 is identical to R10 R7 is identical to R9 G is chosen from a hydrogen atom a linear or branched alkyl group of 1 to 5 carbon atom(s) or the following general formula: [Chem. 163] (there) in which: a chlorine atom a bromine atom B, C, D and E are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms, provided that B is identical to E and D is identical to C Ri, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylmino group of 2 to 20 carbon atoms, provided that: Ri must be different from R5 and / or R2 must be different from R4 R6 must be different from R10 and / or R7 must be different from R9 G is chosen from a hydrogen atom a linear or branched alkyl group of 1 to 5 carbon atom(s) or the following general formula: in which: • X is chosen from - a chlorine atom - a bromine atom • B, C, D and E are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxy group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms, provided that B is identical to E and D is identical to C • Rb, R2, R3, R4, R5, R6, R7, Rs, R9 and Rio are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylmino group of 2 to 20 carbon atoms, provided that: - Ri is different from R5 and / or R2 is different from R4 - R6 is identical to Rio and R7 is identical to R9 Or - R6 must be different from R10 and / or R7 must be different from R9 And - Ri is identical to R5 and R2 is identical to R4 • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s) • or the following general formula: [Chem. 165] (there) in which: • X is chosen from - a chlorine atom - a bromine atom • B, C, D and E are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms bone or a linear or branched dialkylamino group of 2 to 20 carbon atoms, provided that B is identical to E and D is identical to C • Rb, R2, R3, R4, R5, R6, R7, Rs, R9 and Rio are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylmino group of 2 to 20 carbon atoms, provided that: - Ri is identical to R5 - R2 is identical to R4 - R6 is identical to R10 - R7 is identical to R9 • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s) Or • of the following general formula (Ib): [Chem. 166] in which: X is chosen from a chlorine atom a bromine atom M is a coordinating solvent p is chosen from 1, 2, 3, 4 or a decimal number which may vary from a value greater than 0 but less than 4. B, C, D and E are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atom(s), in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxy group of 1 to 10 carbon atom(s) or a linear or branched dialkylamino group of 2 to 20 carbon atoms, at least one of the groups B, C, D or E being different from the others. Rb, R2, R3, R4, R5, R6, R7, Rs, R9 and Rio are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, an alkyl group a linear or branched group of 1 to 10 carbon atom(s), in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atom(s) or a linear or branched dialkylmino group of 2 to 20 carbon atoms, provided that: Ri must be different from R5 and / or R2 must be different from R4 R6 must be different from R10 and / or R7 must be different from R9 G is chosen from a hydrogen atom a linear or branched alkyl group of 1 to 5 carbon atom(s) or the following general formula (Ib): [Chem. 167] (Ib) in which: - a chlorine atom - a bromine atom • M is a coordinating solvent • p is chosen from 1, 2, 3, 4 or a decimal number that can vary from a value greater than 0 but less than 4 • B, C, D, and E are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxy group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms, at least one of the groups B, C, D, or E being different from the others • Ri, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylmino group of 2 to 20 carbon atoms, provided that: • Ri is different from R5 and / or R2 is different from R4 And • R6 is identical to Rio and R7 is identical to R9 Or • R6 must be different from R10 and / or R7 must be different from R9 And • Ri is identical to R5 and R2 is identical to R4 • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s) • or the following general formula (Ib): [Chem. 168] (Ib) in which: • X is chosen from - a chlorine atom - a bromine atom • M is a coordinating solvent • p is chosen from 1, 2, 3, 4 or a decimal number that can vary from a value greater than 0 but less than 4 • B, C, D, and E are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxy group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms, at least one of the groups B, C, D, or E being different from the others • Rb, R2, R3, R4, R5, R6, R7, Rs, R9 and Rio are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylmino group of 2 to 20 carbon atoms, provided that: - Ri is identical to R5 - R2 is identical to R4 - R6 is identical to R10 - R7 is identical to R9 • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s) • or the following general formula (Ib): [Chem. 169] (Ib) in which: • X is chosen from - a chlorine atom - a bromine atom • M is a coordinating solvent • p is chosen from 1, 2, 3, 4 or a decimal number that can vary from a value greater than 0 but less than 4 • B, C, D, and E are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxy group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms, provided that B is identical to E and D is identical to C • Ri, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylmino group of 2 to 20 carbon atoms, provided that: - Ri is different from R5 and / or R2 is different from R4 And - R6 must be different from R10 and / or R7 must be different from R9 • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s) • or the following general formula (Ib): [Chem. 170] (Ib) in which: • X is chosen from - a chlorine atom - a bromine atom • M is a coordinating solvent • p is chosen from 1, 2, 3, 4 or a decimal number that can vary from a value greater than 0 but less than 4 • B, C, D and E are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms, provided that B is identical to E and D is identical to C • Rb, R2, R3, R4, R5, R6, R7, Rs, R9 and Rio are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, an alkyl group a linear or branched group of 1 to 10 carbon atom(s), in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atom(s) or a linear or branched dialkylmino group of 2 to 20 carbon atoms, provided that: - Ri is different from R5 and / or R2 is different from R4 And - R6 is identical to R10 and R7 is identical to R9 Or - R6 must be different from R10 and / or R7 must be different from R9 And - Ri is identical to R5 and R2 is identical to R4 • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s) or the following general formula (Ib): [Chem. 171] (Ib) in which: • X is chosen from - a chlorine atom - a bromine atom M is a coordinating solvent p is chosen from 1, 2, 3, 4 or a decimal number that can vary from a value greater than 0 but less than 4 B, C, D and E are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms, provided that B is identical to E and D is identical to C Ri, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, an alkyl group a linear or branched group of 1 to 10 carbon atom(s), in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atom(s) or a linear or branched dialkylmino group of 2 to 20 carbon atoms, provided that: Ri is identical to R5 R2 is identical to R4 R6 is identical to Rio R7 is identical to R9 G is chosen from a hydrogen atom a linear or branched alkyl group of 1 to 5 carbon atom(s) Or • of the following general formula: [Chem. 172] (THE) in which: B, C, D, and E are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxy group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms, at least one of the groups B, C, D, or E being different from the others Rb, R2, R3, R4, R5, R6, R7, Rs, R9 and Rio are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylmino group of 2 to 20 carbon atoms, provided that: Ri must be different from R5 and / or R2 must be different from R4 R6 is different from Rio and / or R7 is different from R9 G is chosen from a hydrogen atom a linear or branched alkyl group of 1 to 5 carbon atom(s) or the following general formula: (THE) in which: B, C, D, and E are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxy group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms, at least one of the groups B, C, D, or E being different from the others Ri, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylmino group of 2 to 20 carbon atoms, provided that: - Ri is different from R5 and / or R2 is different from R4 And - R6 is identical to Rio and R7 is identical to R9 Or - R6 must be different from R10 and / or R7 must be different from R9 And - Ri is identical to R5 and R2 is identical to R4 • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s) • or the following general formula: [Chem. 174] (THE) in which: B, C, D, and E are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a group a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms, at least one of the groups B, C, D or E being different from the others Rb, R2, R3, R4, R5, R6, R7, Rs, R9 and Rio are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylmino group of 2 to 20 carbon atoms, provided that: Ri is identical to R5 R2 is identical to R4 R6 is identical to R10 R7 is identical to R9 G is chosen from a hydrogen atom a linear or branched alkyl group of 1 to 5 carbon atom(s) or the following general formula: (THE) in which: • B, C, D, and E are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxy group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms, provided that B is identical to E and D is identical to C • Ri, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylmino group of 2 to 20 carbon atoms, provided that: Ri must be different from R5 and / or R2 must be different from R4 And - R6 is different from Rio and / or R7 is different from R9 • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s) • or the following general formula: [Chem. 176] (THE) in which: • B, C, D and E are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms, provided that B is identical to E and D is identical to C • Rb, R2, R3, R4, R5, R6, R7, Rs, R9 and Rio are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylmino group of 2 to 20 carbon atoms, provided that: - Ri is different from R5 and / or R2 is different from R4 And - R6 is identical to Rio and R7 is identical to R9 Or - R6 must be different from R10 and / or R7 must be different from R9 And - Ri is identical to R5 and R2 is identical to R4 • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s) • or the following general formula: [Chem. 177] (THE) in which: B, C, D and E are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms, provided that B is identical to E and D is identical to C Ri, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylmino group of 2 to 20 carbon atoms, provided that: Ri is identical to R5

4. - R2 is identical to R4 - R6 is identical to Rio - R7 is identical to R9 • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s) as catalysts for the Miyaura borylation reaction, in particular for the creation of C(sp3)-B bonds. Use, according to any one of claims 1 to 3, of at least one of the compounds • of the following general formula: [Chem. 178] (there) in which: • X is chosen from - a chlorine atom - a bromine atom • B, C, D and E are fluorine atoms • Ri, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group C F3, a linear or branched alkyl group of 1 to 10 atoms carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s) • or the following general formula (Ib): [Chem. 179] (Ib) in which: X is chosen from a chlorine atom a bromine atom M is a coordinating solvent p is chosen from 1, 2, 3, 4 or a decimal number that can vary from a value greater than 0 but less than 4 B, C, D and E are fluorine atoms Ri, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group C F3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms G is chosen from a hydrogen atom a linear or branched alkyl group of 1 to 5 carbon atom(s) or the following general formula: (THE) in which: • B, C, D and E are fluorine atoms • Rb R2, R3, R4, R5, R6, R7, Rs, R9 and Rio, identical or different nts are chosen from: a hydrogen atom, a halogen e, in particular F or Cl, a trifluoromethyl group C F3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms G is chosen from a hydrogen atom a linear or branched alkyl group of 1 to 5 carbon atom(s) as catalysts for the Miyaura borylation reaction, in particular for the creation of C(sp3)-B bonds.

5. Use of compounds of formula (I), according to any one of claims 1 to 4, selected from: [Chem. 181]

6. Use of at least one of the compounds of formulas (la), (Ib) or (le) according to any one of claims 1 to 5, for the synthesis of one of the compounds of the following formula:

7. Use of at least one of the compounds of formulas (la), (Ib) or (le) according to any one of claims 1 to 6 for carrying out a Miyaura borylation reaction from a compound (SI) [Chem. 183] I \ J ' \ B—B । R^ *11 z (IF) in which Rn is chosen from: in which q is equal to 0, 1 or 2 and Rn represents a linear or branched alkyl group of 1 to 10 carbon atom(s), in particular 1, - a group [Chem. 185] in which q and Rn have the meaning defined above, - a group [Chem. 186] $ with a compound of formula (S2): Z-Hal in which Z is chosen from: - a linear or branched alkyl group of 1 to 20 atom(s) ) of carbons or cyclic of 3 to 12 carbon atoms, notably an octyl, hexyl, cycloheptyl or cyclopentyl group - an 1-adamantyl group with the formula [Chem. 187] - a group: [Chem. 188] possibly substituted by one or two methyl groups, a group a group a group a group [Chem. 192] a group [Chem. 193] and Hal is chosen from among:

8. - a chlorine atom - a bromine atom - an iodine atom - a group of -OTs. Process for preparing a compound of formula (X): [Chem. 194] (X) in which Rn is chosen from: - a group [Chem. 195] in which q is equal to 0, 1 or 2 and Rn represents a linear or branched alkyl group of 1 to 10 carbon atom(s), in particular 1, - a group [Chem. 196] in which q and R[2] have the meaning defined above, - a group [Chem. 197] and in which Tb, T2 and T3 are, identical or different, chosen from: - a hydrogen atom, - a linear or branched alkyl group of 1 to 20 carbon atom(s) or a cyclic group of 3 to 12 carbon atoms, possibly substituted by one or more phenol groups or tert-butyldimethylsilyl ether group, - a linear ether group of 1 to 20 carbon atom(s), - a linear alkylamine group of 1 to 20 carbon atoms, possibly protected, in particular by a tert-butoxycarbonyl group or a carboxybenzyl group - a benzocyclopentane group, possibly Ti, T2 and T3 are linked together to form a polycycloalkane, in particular an adamantyl group, and possibly fused with a phenyl group, possibly two of Tb T2 and T3 are linked to form a cyclic ether group, possibly two of TB, T2 and T3, are linked in such a way as to form a cyclic amine. provided that Tb, T2 and T3 do not simultaneously represent a hydrogen atom, including a step of contacting a compound of Formula (XI): [Chem. 198] 11 (XI) with a compound of Formula (XII): [Chem. 199] in which Hal is chosen from among: a chlorine atom a bromine atom an iodine atom a group of -OTs, in the presence of a compound of formula (I): (I) in which: • A is chosen from: • a grouping -X in which X is chosen from - a chlorine atom - a bromine atom • a group [Chem.201] in which: - M is a coordinating solvent - p is chosen from 1, 2, 3, 4 or a decimal number that can vary from a value greater than 0 but less than 4 a group B, C, D, and E, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atom(s), in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atom(s), or a linear or branched dialkylamino group of 2 to 20 carbon atoms. Ri, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group C F3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms G is chosen from a hydrogen atom a linear or branched alkyl group of 1 to 5 carbon atom(s)

9. and a base. Method for preparing, according to claim 8, a compound of formula (X): [Chem.202] (X) in which Rn is chosen from: - a group [Chem.203] in which q is equal to 0, 1 or 2 and Rn represents a linear or branched alkyl group of 1 to 10 carbon atom(s), in particular 1, - a group [Chem.204] in which q and R[2] have the meaning defined above, - a group [Chem.205] and in which Tb, T2 and T3 are, identical or different, chosen from: - a hydrogen atom, - a linear or branched alkyl group of 1 to 20 carbon atom(s) or a cyclic group of 3 to 12 carbon atoms, possibly substituted by one or more phenol groups or tert-butyldimethylsilyl ether group, - a linear ether group of 1 to 20 carbon atom(s), - a linear alkylamine group of 1 to 20 carbon atoms, possibly protected, in particular by a tert-butoxycarbonyl group or a carboxybenzyl group - a benzocyclopentane group, possibly Ti, T2 and T3 are linked together to form a polycycloalkane, in particular an adamantyl group, and possibly fused with a phenyl group, possibly two of T2 and T3 are linked to form a cyclic ether group, possibly two of T2 and T3 are linked in such a way as to form a cyclic amine provided that Tb, T2 and T3 do not simultaneously represent a hydrogen atom, including a step of bringing into contact a compound of Formula (XI): [Chem.206] 'Ru Rii \ / \ / \ ; b—b ( / \ ' Rn Rll 7 (XI) with a compound of Formula (XII): [Chem.207] 7 Hal---C -----t \ " T 3 in which Hal is chosen from among: - a chlorine atom - a bromine atom - an iodine atom - a group of -OTs, □ in the presence of a compound of formula (la): [Chem.208] (there) in which X is chosen from a chlorine atom a bromine atom B, C, D, and E, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 10 carbon atoms. Ri, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group C F3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms G is chosen from a hydrogen atom a linear or branched alkyl group of 1 to 5 carbon atom(s) Or □ in the presence of a compound of formula (Ib): [Chem.209] (Ib) in which: X is chosen from - a chlorine atom - a bromine atom M is a coordinating solvent p is chosen from 1, 2, 3, 4 or a decimal number that can vary from a value greater than 0 but less than 4 B, C, D, and E, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group from 1 to 10 carbon atoms or a linear or branched dialkylam ino group of 2 to 20 carbon atoms Rb, R2, R3, R4, R5, R6, R7, Rs, R9, and Rio, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms. G is chosen from a hydrogen atom a linear or branched alkyl group of 1 to 5 carbon atom(s), Or □ in the presence of a compound of formula (the): [Chem.210] (THE) in which: B, C, D, and E, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl , a trifluoromethyl group CF3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms, or a linear or branched dialkylamino group of 2 to 20 carbon atoms • Ri, R2, R3, R4, R5, Re, R7, Rs, R9 and Rio, identical or different, are chosen from: a hydrogen atom, a halogen, in particular F or Cl, a trifluoromethyl group C F3, a linear or branched alkyl group of 1 to 10 carbon atoms, in particular a linear or branched alkyl group of 2 to 4 carbon atoms, a linear or branched alkoxyl group of 1 to 10 carbon atoms or a linear or branched dialkylamino group of 2 to 20 carbon atoms • G is chosen from - a hydrogen atom - a linear or branched alkyl group of 1 to 5 carbon atom(s), and a base.

10. A preparation method according to any one of claims 8 or 9, wherein said base is a lithium amide, in particular selected from LiNMeEt, LiNMe2, LiNEt2, LiN(iPr)2, LiNTMS2, LiNPhMe, in particular LiNMeEt or LiNMe2, in particular LiNMeEt. or □ in which said process is carried out in solution in a non-coordinating nonpolar solvent, in particular selected from benzene, hexane, toluene, cyclohexane or methylcyclohexane. Or □ in which said process is carried out in solution in a coordinating solvent selected from diethyl ether, dimethoxymethane, dimethoxyethane, diethoxymethane, tetrahydrofuran, tert-butylmethyl ether, tert-butylethyl ether, methyl tetrahydrofuran, tert-amylmethyl ether or 1,4-dioxane, in particular selected from tetrahydrofuran, tert-butylmethyl ether or tert-amylmethyl ether. Or □ in which said base is LiNMeEt and said process is carried out in solution in tert-amylmethyl ether. Or □ in which said base is LiNMeEt and said process is carried out in solution in tetrahydrofuran.

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