Method for the silylation of a carbon-iodine or carbon-bromine bond with a silylated diazene

Abstract

The present invention relates to a method for forming a silylated compound comprising the step of reacting an organic substrate comprising at least one C-X bond, X being Cl, Br or I, with a mixture comprising: (a) a silylated diazene of formula (I) and (b) a catalyst. The present invention also relates to a composition comprising: (a) a silylated diazene of formula (I) (b) a catalyst and (c) an organic substrate comprising at least one C-X bond.

Description

[0001] Method for the silylation of a carbon-iodine or carbon-bromine bond with a si ly la ted diazene

[0002] Field of the invention

[0003] The present invention relates to a new method for the silylation of a C-X bond, X being an atom of iodine or bromine in an organic substrate using a si lylated diazene derivative.

[0004] Background of the present invention

[0005] Organosilicon compounds, i.e. organic molecules containing at least one C-Si bond, are used in a wide range of applications including organic synthesis, materials science and medicinal chemistry, for a global market estimated at 105 M€ by 2026 with growth potential of around 5.5% per year (Silicon-Based Synthetic Reagents Market, Facts&Factors, 2020). However, this rate of growth and the emergence of new applications is not yet supported by the emergence of new synthetic processes for certain organosilicon compounds, such as those that cannot be obtained by the hydrosilylation of alkenes. In particular, there is a need for new synthetic processes capable of supporting changes in regulatory practices, reducing the environmental impact of existing processes and / or the need to investigate new chemical spaces.

[0006] (Hetero)arylsilanes cannot be made by hydrosilylation but can be prepared by cross-coupling various organic substrates with different silicon sources in the presence of catalytic or stoichiometric mediators. One first option consists in preparing the targeted organosilanes from the corresponding hydrocarbon substrates by silylation of C-H bonds (review: Chem. Rev. 2015, 115, 8946-8975). However, these methods are generally limited by poor siteselectivity unless the substrates are electronically or sterically biased or bear a directing group. For this reason, a critical view on the state-of-the-art shows that (hetero)aryl halides (typically bromides or iodides) are privileged organic substrates to form (hetero)arylsilanes because site-selectivity (i.e. precise introduction of the silyl group) is warranted by the halide atom. In this regard, a first strategy relies on the stoichiometric conversion of the (hetero)aryl bromide or iodide substrates into the corresponding organometallic (hetero)aryllithium or Grignard reagents followed by the addition of electrophilic chlorosilanes (J. Am. Chem. Soc. 1951 , 73, 3798-3803) or alkoxysilanes (Synthesis 2001 , 15, 2231 -2233). Although these century-old methods are well-established, they exhibit intrinsic limitations peculiar to the formation of highly reactive polar organometallic reagents. This generally includes a limited functional group tolerance towards electrophilic and acidic functions as well as practical limitations (cryogenic and anhydrous conditions are often mandatory). In addition, the use of a stoichiometric amount of metal (in the form of the metal itself such as in W02013100166A1 or an alkylmetal reagent such as nBuLi (W02012 / 109108) or iPrMgCl) ultimately leads to the generation of large amounts of metallic wastes that are hardly recyclable and disposal / handling of which becomes problematic on large scale.

[0007] Catalytic alternatives have also been proposed to prepare (hetero)arylsilanes from (hetero)aryl halides and disilanes (RsSi-SiRs, review: Chem. Eur. J. 2019, 25, 2407 -2422), hydrosilanes (R3S1H, review: Synthesis 2015, 47, 3645-3668) or silylboranes (RsSi-Bpin; pin = pinacol; review: Chem. Soc. Rev. 2021 , 50, 2010-2073) silicon sources. These methods usually display improved functional group tolerance and reduced waste generation compared to the stoichiometric aforementioned routes. However, they often require catalysts based on expensive noble metals (Pd, Ir, Pt or Rh) and / or specialized ligands that operate at high temperature. In addition, these methods remain limited by the formation of undesired byproducts and / or they lack generality, notably in terms of the diversity of silyl groups that can be installed (e.g. trialkylsilyl, alkoxysilyl...). For examples, the Rh-based method developed by Yamanoi and Nishihara (J. Org. Chem. 2008, 73 (17), 6671-6678) only works with aryl iodides (more expensive and less available than the corresponding bromide) and triethylsilane (EtsSiH), needs a long time of reaction (at least 4 days) and requires a specific suitable solvent / catalyst system to avoid the formation of products arising from the hydrodehalogenation of the substrates. Another system developed by Shimokawa and Yorimitsu (ACS Catal. 2021, 11 (16), 10095-10103) uses an elaborated palladium-based catalyst and silylsilanoates as silicon sources, preparation of which requires multistep synthesis involving reactive organometallic reagents.

[0008] Therefore, there is a strong need of a silylation method that would convert halogenated substrates into the corresponding organosilanes via an operationally-simple and cost- effective catalytic procedure not involving transition metals and operating under mild conditions (ambient conditions). Furthermore, there is a need for such a method that displays a broad scope regarding both the functional group tolerance and the nature of the silyl groups that can be efficiently transferred.

[0009] The inventors of the present invention have unexpectedly discovered and then developed a new method for the regioselective silylation of a C-X bond, with X being a bromine or an iodine atom, in an organic substrate by using silylated diazenes as silicon sources. The latter reagents are readily accessible in two steps from commercially available precursors and they enable the selective C-X bond silylation of a range of halogenated substrates, including (hetero)aryl bromides and iodides, alkynyl and vinyl iodides or bromides as well as cyclopropyl bromide or iodides. The developed silylation process operates under ambient conditions with transition metal-free and inexpensive catalysts, displays a large functional group tolerance and allows a range of structurally diverse silyl groups to be introduced.

[0010] Summary of the invention

[0011] The present invention relates to a method for forming a silylated compound comprising the step of reacting an organic substrate comprising at least one C-X bond, X being Br or I, with a mixture comprising:

[0012] (a) a silylated diazene of formula (I) wherein

[0013] R is selected in the group consisting of C1-C18 alkyl, C2-C18 alkenyl, C2-C18 alkynyl, aryl, heteroaryl, heterocycloalkyl, C3-C7 cycloalkyl, Si(C1-C12alkyl)3 and Si(O-C1-C12alkyl)3, said alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocycloalkyl and cycloalkyl being optionally substituted, and

[0014] R1, R2and R3are each independently selected in the group consisting of H, C1-C12 alkyl, C2- C12 alkenyl, C2-C12 alkynyl, C1-C12 alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, heterocycloalkyl, C3-C7 cycloalkyl, halogen and siloxy, said alkyl, alkenyl, alkynyl, alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, siloxy, heterocycloalkyl and cycloalkyl being optionally substituted, and

[0015] (b) a catalyst.

[0016] The present invention also relates to a composition comprising: (a) a silylated diazene of formula (I) wherein R is selected in the group consisting of C1-C18 alkyl, C2-C18 alkenyl, C2-C18 alkynyl, aryl, heteroaryl, heterocycloalkyl, C3-C7 cycloalkyl, Si(C1-C12alkyl)3 and Si(O-C1-C12alkyl)3, said alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocycloalkyl and cycloalkyl being optionally substituted, and

[0017] R1, R2and R3are each independently selected in the group consisting of H, C1-C12 alkyl, C2- C12 alkenyl, C2-C12 alkynyl, C1-C12 alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, heterocycloalkyl, C3-C7 cycloalkyl, halogen and siloxy, said alkyl, alkenyl, alkynyl, alcoxy, aryl, aryloxy heteroaryl, heteroaryloxy, siloxy, heterocycloalkyl and cycloalkyl being optionally substituted,

[0018] (b) a catalyst and

[0019] (c) an organic substrate comprising at least one C-X bond.

[0020] The present invention also relates to the use of a silylated diazene of formula (I) in a method for forming a silylated compound using an organic substrate comprising at least one C-X bond.

[0021] Detailed description

[0022] Definitions

[0023] As described herein, the present invention relates to methods and compositions for transforming an organic substrate into the corresponding silylated compound.

[0024] In other words, the methods and the compositions of the present invention enable to introduce a silyl group in an organic substrate. In particular, the present invention aims at silylating one or more C-X bond(s) in an organic substrate, meaning that the C-X bond(s) is (are) replaced by a C-Si bond(s), with X being Br or I.

[0025] The term “stereoisomers” used in this invention refers to configurational stereoisomers and more particularly to optical isomers. Optical isomers that are not mirror images of one another are thus designated as “diastereoisomers”, and optical isomers, which are non- superimposable mirror images are designated as “enantiomers”. An equimolar mixture of two enantiomers of a chiral compound is designated as a racemic mixture or racemate. The term "organic substrate enriched with an isotope" means that the organic substrate of interest has a proportion of said isotope that is significantly greater than the natural isotopic abundance.

[0026] The term “halogen”, as used in the present invention, refers to a fluorine, bromine, chlorine or iodine atom.

[0027] The term “ambient conditions”, as used in the present inventions, refers to room temperature (20-25 °C) and atmospheric pressure (ca. 760 mmHg or 1 atm).

[0028] The term “Cx-Cyaliphatic chain" designates a linear or branched hydrocarbon chain, completely saturated or containing one or more unsaturations, but not aromatic, comprising from x to y carbon atoms, notably from 1 to 12 carbon atoms, preferably from 1 to 6 carbon atoms. According to the present invention, the term "aliphatic chain" includes substituted or unsubstituted, linear or branched, alkyl, alkenyl or alkynyl groups.

[0029] The term “Cx-Cyalkyl”, as used in the present invention, refers to a straight or branched monovalent saturated hydrocarbon chain containing from x to y carbon atoms, notably 1 to 12, including, but not limited to, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, secbutyl, t-butyl, n-pentyl, n-hexyl, and the like.

[0030] The term “alkene”, as used in the present invention, refers to a straight or branched mono- or polyunsaturated hydrocarbon compound comprising at least one double bond. Preferably, the alkene according to the present invention contains from 2 to 18 carbon atoms, more preferably from 2 to 12 carbon atoms. Examples of alkene include, but are not limited to, ethylene, propene, butene, pentene, hexene and the like.

[0031] The term “Cx-Cyalkenyl”, as used in the present invention, refers to a straight or branched monovalent unsaturated hydrocarbon chain containing from x to y carbon atoms, notably from 2 to 12, and comprising at least one double bond including, but not limited to, ethenyl, propenyl, butenyl, pentenyl, hexenyl and the like.

[0032] The term “alkyne” as used in the present invention, refers to a straight or branched unsaturated hydrocarbon compound comprising at least one triple bond. Preferably, the alkyne according to the present invention contains from 2 to 18 carbon atoms, more preferably from 2 to 12 carbon atoms. Examples of alkyne include, but are not limited to, acetylene, propyne, butyne, pentyne, hexyne and the like.

[0033] The term “Cx-Cyalkynyl”, as used in the present invention, refers to a straight or branched monovalent unsaturated hydrocarbon chain containing from x to y carbon atoms, notably from 2 to 12, and comprising at least one triple bond including, but not limited to, ethynyl, propynyl, propynyl, butynyl, pentynyl, hexynyl and the like.

[0034] The term "Cx-Cyhaloalkyl" refers to a Cx-Cyalkyl chain as defined above wherein one or more hydrogen atoms are replaced by a halogen atom selected from fluorine, chlorine, bromine or iodine, preferably a fluorine atom. For example, it is a CF3 group.

[0035] The term “cycloalkyl” refers to a saturated hydrocarbon ring, preferably comprising from 3 to 7 carbons, including cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cycloheptyl.

[0036] The term “cycloalkenyl” refers to a hydrocarbon ring, non aromatic, comprising at least one unsaturation, preferably comprising from 3 to 7 carbons, including cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl and cycloheptenyl.

[0037] The term “heterocycloalkyl” as used in the present invention refers to a non-aromatic, saturated or unsaturated monocycle or polycycle (comprising fused, bridged or spiro rings) comprising preferably 5 to 10, notably 5 or 6, atoms in the ring(s), in which the atoms of the ring(s) consist of carbon atoms and one or more, advantageously 1 to 4, and more advantageously 1 or 2, heteroatoms, such as a nitrogen, oxygen or sulphur atom, the remainder being carbon atoms. In particular, it can be an unsaturated ring, such as an unsaturated 5 or 6-membered monocycle. Preferably it comprises 1 or 2 nitrogen(s), in particular one. A heterocycle can be notably piperidinyl, piperizinyl, pyrrolidinyl, pyrazolidinyl, imidazolidinyl, azepanyl, thiazolidinyl, isothiazolidinyl, oxazocanyl, thiazepanyl, benzimidazolonyl.

[0038] The term “arene”, as used in the present invention, refers to an aromatic hydrocarbon compound comprising one or more fused rings. Preferably, the arene according to the present invention comprises from 6 to 12 carbon atoms, more preferably from 6 to 10 carbon atoms. Examples of arene include, but are not limited to, benzene, naphthalene or anthracene. The term "aryl" refers to an aromatic hydrocarbon group preferably comprising from 6 to 12 carbon atoms and comprising one or more fused rings, such as, for example, a phenyl, a naphthyl or an anthracenyl group. Advantageously, it is a phenyl group.

[0039] The term “heteroarene” as used in the present invention, refers to an aromatic compound comprising one or several, notably one or two, fused hydrocarbon cycles in which one or several, notably one to four, advantageously one or two, carbon atoms each have been replaced with heteroatoms selected from a sulfur atom, an oxygen atom and a nitrogen atom, preferably selected from an oxygen atom and a nitrogen atom. Preferably, the heteroarene according to the present invention comprises from 5 to 12 carbon atoms, preferably from 5 to 10 carbon atoms. Examples of heteroarene include, but are not limited to, pyridine, pyrazine, pyridazine, pyrimidine, triazine, furan, benzofuran, benzopyrrole, benzothiophene, isobenzofuran, isobenzopyrrole, isobenzothiophene, pyrrole, indole, isoindole, indolizine, imidazole, pyrazole, triazole, pyrazine, thiophene, oxazole, thiazole, isoxazole, isothiazole, oxadiazole, quinoline, isoquinoline and thiadiazole.

[0040] The term “heteroaryl”, as used in the present invention, refers to an aromatic group comprising one or several, notably one or two, fused hydrocarbon cycles in which one or several, notably one to four, advantageously one or two, carbon atoms each have been replaced with heteroatoms selected from a sulfur atom, an oxygen atom and a nitrogen atom, preferably selected from an oxygen atom and a nitrogen atom. Preferably, the heteroaryl contains 5 to 12 carbon atoms, notably 5 to 10. It can be a furyl, thienyl, pyrrolyl, pyridyl, benzofuranyl, benzopyrrolyl, benzothipohenyl, isobenzofuranyl, isobenzopyrrolyl, isobenzothiophenyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, quinolyl, isoquinolyl, quinoxalyl or indyl.

[0041] The terms “Cx-Cy-alkoxy”, “aryloxy” or “heteroaryloxy” refer to those Cx-Cyalkyl, aryl or heteroaryl groups as defined above attached to the remainder of the molecule by an oxygen atom. Examples of alkoxy groups include, but are not limited to, methoxy and ethoxy. Examples of aryloxy groups include, but are not limited to, phenoxy and naphtoxy.

[0042] The term “siloxy” refers to a univalent silyl group attached to the remainder of the molecule by an oxygen atom. A “silyl group” refers to a group constituted by a silicon atom to which 3 substituents are attached, said substituents being typically, independently of one another, selected in the group formed by, but not limited to: H, C1-C12 alkyl, C1-C12 haloalkyl, aryl, alkoxy, aryloxy and siloxy. Examples of siloxy groups include, but are not limited to, trimethylsiloxy (-O-SiMes) and triethylsiloxy (-O-SiEts).

[0043] In the context of the present invention, “unsaturated” means that the hydrocarbon chain may contain one or more unsaturation(s), i.e. a double bond C=C or a triple bond C=C, advantageously one unsaturation.

[0044] In the context of the present invention, "optionally substituted" means that the group in question is optionally substituted with one or more substituents which may be selected in particular from halogen, C1-C12 alkyl, C1-C12 haloalkyl, C2-C12 alkenyl, C2-C12 alkynyl, aryl, - N3, -NRaRb, -CORC, -CO2Rd, -CONReRf, -OR8, -SRh, -OC(O)Rj, -NC(O)Rj, -OC(O)NRkRl, -S(O)Rm, - PRnR°, -BRpRq, -SiRrRsRl, -OSiRuRvRw, CN and NO2, wherein Rato Rmare, independently of one another, H, C1-C12 alkyl, C1-C12 haloalkyl, C2-C12 alkenyl, aryl or heteroaryl, and Rnto Rware, independently of one another, selected in the group formed by, but not limited to: H, Ci - C12 alkyl, C1-C12 haloalkyl, aryl, C1-C12 alkoxy and aryloxy. Preferably, Rato Rwis H or C1-C12 alkyl.

[0045] The term “transition metal” refers to a chemical class of metallic atom including: scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, rutherfordium, dubnium, seaborgium, bohrium, hassium, meitnerium, darmstadtium, roentgenium and copernicium.

[0046] The term “alkali metal” refers to another chemical class of metallic atoms including lithium, sodium, potassium, rubidium, cesium and francium.

[0047] The term “alkaline earth metal” refers to the second-row metals of the periodic table: beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and radium (Ra).

[0048] The term “salt” refers to a neutral chemical entity composed of an anion (negatively charged) and a cation (positively charged). Examples of salts include, but are not limited to, sodium tert-butoxide (tBuONa), sodium hydroxide (NaOH), lithium tert-butoxide (tBuOLi) or potassium tert-butoxide (tBuOK). The term “Electron-withdrawing group” (EWG) refers to an atom or a chemical group able to remove electron density to neighboring atoms from itself, usually by resonance or inductive effect. EWG include, but are not limited to, NO2, CN, halogen, in particular fluorine, C1-C6 haloalkyl, such as CF3, CBn or CCI3, haloformyl group such as COCI, COBr and COI, COR', C(O)OR" and CONR"'R'Vwith R', R", R'" and R'veach independently representing H, C1-C6 alkyl, C1-C6 haloalkyl or cycloalkyl, such as CHO, CO-C1-C6 alkyl, COOH, C(0)0-C1-C6 alkyl, CONH2, CONH-CI-C6alkyl or C(O)O-cycloalkyl.

[0049] The term “Electron-donating group” (EDG) (also called electron-releasing group) refers to an atom or a chemical group able to release electron density to neighboring atoms from itself, usually by resonance or inductive effect. EDG includes, but are not limited to, C1-C6 alkyl, ORm, NRnR°, OC(O)RPand NRqC(O)Rr, with Rm, Rn, R°, Rp, Rqand Rreach independently representing H or C1-C6 alkyl, such as OH, C1-C6 alkoxy group, NH2, NH-C1-C6alkyl, OC(O)- C1- C6alkyl or NHC(O)- C1-C6 alkyl.

[0050] In the context of the present invention, the notations « C(sp) », « C(sp2) » and « C(sp3) » refer to the hybridization of the atomic orbitals of the carbon atom, for example of the carbon atom in the C-X bond in question. The hybridization refers to the geometry of the atomic orbitals in which the valence electrons are distributed. When the carbon atom of the C-X bond is linked to a triple bond, i.e. EC-X, the carbon atom is said « sp ». When the carbon atom of the C-X bond is linked to a double bond, i.e. =C-X, the carbon atom is said « sp2». When the carbon atom is linked to a simple bond, i.e. -C(R)-X (R optionally being H), the carbon atom is said « sp3». The hybridization of the carbon atom affects the ease with which the silylation of the C-X bond may occur.

[0051] Unless stated otherwise, the term “equivalent(s)” refers to molar equivalent(s).

[0052] The method of the invention

[0053] According to the present invention, there is provided a method for silylating an organic substrate comprising at least one C-X bond, with X being Br or I, said method comprising the step of reacting said organic substrate with a mixture comprising:

[0054] (a) a silylated diazene of formula (I): wherein

[0055] R is selected in the group consisting of C1-C18 alkyl, C2-C18 alkenyl, C2-C18 alkynyl, aryl, heteroaryl, heterocycloalkyl, C3-C7 cycloalkyl, Si(C1-C12alkyl)3 and Si(0- C1-C12 alkyl)3, said alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocycloalkyl and cycloalkyl being optionally substituted, and

[0056] R1, R2and R3are each independently selected in the group consisting of H, C1-C12 alkyl, C2- C12 alkenyl, C2-C12 alkynyl, C1-C12 alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, heterocycloalkyl, C3-C7 cycloalkyl, halogen and siloxy, said alkyl, alkenyl, alkynyl, alkoxy, aryl, aryloxy heteroaryl, heteroaryloxy, siloxy, heterocycloalkyl and cycloalkyl being optionally substituted, and

[0057] (b) a catalyst.

[0058] One of the main advantages of the present invention lies in the possibility to use various chemical classes of organic substrates to be silylated. Indeed, the methods and compositions of the invention are not limited to a particular class of activated substrates such as activated aromatic compounds, terminal alkynes nor specific to one carbon-halogen bond such as carbon-iodine bond. In the present invention, the silylation of a C-X bond is notably possible whatever the carbon hybridization. Moreover, the present invention does not rely on a transition metal-based catalyst and is advantageously carried out under ambient conditions (room temperature, atmospheric pressure).

[0059] As compared to the silylation of a C-H bond using a silylated diazene as described in W02023 / 012494, the method of the present invention presents a better regioselectivity. The inventors have surprisingly discovered that the silylation occurs selectively on the C-X bond, no matter the other bonds present on the substrate, and even in presence of several silylatable C-H bonds. A “silylatable C-H bond” as employed herein refers to the C-H bond(s) within an organic substrate that could be silylated using said silylated. Another improvement lies in a better versatility with respect to functional groups on the organic substrate. While in the silylation method of a C-H bond of W02023 / 012494, the presence of some functional groups such as ester or nitrile prevents the silylation or decrease the yield, the silylation of a C-X bond of the present invention tolerates a broader array of functional groups. The silylation occurs on a C-X bond when X is I or Br. The silylation of the present invention does not occur on a C-F or C-Cl bonds. The silylation of the C-X bond according to the present invention operates faster when X is I than when X is Br. Consequently, when the organic substrate is substituted by both a Br atom and by a I atom, the silylation typically occurs selectively on the C-l bond, and the C-Br bond is not or only marginally modified.

[0060] The organic substrate comprising at least one C-X bond according to the present invention can be in the form of a stereoisomer or a mixture of stereoisomers, such as a mixture of enantiomers or diastereoisomers, notably a racemic mixture.

[0061] The organic substrate comprising at least one C-X bond may be enriched with one or more isotope, such as deuterium (2H), tritium (3H),13C,18F or15N.

[0062] Thus, according to some embodiments, the organic substrate comprising at least one C-X bond may be selected in the group consisting of optionally substituted arenes, optionally substituted heteroarenes, optionally substituted alkanes, optionally substituted alkenes and optionally substituted alkynes, in particular optionally substituted arenes and optionally substituted heteroarenes.

[0063] Preferably, the organic substrate comprises only one C-X bond to be silylated. Nevertheless, in other embodiments, the organic substrate may comprise several C-X bonds and the silylation then occurs on each of the C-X bond present on the substrate when a suitable amount of the silylated diazene is employed.

[0064] In some specific embodiments, the organic substrate to be silylated by the method of the invention responds to one of the following formulae: wherein

[0065] • X is Br or I,

[0066] • Y1is N or CR5, Y2is N or CR7and Y3is N or CR9,

[0067] • R4, R5, R6, R7, R8and R9are independently selected in the group consisting of H, halogen, aryl, cycloalkyl, heteroaryl, heterocycloalkyl, OH, CN, NO2, and a C1-C12 aliphatic chain wherein one or more, preferably 1 to 4, methylene unit(s) is eventually replaced by -O-, - C(O)-, -N-, NR’-, -S-, -S(O)-, -S(O)2-, -P-, -B- or -Si-, said aliphatic chain, cycloalkyl, aryl, heterocycloalkyl or heteroaryl being optionally substituted, or two or more of R4, R5, R6, R7, R8and R9, together with the atoms to which they are bonded, form an aryl, a heteroaryl, a cycloalkyl, a cycloalkenyl or a heterocycloalkyl, said aryl, heteroaryl, cycloalkyl, cycloalkenyl and heterocycloalkyl being optionally substituted, provided that at least one of R4, R5, R6, R7, R8and R9is X, . Z1is CR12R13, N-R”, 0 or S, . Z2is CR14or N, . Z3is CR15or N,

[0068] • R” is selected in the group consisting of H, aryl or a C1-C12 aliphatic chain wherein one or more, preferably 1 to 4, methylene unit(s) is eventually replaced by -O-, -C(O)-, -N-, NR’-, -S-, -S(O)- or-S(O)2-,

[0069] • R10, R11, R12and R13, are independently selected in the group consisting of H, halogen, aryl, cycloalkyl, heteroaryl, heterocycloalkyl, OH, CN, NO2, and a C1-C12 aliphatic chain wherein one or more, preferably 1 to 4, methylene unit(s) is eventually replaced by -O-, -C(O)-, -N- , NR’-, -S-, -S(O)-, -S(O)2-, -P-, -B- or -Si-, said aliphatic chain, cycloalkyl, aryl, heterocycloalkyl or heteroaryl being optionally substituted,

[0070] R14and R15are independently selected in the group consisting of H, aryl or a C1-C12 aliphatic chain wherein one or more, preferably 1 to 4, methylene unit(s) is eventually replaced by - O-, -C(O)-, -N-, NR’-, -S-, -S(O)- or-S(O)2-, or

[0071] R10and R11or R11and R15or R14and R15or R12and R14, together with the atoms to which they are bonded, form a fused aryl, heteroaryl, cycloalkyl, cycloalkenyl or heterocycloalkyl, said aryl, heteroaryl, cycloalkyl, cycloalkenyl and heterocycloalkyl being optionally substituted, provided that at least one of R10, R11, R12, R13, R14and R15is X,

[0072] • R’ is H, C1-C12 alkyl, aryl or heteroaryl, said alkyl, aryl or heteroaryl being optionally substituted,

[0073] • R16, R17and R18are independently selected in the group consisting of H, halogen, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, OH, CN, and a C1-C12 aliphatic chain wherein one or more, preferably 1 to 4, methylene unit(s) is eventually replaced by -O-, -C(O)-, -N-, NR’-, -S-, - S(O)-, -S(O)2-, -P-, -B- or -Si-, said aliphatic chain, cycloalkyl, aryl, heterocycloalkyl or heteroaryl being optionally substituted, or

[0074] R16and R17or R16and R18or R17and R18, together with the atoms to which they are bonded, form a fused cycloalkyl, cycloalkenyl or heterocycloalkyl, said cycloalkyl, cycloalkenyl and heterocycloalkyl being optionally substituted, provided that at least one of R16, R17and R18is X, • R19, R20, R21, are independently selected in the group consisting of H, halogen, cycloalkyl, aryl, heteroaryl, heterocycloalkyl and a C1-C12 aliphatic chain wherein one or more, preferably 1 to 4, methylene unit(s) is eventually replaced by -O-, -C(O)-, -N-, NR’-, -S-, - S(O)-, -S(O)2-, -P-, -B- or -Si-, said aliphatic chain, cycloalkyl, aryl, heterocycloalkyl or heteroaryl being optionally substituted, or

[0075] R19and R20or R20and R21, together with the atoms to which they are bonded, form a cycloalkyl, a cycloalkenyl or heterocycloalkyl, said cycloalkyl, cycloalkenyl and heterocycloalkyl being optionally substituted,

[0076] • R23is independently selected in the group consisting of H, aryl, heteroaryl and a C1-C12 aliphatic chain wherein one or more, preferably 1 to 4, methylene unit(s) is eventually replaced by -O-, -C(O)-, -N-, NR’-, -S-, -S(O)-, -S(O)2-, -P-, -B- or -Si-, said aliphatic chain, aryl or heteroaryl being optionally substituted.

[0077] According to the above definitions, the compound of formula (II), (III), (IV), (V) or (VI) comprises at least one C-X bond, with X being selected in the group consisting of I and Br.

[0078] The method of silylation of the invention is versatile and tolerates the presence of many functional groups, irrespective of their EWG or EDG nature.

[0079] Thus, in some embodiments, the compounds of formula (II) or (III) are substituted with electron-withdrawing group, including CN, F, Cl, CF3, C(O)O-CrC6alkyl, such as C(O)OfBu, or C(O)O-cycloalkyl, such as C(O)O-cyclopentyl, and / or with electron-donating group such as O-CrCealkyl, notably OMe, Ci<6 alkyl or N-(CrC6alkyl)2, such as NMe2.

[0080] In a preferred embodiment, the organic substrate responds to the formula (II): in which Y1, Y2, Y3, R4, R6and R8are as defined above.

[0081] In some embodiments, only one of Y1, Y2and Y3represents N. In preferred embodiments, Y1 is CR5, Y2is CR7and Y3is CR9.

[0082] Preferably, R4, R5, R6, R7, R8and R9are independently selected in the group consisting of H, halogen, aryl, heteroaryl, heterocycloalkyl, OH, CN, NO2 and a C1-C12 aliphatic chain wherein one or more, preferably 1 to 4, methylene unit(s) is eventually replaced by -O-, -C(O)-, -N- , NR’-, -S-, -S(O)-, -S(O)2-, -P-, -B- or -Si-, said aliphatic chain, aryl or heteroaryl being optionally substituted, provided that at least one, preferably one, of R4, R5, R6, R7, R8and R9is X, with X being selected in the group consisting of I and Br.

[0083] In a preferred specific embodiment, one of R4, R5, R6, R7, R8and R9is I or Br and one, two, three, four or five of the others is(are) independently selected in the group consisting of Cr Cealkyl F, Cl, CF3, O-CrCealkyl, notably OMe, NH(CrC6alkyl), notably NHMe, N(CrC6alkyl)2, notably NMe2, CN, an allyl group, an O-allyl group, an alkyne, such as trimethylsilylpropargyl, an aryl such as a phenyl, a heteroaryl such as pyridinyl, OC(O)N(CrC6alkyl)2, C(O)- heterocycloalkyl, C(O)O-heterocycloalkyl and C(O)O-CrC6alkyl, S(O)2-heterocycloalkyl.

[0084] In other embodiments, two of R4, R5, R6, R7, R8and R9, together with the atoms to which they are bonded, form an aryl, notably a phenyl, provided that at least one, preferably one, of R4, R5, R6, R7, R8and R9is X, with X being selected in the group consisting of I and Br.

[0085] In such embodiments, the compound of formula (II) is notably a naphtyl.

[0086] In particular, the organic substrate of formula (II) may advantageously correspond to the following compounds:

[0087] in which X is Br or I, notably Br and R is H or methyl.

[0088] According to another preferred embodiment, the organic substrate responds to the formula (HI): in which R10, R11, Z1, Z2and Z3are as defined above.

[0089] In some embodiments, R10, R11, R12and R13are independently selected in the group consisting of H, heteroaryl, OH, CN, NO2 and a C1-C12 aliphatic chain wherein one or more, preferably 1 to 4, methylene unit(s) is eventually replaced by -O-, -C(O)-, -N-, NR’-, -S-, -S(O)-, -P-, - B- or -Si-,

[0090] R’ being as defined above, and

[0091] R14and R15are independently selected in the group consisting of H or a C1-C6 alkyl, -provided that at least one, preferably one, of R10, R11, R12, R13, R14and R15is Br or I.

[0092] Z1is preferably 0, S or N-R”, with R” typically selected in the group consisting of C1-C12 alkyl, C1-C12 alkenyl, aryl, heteroaryl or -C(0)-CrC6 alkyl, said alkyl, alkenyl, aryl or heteroaryl being optionally substituted. In particular, R” is a C1-C6 alkyl, such as methyl, or aryl, such as phenyl, more preferably R” is a phenyl.

[0093] Z2and Z3are preferably N or CH.

[0094] According to these embodiments, Z1is preferably 0, S or N-R”, Z2and Z3are preferably N or CH, one of R10and R11is I or Br and the other is selected in the group consisting of H, heteroaryl, OH, CN, NO2 and a C1-C12 aliphatic chain wherein one or more, preferably 1 to 4, methylene unit(s) is eventually replaced by -0-, -C(0)-, -N-, NR’-, -S-, -S(0)-, -P-, -B- or -Si-, more preferably the other is H.

[0095] The organic substrate of formula (III) may thus advantageously correspond to the following compounds: in which X is Br or I, notably Br.

[0096] According to another embodiment, the organic substrate responds to the formula (IV): in which R16, R17and R18are as defined above.

[0097] Preferably one of R16, R17and R18is Br or I and the two others are independently selected in the group consisting of H and aryl, notably phenyl.

[0098] The organic substrate of formula (IV) may thus advantageously correspond to the following compounds: , in which X is Br or I, notably Br.

[0099] According to another embodiment, the organic substrate responds to the formula (V): in which R19, R20and R21are as defined above. R19, R20and R21may be independently selected in the group consisting of H, aryl, notably phenyl, and C1-C6 alkyl.

[0100] Preferably, R19and R20form, together with the atoms to which they are bonded, a cycloalkyl or heterocycloalkyl, said cycloalkyl and heterocycloalkyl being optionally substituted, and R21is H.

[0101] The organic substrate of formula (V) may thus advantageously correspond to the following compound: in which X is Br or I, notably Br.

[0102] According to another embodiment, the organic substrate responds to the formula (VI):

[0103] {VI;

[0104] In which R23 is preferably selected in the group consisting of aryl, heteroaryl and a C1-C12 aliphatic chain wherein one or two methylene unit(s) is eventually replaced by -O-, -C(O)-, -N-, NR’-, -S-, -S(O)-, -S(O)2- or -Si-.

[0105] The organic substrate of formula (VI) may thus advantageously correspond to the following compound: which X is Br or I, notably Br.

[0106] According to some other embodiments, the organic substrate to be silylated by the method of the invention is a polymer bearing a substituent X where X is Br or I, for example selected in the group consisting in polystyrene, polystyrene derivatives, polyethers or polysilanes. Preferably, the polymer comprises one or several aromatic or heteroaromatic ring(s), which bear the substituent X. The term “polystyrene derivatives” refers to homo- or copolymers derived from the parent polystyrene in which the phenyl ring of the styrenyl repeating unit is substituted, or attached to the main chain by a linker, such a C1-C12 aliphatic chain wherein one or more, preferably 1 to 4, methylene unit(s) is eventually replaced by -O-, -C(O)-, -N- , NR’-, -S-, -S(O)-, -S(O)2-, -P-, -B- or -Si-.

[0107] According to some other embodiments, the organic substrate to be silylated by the method of the invention is a ferrocene derivative such as : which X is Br or I, notably Br.

[0108] In some embodiments, in the silylated diazene of formula (I): the substituent R is preferably linked to the nitrogen atom via a quaternary carbon atom, i.e. a carbon atom that does not bear a hydrogen atom. R is preferably selected in the group consisting of C4-C12 alkyl and aryl. More preferably, R is C4-C12 alkyl notably a tert-butyl or an adamantyl, in particular a tert-butyl.

[0109] When R is an aryl, such as a phenyl, the halogenated organic substrate preferably bears an EWG group as defined above.

[0110] R1, R2and R3are preferably each independently selected in the group consisting of H, C1-C6 alkyl, C1-C6 alkoxy and aryl. In particular, R1, R2and R3are each independently H, a methyl, an ethyl, an isopropyl, a tert-butyl, a methoxy, an ethoxy, an isopropyloxy, a terbutyloxy or a phenyl group.

[0111] According to a particular embodiment, R1, R2and R3may be identical.

[0112] In particular, the silylated diazene of formula (I) may be advantageously chosen among the following compounds: The silylated diazenes of formula (I) are typically obtained by oxidation of the corresponding silylated hydrazines, according to methods well-known from the skilled person (see Neil et al., ACS Catal. 2021 , 11,13085-13090).

[0113] The silyl group introduced into the organic substrate corresponds to the group SiR1R2R3as defined above.

[0114] In some embodiments, the catalyst used in the present invention is an alkoxide, siloxide or hydroxide of an alkali metal or alkaline earth metal, or a salt of an ammonium, a phosphonium, an alkali metal, an alkaline earth metal or mixtures thereof, notably an alkali or alkali earth metal alkoxide, aryloxide or fluoride. Preferably, the catalyst is a lithium- salt, a sodium-salt, a potassium-salt, a cesium-salt or mixtures thereof, in particular a sodium salt or a lithium salt. For example, the catalyst is selected in the group consisting of tBuOLi, tBuOK, tBuONa, MeONa, NaOH, KOH, and mixtures thereof. More preferentially, the catalyst is tBuONa, MesSiONa or tBuOLi.

[0115] According to a preferred embodiment, the catalyst is a transition metal-free catalyst.

[0116] Indeed, the reaction operates well in the complete absence of transition metal-based complexes. Likewise, the method is also operable in the absence or substantially complete in the absence of other electromagnetic or thermal triggers needed for initiation or propagation reactions. That is, these embodiments do not need UV irradiation or electric or plasma discharge conditions to operate.

[0117] The mixture optionally comprises one or more additives. The additive refers to any component able to improve the selectivity and / or the kinetic of the silylation reaction. In particular, the additives may be compounds or ligands able to coordinate the alkali or alkaline earth metal ions of the catalyst so as to improve the selectivity and / or the kinetic of the reaction. According to preferred embodiments, the mixture involved in the reaction of the present invention may comprise additives selected in the group consisting of crown ethers such as 18-crown-6, 15-crown-5, 12-crown-4, cryptands, polyamino compounds such as N,N,N’,N’-tetramethylenediamine (TMEDA) and nitrogen heterocycles such as pyridine, bipyridine or phenantroline. The additive is typically in an amount from 1 equivalent to 3 equivalents relative to the catalyst.

[0118] The conditions sufficient to form the silylated compound according to the method of the present invention notably include the solvent, the reaction time, the atmosphere of the reaction medium, the temperature of the reaction medium and the quantity of each component involved in the reaction, each feature being set up so as to form the silylated compound. These features depend on the nature of the organic substrate to be silylated, the nature of the silylated diazene and the catalyst used in the reaction. The skilled person is able to set up each feature in order to obtain the optimal conditions to achieve the method of the present invention.

[0119] The reaction is typically carried out in a solvent selected among aprotic solvents such as hexane, tetrahydrofuran (THF), diethylether (EtzO) or dimethoxyethane (DME). In another embodiment, the reaction can optionally be carried in the absence of solvent when the substrate is a liquid under the temperature and pressure conditions of the reaction.

[0120] The reaction is preferably carried out at ambient temperature, i.e. between 18 °C and 40 °C, notably between 18 °C and 25 °C.

[0121] The reaction is preferably carried out under inert atmosphere such as nitrogen (N2) or argon (Ar) atmosphere but can be run under air without significant impact on the reaction yield.

[0122] The mixture is substantially free of a transition-metal compound, or where present, the transition metal may be considered as a spectator to the reaction. The term "substantially free of a transition-metal compound" is defined to reflect that the total level of transition metal within the composition, independently or in the presence of organic substrate, is less than about 5 ppm, as measured by ICP-MS.

[0123] According to preferred embodiments, the reaction is carried out until full conversion of the organic substrate is observed as can be inferred from the monitoring of the reaction by TLC (Thin Layer Chromatography), NMR spectroscopy or gas chromatography (GC). Typically, the reaction is carried out for a time of less than 24 hours, in particular less than 18h, in particular less than 6 hours, in particular less than 3 hours, in particular less than 2 hours. Preferably, the time reaction is comprised between 5 min and 2 hours, preferably between 30 min and 90 min. Indeed, one of the advantages of the method of the invention is that the maximum conversion rate is generally obtained in a short time, i.e. in less than 2 hours under ambient conditions.

[0124] The reaction of the present invention is thermodynamically favorable due to the liberation of dinitrogen which drives the reaction to the formation of the expected silylated compound. The diazene of formula (I) is typically used in the method of the invention in a stochiometric quantity or in excess relative to the halogenated organic substrate. In particular, the diazene of formula (I) is used in an amount from 1 equivalent to 6 equivalents relative to the organic substrate, preferably from 1 equivalent to 3 equivalents, more preferably from 1 equivalent to 2 equivalents. The amount of the diazene of formula (I) may be function of the number of the C-X bonds to be silylated on the organic substrate. According to some embodiments, the number of equivalents of the diazene of formula (I) will be equal to or in slight excess of the number of C-X bonds to be silylated. Typically, when there is one C-X bond to be silylated, the diazene of formula (I) is preferably used in an amount from 1 to 2 equivalents. When there are two C-X bonds to be silylated, the diazene of formula (I) is preferably used in an amount from 2 to 3.5, notably from 2 to 2.5 equivalents.

[0125] The catalyst is typically used in substoichiometric quantities. In other terms, the catalyst is typically used in an amount comprised from 1 mol% to 40 mol%, preferably from 5 mol% to 30 mol%, more preferably from 5 mol% to 15 mol%, in particular at 10 mol%, with respect to the amount of the organic substrate comprising at least one C-X bond.

[0126] The amount of catalyst used in the reaction may also be function of the number of C-X bonds to be silylated on the organic substrate. When there is more than one C-X bonds to be silylated, the amount of the catalyst therefore may be adapted accordingly by the skilled person in the art.

[0127] When the organic substrate to be silylated according to the method of the present invention comprises more than one C-X bond to be silylated, the silylation may thus occur for only one C-X bond, for a part of the C-X bonds or for the whole C-X bonds present on the substrate. In this respect, the number of C-X bonds that will be silylated according to the method of the present invention may depend on the amount of the diazene of formula (I).

[0128] The method of the present invention typically comprises the following steps:

[0129] (i) preparing a silylated diazene of formula (I) as defined above by oxidation of the corresponding hydrazine,

[0130] (ii) reacting an organic substrate comprising at least one C-X bond as defined above, with a mixture comprising said silylated diazene of formula (I) and a catalyst, under conditions appropriate to form the silylated compound. Advantageously, step (ii) is achieved in the presence of a solvent, notably an aprotic solvent.

[0131] Preferably, step (ii) comprises the following sub-steps:

[0132] (ii - 1 ) charging a reactor with a reaction medium comprising the organic substrate comprising at least one C-X bond, and a solvent,

[0133] (ii-2) adding to the reaction medium the catalyst,

[0134] (ii-3) adding to the reaction medium the diazene of formula (I),

[0135] (iii-4) recovering the silylated compound.

[0136] According to some embodiments, step (ii-2) may be carried out concomitantly with step (ii- 1 ) or with step (ii-3), or step (ii-2) may be carried out after step (ii-3).

[0137] According to a preferred embodiment, the reaction medium is stirred during the implementation of the method.

[0138] The recovering of the silylated compound may include a purification step. Such a purification step may be carried out by methods well known to the person skilled in the art, such as by recrystallisation, by distillation, by chromatography on a column of silica gel or by high performance liquid chromatography (HPLC).

[0139] The present invention also relates to a method for silylating an organic substrate comprising at least one C-X bond, X being Br or I, said method comprising the step of reacting said organic substrate with a mixture comprising:

[0140] (a) a silylated diazene of formula (I) as defined above,

[0141] (b) a catalyst.

[0142] Said method is notably carried out under conditions appropriate to form a silylated compound, as defined above.

[0143] The composition of the invention

[0144] According to the present invention, there is provided a composition for silylating an organic substrate comprising at least one C-X bond, X being Br or I, said composition comprising: (a) a silylated diazene of formula (I) wherein

[0145] R is selected in the group consisting of C1-C18 alkyl, C2-C18 alkenyl, C2-C18 alkynyl, heteroaryl, heterocycloalkyl, C3-C7 cycloalkyl, Si( C1-C12alkyl)3 and Si(O-C1-C12 alkyl)3, said alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocycloalkyl and cycloalkyl being optionally substituted, and

[0146] R1, R2and R3are each independently selected in the group consisting of H, C1-C12 alkyl, C2- C12 alkenyl, C2-C12 alkynyl, C1-C12 alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, heterocycloalkyl, C3-C7 cycloalkyl, halogen and siloxy, said alkyl, alkenyl, alkynyl, alcoxy, aryl, aryloxy heteroaryl, heteroaryloxy, siloxy, heterocycloalkyl and cycloalkyl being optionally substituted,

[0147] (b) a catalyst and

[0148] (c) an organic substrate comprising at least one C-X bond.

[0149] All the features described above for the method of silylation of the present invention, notably those regarding the definition of the organic substrate, the silylated diazene of formula (I) and the catalyst are also relevant for the composition for silylating said organic substrate according to the invention, provided that R in formula (I) is not an aryl.

[0150] The composition according to the invention may be implemented in the method of the invention for silylating an organic substrate comprising at least one C-X bond.

[0151] Preferably, the composition for silylating an organic substrate is substantially free of a transition-metal compound, or where present, the transition metal may be considered as a spectator to the reaction.

[0152] According to some embodiments, the composition comprises one or more additives as defined above. The composition also typically includes a solvent suitable for the implementation of the silylation of the organic substrate.

[0153] The following examples are provided to illustrate some of the concepts described within this disclosure. While each example is considered to provide specific individual embodiments of composition, methods of preparation of the compounds and methods for silylating an organic substrate, none of the examples should be considered to limit the scope of the present invention.

[0154] EXAMPLES

[0155] 1 . General information

[0156] Reactions were performed in flame-dried glassware using an MBraun glove box (O2 < 0.5 ppm, H2O < 0.5 ppm) or conventional Schlenk techniques under a static pressure of argon unless otherwise stated. Glassware for reactions was flame-dried under vacuum prior to use. Liquids and solutions were transferred with syringes. All stated temperatures refer to external temperatures.

[0157] Tetrahydrofuran (THF) was dried over sodium / benzophenone, thermally distilled, degassed with three freeze-pump-thaw cycles and stored in a glove box over thermally activated 4 A molecular sieves (MS). n-Pentane was obtained from Aldrich and degassed by argon bubbling (> 30 min) prior to use. Unless otherwise stated, standard solvents and reagents were obtained from Doug Discovery, Acros, Alfa Aesar, Sigma-Aldrich, Tokyo Chemical Industry (TCI), or BLD Pharmatech Ltd. and used as received. MesSiOK (Aldrich) as well as tBuOLi, tBuONa (Aldrich) and tBuOK (Aldrich) were sublimed under high vacuum prior to use. Diazenes 1a-e were prepared according to an already published protocol1.

[0158] Flash column chromatography was performed on Silica 60 M (40-63 pm, Macherey Nagel) silica gel. Technical grade solvents were distilled prior to use. TLC analyses were performed on Merck 60 F254 silica gel pre-coated aluminum-backed plates with a layer thickness of 200 pm. Product spots were visualized under UV light ( / \max = 254 nm) and / or by staining with a potassium permanganate or a phosphomolybdic acid solution.

[0159] 1H,13C,29Si and19F NMR spectra were recorded on Bruker AV300 and AV400 instruments. CDCI3 and CD2CI2 were purchased from Eurisotop and used as received. THF-d8 (Eurisotop or Sigma-Aldrich) was degassed with argon and stored over activated 4 A molecular sieves prior to use. Chemical shifts are reported in parts per million (ppm) and are referenced to the residual solvent signals as the internal standard (THF-d8: δ = 3.58 ppm and 1.72 ppm, CDCI3: 6 = 7.26 ppm, CD2CI2: δ = 5.32 ppm for1H NMR and CDCl3: δ = 77.16 ppm, CD2CI2 6 = 53.84 ppm for 13C NMR). Data are reported as follows: chemical shift, multiplicity (s = singlet, d = doublet, dd = doublet of doublets, dt = doublet of triplets, t = triplet, tt = triplet of triplets, q = quartet, hept = heptuplet, m = multiplet, b = broad), coupling constants (Hz) and integration.29Si and19F NMR spectra were calibrated according to the IUPAC recommendation using a unified chemical shift scale based on the proton resonance of Me4Si as primary reference. Melting points (M.p.) were determined with a Stuart Scientific SMP3 melting point apparatus and are not corrected.

[0160] High resolution mass spectrometry (HRMS) analyses were obtained using a S3 mass spectrometer MicroTOF from Bruker with an electron spray ion source (ESI) and a TOF detector at the Institut Parisien de Chimie Moleculaire (Sorbonne Universite). Compound names were generated by the computer program ChemDraw according to the guidelines specified by the International Union of Pure and Applied Chemistry (IUPAC).

[0161] Gas liquid chromatography (GLC) was performed on an Agilent Technologies 7820A gas chromatograph equipped with a HP-5 capillary column (30 m x 0.32 mm, 0.25 pm film thickness) by Agilent Technologies / CS-Chromatographie Service using the following sequence: H2 carrier gas, injection temperature 220 °C, detector temperature 300 °C, flow rate: 2.4 mL / min; temperature program: start temperature 35 °C during 10 min then heating rate of 10 °C / min, end temperature 200 °C for 10 min.

[0162] The following diazenes have been synthesized according to or by slight modification of a reported procedure (ACS Catal. 2021 , 11,13085-13090):

[0163] 2. Variation of the synthetic conditions

[0164] The method has been carried out and validated under various conditions including different solvents, time, amounts of catalyst, amounts of diazene and especially catalysts: T able 1: Optimization of the silylation of 1-bromo-4-methoxybenzene with N-tert_butyl-N - trimethylsilyldiazene. Conversion and yields were determined by calibrated GC using tetracosane as an internal standard. THP = tetrahydropyran.

[0165] 3. Variation of the silylated diazene The method has been carried out and validated with different silylated diazenes:

[0166] Table 2 : Silylation of 1 -bromo-4-methoxyphenyl with different silylated diazenes using tBuONa as catalyst, in THF, at room temperature. Conversions and yields were determined by1H NMR spectroscopy using 1 ,3,5-trimethoxybenzene as internal standard.alsolated yield after purification by flash column chromatography.

[0167] 4. Selectivity of the silylation of the C-X bond over C-H bonds a) C-H silylation of toluene

[0168] 3 eq. toluene 78 % b) Discovery of C-Br silylation of 4-bromotoluene

[0169] 3 eq.

[0170] 4-bromotoluene not observed 03. 45% c) Optimized C-Br silylation of 4-bromotoluene 4-bromotoluene a) Toluene is silylated according to the method described in W02023 / 012494 using a silylated diazene and tBuOK as catalyst. b) Using same catalyst and a similar diazene, the 4-bromo-toluene is used in the silylation reaction. The cleavage of the C-H bond is not observed and the silylation takes place only on the C-Br bond. c) Using the optimized conditions (tBuONa as catalyst, 2eq. of diazene), the silylation of the C-Br bond of 4-bromotoluene is achieved selectively with high yield (>90%) in a short time (20 min versus 4 h in b)). 5. Synthesis and characterization data of silylated products

[0171] 5. 1. General procedure

[0172] General procedure (GP): A 10-mL microwave vial equipped with a magnetic stirring bar was charged with sodium tert-butoxide (tBuONa, 10 to 30 mol%), THF (2 mL) and the corresponding substrate (0.5 mmol, prior to adding the solvent). To the resulting vigorously stirred mixture was then added dropwise a solution of the silylated tert-butyldiazene in THF (1.5 mL) at room temperature. When full conversion of the substrate was reached (usually < 20 min reaction time as judged by TLC or1H NMR analysis but the reactions were generally left stirring ca. 1 h), the reaction mixture was concentrated by rotary evaporation and the resulting crude residue was directly purified by column chromatography on silica gel.

[0173] 5.2. Characterization data

[0174] (4-methoxyphenyl)trimethylsilane mw: 180.32 g / mol

[0175] Prepared according to GP from the corresponding diazene a (158.3 mg, 1.0 mmol, 2.0 eq.), sodium tert-butoxide (4.8 mg, 0.05 mmol, 10 mol%) and 1 -bromo-4-methoxybenzene (93.5 mg, 0.50 mmol, 1.0 eq.). The reaction mixture was stirred for 1 h at room temperature. Purification by column chromatography on silica gel using petroleum ether / ethyl acetate (100:1 ) as eluent afforded the title compound 1a (82.7 mg, 0.46 mmol, 92 %) as a paleyellow oil.

[0176] Rz(PE / AcOEt 100:1 ) = 0.37.1H NMR (300 MHz, CDCl3): δ / ppm = 7.46 (d, J = 8.6 Hz, 2H), 6.92 (d, J = 8.5 Hz, 2H), 3.82 (s, 3H), 0.26 (s, 9H).13C{1H} NMR (75 MHz, CDCI3): δ / ppm = 160.4, 134.9, 131.5, 113.7, 55.2, -0.8.1H / 29Si HMQC NMR (300 / 60 MHz, CDCI3): δ / ppm = 0.25 / -4.7. The spectroscopic data match the literature report (J. Am. Chem. Soc. 2017, 139 (36), 12386-12389). triethyl(4-methoxyphenyl)silane 1b Ci3H22OSi mw: 222.40 g / mol

[0177] Prepared according to GP1 from the corresponding diazene XXX (200.4 mg, 1.0 mmol, 2.0 eq.), sodium tert-butoxide (9.6 mg, 0.1 mmol, 20 mol%) and 1 -bromo-4-methoxybenzene (93.5 mg, 0.50 mmol, 1.0 eq.). The reaction mixture was stirred for 15 h at room temperature. Purification by column chromatography on silica gel using petroleum ether / ethyl acetate (100:0— >100:1— >100:2) as eluent afforded the title compound 1b (86.8 mg, 0.39 mmol, 78%) as a yellow oil.

[0178] Rz(PE / AcOEt 100:2) = 0.55.1H NMR (300 MHz, CDCl3): δ / ppm = 7.42 (d, J = 8.6 Hz, 2H), 6.92 (d, J = 8.6 Hz, 2H), 3.82 (s, 3H), 1.00 - 0.92 (m, 9H), 0.82 - 0.72 (m, 6H).13C{1H} NMR (75 MHz, CDCI3): δ / ppm = 160.3, 135.7, 128.3, 113.6, 55.1 , 7.6, 3.7.1H / 29Si HMQC NMR (300 / 60 MHz, CDCI3): δ / ppm = 0.94 / 1.3. The spectroscopic data match the literature report (Chem. Sci. 2019, 10, 5338-5344). diisopropyl(4-methoxyphenyl)silane

[0179] 1c

[0180] Ci3H22OSi mw: 222.40 g / mol

[0181] Prepared according to GP from the corresponding diazene c (200.4 mg, 1.0 mmol, 2.0 eq.), sodium tert-butoxide (4.8 mg, 0.05 mmol, 10 mol%) and 1 -bromo-4-methoxybenzene (93.5 mg, 0.50 mmol, 1 .0 eq.). The reaction mixture was stirred for 20 min at room temperature. Purification by column chromatography on silica gel using petroleum ether / ethyl acetate (100:1 ) as eluent afforded the title compound 1c (91.7 mg, 0.41 mmol, 82%) as a pale yellow oil. Rz(PE / AcOEt 100:1 ) = 0.48.1H NMR (300 MHz, CDCl3): δ / ppm = 7.44 (d, J = 8.6 Hz, 2H), 6.91 (d, J = 8.5 Hz, 2H), 3.92 (t, J = 3.0 Hz, 1 H), 3.82 (s, 3H), 1.28 - 1.12 (m, 2H), 1.06 (d, J = 7.1 Hz, 7H), 0.99 (d, J = 7.1 Hz, 6H).13C{1H} NMR (75 MHz, CDCI3): δ / ppm = 160.7, 137.0, 125.0, 113.6, 55.1 , 18.8, 18.6, 11.0.1H / 29Si HMQC NMR (300 / 60 MHz, CDCI3): d / ppm = 0.99 / 5.2. The spectroscopic data match the literature report (J. Am. Chem. Soc. 2023, 145 (29), 16249-16260).

[0182] (4-methoxyphenyl)dimethyl(phenyl)silane mw: 242.39 g / mol

[0183] Prepared according to GP1 from the corresponding diazene XXX (220.4 mg, 1.0 mmol, 2.0 eq.), sodium tert-butoxide (9.6 mg, 0.1 mmol, 20 mol%) and 1 -bromo-4-methoxybenzene (93.5 mg, 0.50 mmol, 1.0 eq.). The reaction mixture was stirred for 20 min at room temperature. Purification by column chromatography on silica gel using petroleum ether / ethyl acetate (100:0— >100:1 ) as eluent afforded the title compound 1d (108.1 mg, 0.45 mmol, 89%) as a clear oil.

[0184] Rf (PE / AcOEt 100:1 ) = 0.19.1H NMR (300 MHz, CDCI3): δ / ppm = 7.57 - 7.51 (m, 2H), 7.48 (d, J = 7.9 Hz, 2H), 7.40 - 7.34 (m, 3H), 6.93 (d, J = 8.0 Hz, 2H), 3.83 (s, 3H), 0.56 (s, 6H).13C{1H} NMR (75 MHz, CDCI3): d / ppm = 160.7, 138.8, 135.8, 134.3, 129.4, 129.1 , 127.9, 113.8, 55.2, -2.1.1H / 29Si HMQC NMR (300 / 60 MHz, CDCI3): d / ppm = 0.56 / -8.4. The spectroscopic data match the literature report (Org. Lett. 2019, 21, 9330-9333). trimethyl(3,4,5-trimethoxyphenyl)silane

[0185] 2a

[0186] C12H20O3S1 mw: 240.37 g / mol Prepared according to GP from the corresponding diazene a (158.3 mg, 1.0 mmol, 2.0 eq.), sodium tert-butoxide (4.8 mg, 0.05 mmol, 10 mol%) and 5-bromo-1 ,2,3-trimethoxybenzene (123.5 mg, 0.50 mmol, 1.0 eq.). The reaction mixture was stirred for 2 h at room temperature. Purification by column chromatography on silica gel using petroleum ether / ethyl acetate (100:5) as eluent afforded the title compound 2a (115.1 mg, 0.48 mmol, 96%) as a yellow liquid.

[0187] Rz(PE / AcOEt 100:5) = 0.19.1H NMR (400 MHz, CDCl3): δ / ppm = 6.71 (s, 2H), 3.89 (s, 6H), 3.86 (s, 3H), 0.27 (s, 9H).13C{1H} NMR (101 MHz, CDCI3): δ / ppm = 153.0, 139.0, 135.6, 110.0, 60.8, 56.2, -1.0.1H / 29Si HMQC NMR (400 / 79 MHz, CDCI3): δ / ppm = 0.27. / -3.15. HRMS (APCI) m / z: [M+H]+Calcd for Ci2H2o03SiH 241.1254. Found 241.1253.

[0188] (2,6-dimethoxyphenyl)trimethylsilane mw: 210.11 g / mol

[0189] Prepared according to GP from the corresponding diazene a (158.3 mg, 1.0 mmol, 2.0 eq.), sodium tert-butoxide (9.6 mg, 0.10 mmol, 20 mol%) and 2-bromo-1 ,3-dimethoxybenzene (108.5 mg, 0.50 mmol, 1.0 eq.). The reaction mixture was stirred for 1 h at room temperature. Purification by filtration on a pad of silica gel using 250 mL of petroleum ether / ethyl acetate (100:5) as eluent afforded the title compound 3a in an inseparable mixture with the corresponding protodebrominated product (93.7 mg, 0.38 mmol, 78 % purity, corrected yield based on purity: 75 %) as a yellow oil.

[0190] 1H NMR (300 MHz, CDCI3): δ / ppm = 7.31 (t, J = 8.2 Hz, 1 H), 6.54 (d, J = 8.2 Hz, 2H), 3.79 (s, 6H), 0.35 (s, 9H).13C{1H} NMR (75 MHz, CDCI3): δ / ppm = 165.5, 131.4, 114.4, 103.7, 55.3, 1.5.1H / 29Si HMQC NMR (400 / 79 MHz, CDCI3): δ / ppm = 0.35 / -6.3. The spectroscopic data match the literature report (J. Am. Chem. Soc. 1993, 115 (24), 11516-11520). N,N-dimethyl-4-(trimethylsilyl)aniline

[0191] NMe20 SiMe34a Cn H'igNSi mw: 193.37 g / mol

[0192] Prepared according to GP from the corresponding diazene a (158.3 mg, 1.0 mmol, 2.0 eq.), sodium tert-butoxide (4.8 mg, 0.05 mmol, 10 mol%) and 4-bromo-N,N-dimethylaniline (100.0 mg, 0.50 mmol, 1.0 eq.). The reaction mixture was stirred for 1 h at room temperature. Purification by column chromatography on silica gel using petroleum ether / ethyl acetate (100:0— >100:1— >100:2) as eluent afforded the title compound 4a in an inseparable mixture with the starting material (85.7 mg, 0.41 mmol, 94 % purity, corrected yield based on purity: 83 %) as a clear oil.

[0193] Rz(PE / AcOEt 100:3) = 0.531H NMR (300 MHz, CDCl3): δ / ppm = 7.48 (d, J = 8.8 Hz, 2H), 6.82 (d, J = 8.9 Hz, 2H), 3.03 (s, 6H), 0.32 (s, 9H).13C{1H} NMR (75 MHz, CDCI3): δ / ppm = 151.1 , 134.5, 125.7, 112.1 , 40.4, -0.7.1H / 29Si HMQC NMR (300 / 60 MHz, CDCI3): δ / ppm = 0.33 / -5.3. The spectroscopic data match the literature report (Chem. Asian J. 2010, 5 (11 ), 2346- 2350).

[0194] N- methy 1-4- (tri methy Isi ly 1 )ani li ne 5a Ci0H17NSi mw: 179.34 g / mol

[0195] Prepared according to GP from the corresponding diazene a (316.6 mg, 2.0 mmol, 4.0 eq.), sodium tert-butoxide (14.4 mg, 0.15 mmol, 30 mol%) and 4-bromo-N-methylaniline (93.0 mg, 0.50 mmol, 1.0 eq.). The reaction mixture was stirred for 1 h at room temperature. Purification by column chromatography on silica gel using petroleum ether / ethyl acetate (100:2) as eluent afforded the title compound 5a (55.5 mg, 0.31 mmol, 62 %) as a yellow oil. Rz(PE / AcOEt 100:3) = 0.25.1H NMR (300 MHz, CDCl3): δ / ppm = 7.41 (d, J = 8.4 Hz, 2H), 6.67 (d, J = 8.4 Hz, 2H), 3.78 (s, 1 H), 2.88 (s, 3H), 0.29 (s, 9H).13C{1H} NMR (75 MHz, CDCI3): d / ppm = 150.0, 134.6, 126.8, 112.1 , 30.6, -0.7.1H / 29Si HMQC NMR (300 / 60 MHz, CDCI3): d / ppm = 0.28 / -5.3. HRMS (ESI) m / z: [M+H]+ Calcd for C10H17NS1H 180.1203. Found 180.1202.

[0196] (2-isopropylphenyl)trimethylsilane

[0197] 6a

[0198] Ci2H2oSi mw: 192.38 g / mol

[0199] Prepared according to GP from the corresponding diazene a (158.3 mg, 1.0 mmol, 2.0 eq.), sodium tert-butoxide (9.6 mg, 0.10 mmol, 20 mol%) and 1 -bromo-2-isopropylbenzene (99.5 mg, 0.50 mmol, 1.0 eq.). The reaction mixture was stirred for 1 h at room temperature. Purification by filtration on a pad of silica gel using 250 mL of petroleum ether / ethyl acetate (100:5) as eluent afforded the title compound 6a (89.4 mg, 0.46 mmol, 93 %) as a yellow oil.

[0200] 1H NMR (400 MHz, CDCI3): δ / ppm = 7.51 (dd, J = 7 A, 1 .5 Hz, 1 H), 7.40 (dtd, J = 15.5, 7.9, 1.5 Hz, 2H), 7.23 (td, J = 7.2, 1.6 Hz, 1 H), 3.21 (hept, J = 6.8 Hz, 1 H), 1.33 (d, J = 6.8 Hz, 6H), 0.40 (s, 9H).13C{1H} NMR (101 MHz, CDCI3): δ / ppm = 155.2, 137.3, 134.4, 129.7, 125.3, 125.3, 33.9, 24.8, 0.6.1H / 29Si HMQC NMR (400 / 79 MHz, CDCI3): δ / ppm = 0.40 / -5.1. The spectroscopic data match the literature report (ACS Catal. 2018, 8 (8), 7484-7488). trimethyl(4-((trimethylsilyl)ethynyl)phenyl)silane mw: 246.50 g / mol

[0201] Prepared according to GP from the corresponding diazene a (158.3 mg, 1.0 mmol, 2.0 eq.), sodium tert-butoxide (4.8 mg, 0.05 mmol, 10 mol%) and ((4- bromophenyl)ethynyl)trimethylsilane (126.6 mg, 0.50 mmol, 1.0 eq.). The reaction mixture was stirred for 1 h at room temperature. Purification by filtration on a pad of silica gel using petroleum ether / ethyl acetate (100:5, 250 mL) as eluent afforded the title compound 7a (114.1 mg, 0.46 mmol, 93 %) as a yellow oil.1H NMR (400 MHz, CDCI3): δ / ppm = 7.48 (s, 4H), 0.30 (s, 9H), 0.30 (s, 9H).13C{1H} NMR (101

[0202] MHz, CDCI3): δ / ppm = 141.4, 133.2, 131.2, 123.6, 105.5, 94.6, 0.2, -1.1.1H / 29Si HMQC NMR (400 / 79 MHz, CDCI3): δ / ppm = 0.30 / -17.8, 0.30 / -3.7. The spectroscopic data match the literature report (Angew. Chem. Int. Ed. 2022, 61 (24), e202203347). trimethyl(4-vinylphenyl)silane mw: 176.33 g / mol

[0203] Prepared according to GP from the corresponding diazene a (158.3 mg, 1.0 mmol, 2.0 eq.), sodium tert-butoxide (4.8 mg, 0.05 mmol, 10 mol%) and 1 -bromo-4-vinylbenzene (91.5 mg, 0.50 mmol, 1.0 eq.). The reaction mixture was stirred for 30 min at room temperature. Purification by filtration on a pad of silica gel using petroleum ether / ethyl acetate (100:1 , 250 mL) as eluent afforded the title compound 8a (81.0 mg, 0.46 mmol, 92 %) as a yellow oil.

[0204] 1H NMR (300 MHz, CDCI3): δ / ppm = 7.55 (d, J = 8.1 Hz, 2H), 7.45 (d, J = 8.0 Hz, 2H), 6.77 (dd, J = 17.6, 10.9 Hz, 1 H), 5.83 (dd, J = 17.6, 1.0 Hz, 1 H), 5.31 (dd, J = 10.9, 1.0 Hz, 1 H), 0.33 (s, 9H).13C{1H} NMR (75 MHz, CDCI3): δ / ppm = 140.3, 138.2, 137.1 , 133.7, 125.7, 114.2, -1.0.1H / 29Si HMQC NMR (300 / 60 MHz, CDCI3): δ / ppm = 0.33 / -4.1. The spectroscopic data match the literature report (Chem. Eur. J. 2023, 29 (3), e202202373). trimethyl(naphthalen-1-yl)silane

[0205] 9a

[0206] Ci3Hi6Si mw: 200.36 g / mol

[0207] Prepared according to GP from the corresponding diazene a (158.3 mg, 1.0 mmol, 2.0 eq.), sodium tert-butoxide (9.6 mg, 0.10 mmol, 20 mol%) and 1 -bromonaphthalene (103.5 mg, 0.50 mmol, 1.0 eq.). The reaction mixture was stirred for 1 h at room temperature. Purification by filtration on a pad of silica gel using petroleum ether (250 mL) as eluent afforded the title compound 9a in an inseparable mixture with the protodebrominated product (89.4 mg, 0.43 mmol, 94% purity, yield based on purity: 86 %) as a clear oil.

[0208] 1H NMR (400 MHz, CDCl3): δ / ppm = 8.23 (d, J = 7.9 Hz, 1 H), 7.99 - 7.91 (m, 2H), 7.82 (dd, J = 6.7, 1.3 Hz, 1 H), 7.66 - 7.50 (m, 3H), 0.60 (s, 9H).13C{1H} NMR (101 MHz, CDCI3): δ / ppm = 138.3, 137.1 , 133.6, 133.3, 129.9, 129.3, 128.3, 125.7, 125.4, 125.2, 0.4.1H / 29Si HMQC NMR (300 / 60 MHz, CDCI3): δ / ppm = 0.60 / -4.1. The spectroscopic data match the literature report (Chem. - Eur. J. 2012, 18 (10), 2931-2937). trimethyl(naphthalen-2-yl)silane

[0209] 10a

[0210] Ci 3H16Si mw: 200.36 g / mol

[0211] Prepared according to GP from the corresponding diazene a (158.3 mg, 1.0 mmol, 2.0 eq.), sodium tert-butoxide (4.8 mg, 0.05 mmol, 10 mol%) and 2-bromonaphthalene (103.5 mg,

[0212] 0.50 mmol, 1.0 eq.). The reaction mixture was stirred for 1 h at room temperature. Purification by column chromatography on silica gel using petroleum ether as eluent afforded the title compound 10a (88.6 mg, 0.44 mmol, 88 %) as a clear liquid.

[0213] Rf (PE) = 0.52.1H NMR (400 MHz, CDCI3): δ / ppm = 8.13 (s, 1 H), 7.99 - 7.88 (m, 3H), 7.72 (dd, J = 8.1 , 1.2 Hz, 1 H), 7.58 (dt, J = 6.2, 3.4 Hz, 2H), 0.48 (s, 9H).13C{1H} NMR (101 MHz, CDCI3): δ / ppm = 138.0, 133.9, 133.8, 133.1 , 129.9, 128.2, 127.9, 127.1 , 126.4, 126.0, -0.9.1H / 29Si HMQC NMR (400 / 79 MHz, CDCI3): δ / ppm = 0.48 / -3.7. The spectroscopic data match the literature report (J. Am. Chem. Soc. 2017, 139 (36), 12386-12389).

[0214] [1,1 '-biphenyl]-4-yltrimethylsilane

[0215] 11a

[0216] Ci 5H1 sSi mw: 226.39 g / mol

[0217] Prepared according to GP from the corresponding diazene a (158.3 mg, 1.0 mmol, 2.0 eq.), sodium tert-butoxide (4.8 mg, 0.05 mmol, 10 mol%) and 4-bromo-1 ,1'-biphenyl (116.6 mg, 0.50 mmol, 1.0 eq.). The reaction mixture was stirred for 1 h at room temperature. Purification by filtration on a pad of silica gel using petroleum ether / ethyl acetate (100:5, 250 mL) as eluent afforded the title compound 11a (113.0 mg, 0.50 mmol, 100 %) as a yellow solid.

[0218] 1H NMR (400 MHz, CDCl3): δ / ppm = 7.75 - 7.69 (m, 6H), 7.54 (t, J = 7.5 Hz, 2H), 7.47 - 7.43 (m, 1 H), 0.44 (s, 9H).13C{1H} NMR (101 MHz, CDCI3): δ / ppm = 141.8, 141.3, 139.3, 134.0,

[0219] 128.9, 127.5, 127.3, 126.7, -0.9.1H / 29Si HMQC NMR (400 / 79 MHz, CDCI3): δ / ppm = 0.44 / -

[0220] 3.9. The spectroscopic data match the literature report (Eur. J. Org. Chem. 2015, 2015 (9), 1920-1924).

[0221] (4-chlorophenyl)trimethylsilane

[0222] 12a

[0223] C9H13CISi mw: 184.74 g / mol

[0224] Prepared according to GP from the corresponding diazene a (158.3 mg, 1.0 mmol, 2.0 eq.), sodium tert-butoxide (4.8 mg, 0.05 mmol, 10 mol%) and 1 -bromo-4-chlorobenzene (95.7 mg, 0.50 mmol, 1.0 eq.). The reaction mixture was stirred for 30 min at room temperature. Purification by filtration on a pad of silica gel using petroleum ether / ethyl acetate (100:10, 250 mL)) as eluent afforded the title compound 12a (86.4 mg, 0.47 mmol, 94%) as a yellow oil.

[0225] 1H NMR (400 MHz, CDCI3): δ / ppm = 7.47 (dd, J = 8.4, 2.3 Hz, 2H), 7.35 (dd, J = 8.3, 2.1 Hz, 2H), 0.30 (s, 9H).13C{1H} NMR (101 MHz, CDCI3): δ / ppm = 138.9, 135.2, 134.8, 128.1 , -1.0.1H / 29Si HMQC NMR (400 / 79 MHz, CDCI3): δ / ppm = 0.31 / -3.5. The spectroscopic data match the literature report (J. Am. Chem. Soc. 2017, 139 (36), 12386-12389).

[0226] 2-(trimethylsilyl)phenyl diisopropylcarbamate mw: 293.18 g / mol Prepared according to GP from the corresponding diazene a (158.3 mg, 1.0 mmol, 2.0 eq.), sodium tert-butoxide (4.8 mg, 0.05 mmol, 10 mol%) and 2-bromophenyl diisopropylcarbamate (150.1 mg, 0.50 mmol, 1.0 eq.). The reaction mixture was stirred for 20 min at room temperature. Purification by filtration on a pad of silica gel using petroleum ether / ethyl acetate (100:10, 250 mL) as eluent afforded the title compound 15a (145.0 mg, 0.49 mmol, 99 %) as a white solid.

[0227] 1H NMR (300 MHz, CDCl3): δ / ppm = 7.49 (dd, J = 7.3, 1 .8 Hz, 1 H), 7.39 (td, J = 7.3, 1 .8 Hz, 1 H), 7.20 (td, J = 7.3, 1.1 Hz, 1 H), 7.04 (dd, J = 8.1 , 1.0 Hz, 1 H), 4.40 (hept, J = 6.8 Hz, 1 H), 3.76 (hept, J = 6.8 Hz, 1 H), 1.40 (d, J = 6.8 Hz, 6H), 1.33 (d, J = 6.8 Hz, 6H), 0.33 (s, 9H).13C{1H} NMR (75 MHz, CDCI3): δ / ppm = 156.4, 153.3, 134.9, 131.8, 130.4, 124.8, 122.5, 47.2, 46.0, 21.3, 20.6, -0.7.1H / 29Si HMQC NMR (300 / 60 MHz, CDCI3): δ / ppm = 0.33 / -5.1. The spectroscopic data match the literature report (Chem. Eur. J. 2022, 28 (37), e202201154).

[0228] 2-(trimethylsilyl)phenyl diethylcarbamate

[0229] 16a

[0230] C-,4H23NO2Si mw: 265.43 g / mol

[0231] Prepared according to GP from the corresponding diazene a (158.3 mg, 1.0 mmol, 2.0 eq.), sodium tert-butoxide (9.6 mg, 0.1 mmol, 20 mol%) and 2-bromophenyl diethylcarbamate (136.1 mg, 0.50 mmol, 1.0 eq.). The reaction mixture was stirred for 20 min at room temperature. Purification by column chromatography on silica gel using petroleum ether / ethyl acetate (100:5) as eluent afforded the title compound 16a in an inseparable mixture with the protodebrominated product (119.9 mg, 0.41 mmol, 89% purity, yield based on purity: 83 %) as a yellow oil.

[0232] Rf (PE / AcOEt 100:5) = 0.13.1H NMR (300 MHz, CDCI3): δ / ppm = 7.46 (dd, J = 7.3, 1.8 Hz, 1 H), 7.41 - 7.32 (m, 1 H), 7.18 (td, J = 7.3, 1.1 Hz, 1 H), 7.04 (dd, J = 8.1 , 1.1 Hz, 1 H), 3.49 (q, J = 7.1 Hz, 2H), 3.40 (q, J = 7.1 Hz, 2H), 1 .26 (t, J = 7.1 Hz, 4H), 1 .20 (t, J = 7.1 Hz, 4H), 0.29 (s, 9H).13C{1H} NMR (75 MHz, CDCI3): δ / ppm = 156.5, 154.6, 135.0, 131 .7, 130.5, 124.9, 122.4, 42.1 , 41.7, 14.3, 13.4, -0.7.1H / 29Si HMQC NMR (300 / 60 MHz, CDCI3): δ / ppm = 0.29 / - 4.9. The spectroscopic data match the literature report (ACS Catal. 2018, 8 (8), 7484-7488). 4-(trimethylsilyl)benzonitrile 17a C10H13NSi mw: 175.31 g / mol

[0233] Prepared according to GP from the corresponding diazene a (158.3 mg, 1.0 mmol, 2.0 eq.), sodium tert-butoxide (14.4 mg, 0.15 mmol, 30 mol%) and 4-bromobenzonitrile (91.0 mg, 0.50 mmol, 1.0 eq.). The reaction mixture was stirred for 1 h at room temperature. Purification by column chromatography on silica gel using petroleum ether / diethyl ether (100:0^100:1 ^100:2^100:5) as eluent afforded the title compound 17a (49.6 mg, 0.28 mmol, 57 %) as a yellow oil.

[0234] Rf (PE / Et2O 100:5) = 0.50.1H NMR (300 MHz, CDCI3): δ / ppm = 7.61 (s, 4H), 0.29 (s, 9H).13C{1H} NMR (75 MHz, CDCI3): δ / ppm = 147.5, 133.9, 131.1 , 119.2, 112.5, -1.4.1H / 29Si HMQC NMR (300 / 60 MHz, CDCI3): δ / ppm = 0.29 / -2.6. The spectroscopic data match the literature report (Org. Lett. 2022, 24 (51 ), 9403-9407).

[0235] 4-((4-(trimethylsilyl)phenyl)sulfonyl)morpholine mw: 299.46 g / mol

[0236] Prepared according to GP from the corresponding diazene a (158.3 mg, 1.0 mmol, 2.0 eq.), sodium tert-butoxide (14.4 mg, 0.15 mmol, 30 mol%) and 4-((4- bromophenyl)sulfonyl)morpholine (153.1 mg, 0.50 mmol, 1.0 eq.). The reaction mixture was stirred for 1 h at room temperature. Purification by column chromatography on silica gel using petroleum ether / diethyl ether (100:10— >100:20— >100:30— >2:1 — >1 :1 ) as eluent afforded the title compound 18a (109.8 mg, 0.37 mmol, 73 %) as a white solid. Rf (PE / Et2O 1 :1 ) = 0.52.1H NMR (300 MHz, CDCl3): δ / ppm = 7.72 - 7.63 (m, 4H), 3.71 (t, 4H), 2.98 (t, 4H), 0.29 (s, 9H).13C{1H} NMR (75 MHz, CDCI3): δ / ppm = 147.5, 135.2, 134.0, 126.8, 66.1 , 46.0, -1.3.1H / 29Si HMQC NMR (300 / 60 MHz, CDCI3): 6 / ppm = 0.29 / -2.8. The spectroscopic data match the literature report (Chem. Sci. 2021 , 12 (18), 6437-6441 ). morpholino(4-(trimethylsilyl)phenyl)methanone 19a C14H21 NO2Si mw: 263.41 g / mol

[0237] Prepared according to GP from the corresponding diazene a (158.3 mg, 1.0 mmol, 2.0 eq.), sodium tert-butoxide (14.4 mg, 0.15 mmol, 30 mol%) and (4- bromophenyl)(morpholino)methanone (135.1 mg, 0.50 mmol, 1.0 eq.). The reaction mixture was stirred for 1 h at room temperature. Purification by column chromatography on silica gel using petroleum ether / diethyl ether (100:10— >100:20— >100:30— >2:1 — >1 :1 ) as eluent afforded the title compound 19a (70.2 mg, 0.27 mmol, 53 %) as a pale yellow solid.

[0238] Rf (PE / Et2O 1 :1 ) = 0.28.1H NMR (400 MHz, CDCI3): δ / ppm = 7.54 (d, J = 7.5 Hz, 2H), 7.35 (d, J = 7.5 Hz, 2H), 3.58 (d, J = 107.8 Hz, 8H), 0.26 (s, 9H).13C{1H} NMR (101 MHz, CDCI3): 6 / ppm = 170.5, 143.0, 135.6, 133.5, 126.2, 67.0, -1.2.1H / 29Si HMQC NMR (400 / 79 MHz, CDCI3): δ / ppm = 0.27 / -3.5. HRMS (ESI) m / z: [M+H]+ Calcd for Ci4H2iNO2SiH 264.1414. Found 264.1405. tert-butyl 4-(trimethylsilyl)benzoate mw: 250.41 g / mol Prepared according to GP from the corresponding diazene a (158.3 mg, 1.0 mmol, 2.0 eq.), sodium tert-butoxide (14.4 mg, 0.15 mmol, 30 mol%) and tert-butyl 4-bromobenzoate (128.6 mg, 0.50 mmol, 1.0 eq.). The reaction mixture was stirred for 1 h at room temperature. Purification by column chromatography on silica gel using petroleum ether / ethyl acetate (100:0— >100:1 — >100:2) as eluent afforded the title compound 20a in an inseparable mixture with the protodebrominated product (113.2 mg, 0.40 mmol, 85% purity, yield based on purity: 80 %) as a yellow oil. fy (PE / AcOEt 100:2) = 0.44.1H NMR (300 MHz, CDCl3): δ / ppm = 7.96 (d, J = 8.3 Hz, 2H), 7.58 (d, J = 8.3 Hz, 2H), 1.60 (s, 9H), 0.29 (s, 9H).13C{1H} NMR (75 MHz, CDCI3): δ / ppm = 166.1 , 146.3, 133.3, 132.4, 128.5, 81.0, 28.3, -1.2.1H / 29Si HMQC NMR (300 / 60 MHz, CDCI3): δ / ppm = 0.29 / -3.6. The spectroscopic data match the literature report (J. Am. Chem. Soc. 2008, 130 (47), 15982-15989).

[0239] 1 -methyl-5-(trimethylsilyl)- 1 H-indole mw: 203.36 g / mol

[0240] Prepared according to GP from the corresponding diazene a (158.3 mg, 1.0 mmol, 2.0 eq.), sodium tert-butoxide (4.8 mg, 0.05 mmol, 10 mol%) and 5-bromo-1 -methyl-1 H-indole (105.0 mg, 0.50 mmol, 1.0 eq.). The reaction mixture was stirred for 30 min at room temperature. Purification by column chromatography on silica gel using petroleum ether as eluent afforded the title compound 21a (92.8 mg, 0.46 mmol, 91 %) as a yellow oil.

[0241] R / (PE) = 0.17.1H NMR (400 MHz, CDCI3): δ / ppm = 7.97 (s, 1 H), 7.52 (d, J = 8.2 Hz, 1 H), 7.45 (d, J = 8.2 Hz, 1 H), 7.12 (d, J = 3.2 Hz, 1 H), 6.62 (d, J = 3.2 Hz, 1 H), 3.85 (s, 3H), 0.46 (s, 9H).13C{1H} NMR (101 MHz, CDCI3): δ / ppm = 137.3, 129.3, 128.9, 128.6, 126.5, 126.3, 109.0, 101.1 , 32.8, -0.5.1H / 29Si HMQC NMR (400 / 79 MHz, CDCI3): d / ppm = 0.46 / -3.9. The spectroscopic data match the literature report (Org. Chem. Front. 2023, 10 (2), 524-530). (4-fluoro-3-methylphenyl)trimethylsilane mw: 182.31 g / mol

[0242] Prepared according to GP from the corresponding diazene a (158.3 mg, 1.0 mmol, 2.0 eq.), sodium tert-butoxide (4.8 mg, 0.05 mmol, 10 mol%) and 4-bromo-1 -fluoro-2-methylbenzene (94.5 mg, 0.50 mmol, 1.0 eq.). The reaction mixture was stirred for 30 min at room temperature. Purification by column chromatography on silica gel using petroleum ether as eluent afforded the title compound 22a (78.6 mg, 0.43 mmol, 86 %) as a yellow oil.

[0243] Rf (PE) = 0.85.1H NMR (300 MHz, CDCl3): δ / ppm = 7.39 - 7.30 (m, 2H), 7.03 (dd, J = 10.1 , 8.2 Hz, 1 H), 2.33 (d, J = 2.0 Hz, 3H), 0.30 (s, 9H).13C{1H} NMR (75 MHz, CDCI3): δ / ppm = 162.4 (d, J = 246.5 Hz), 136.8 (d, J = 4.9 Hz), 135.8 (d, J = 4.5 Hz), 132.7 (d, J = 7.4 Hz), 124.3 (d, J = 15.8 Hz), 114.7 (d, J = 20.6 Hz), 14.6 (d, J = 4.0 Hz), -0.9.1H / 29Si HMQC NMR (300 / 60 MHz, CDCI3): δ / ppm = 0.31 / -4.1.19F NMR{1H} (282 MHz, CDCI3): δ / ppm = -116.97. GC / MS (El, 70 eV): m / z = 182 (17%, M+), 167 (100%, M-Me), 105 (8%), 91 (6%), 77 (18%), 73 (5%, MesSr), 63 (6%). Note: HRMS could not be obtained for this compound as ionization using ESI or APCI techniques coupled with MeOH or MeCN elution did not occur.

[0244] (4-(methoxymethyl)phenyl)trimethylsilane

[0245] 23a

[0246] On H18OSi mw: 194.35 g / mol

[0247] Prepared according to GP from the corresponding diazene a (158.3 mg, 1.0 mmol, 2.0 eq.), sodium tert-butoxide (4.8 mg, 0.05 mmol, 10 mol%) and 1 -bromo-4- (methoxymethyl)benzene (100.5 mg, 0.50 mmol, 1.0 eq.). The reaction mixture was stirred for 1 h at room temperature. Purification by column chromatography on silica gel using petroleum ether / ethyl acetate (100:2^100:4) as eluent afforded the title compound 23a (82.3 mg, 0.42 mmol, 85 %) as a pale-yellow oil.

[0248] Rz(PE / AcOEt 100:2) = 0.19.1H NMR (300 MHz, CDCl3): δ / ppm = 7.56 (d, J = 7.8 Hz, 2H), 7.37 (d, J = 7.6 Hz, 2H), 4.50 (s, 2H), 3.43 (s, 3H), 0.32 (s, 9H).13C{1H} NMR (75 MHz, CDCI3): d / ppm = 139.9, 138.9, 133.5, 127.2, 74.8, 58.2, -1.0.1H / 29Si HMQC NMR (300 / 60 MHz, CDCI3): δ / ppm = 0.31 / -4.1. HRMS (APCI) m / z: [M+H]+Calcd for CnHwOSiH 195.1200. Found 195.1200.

[0249] (2-methoxy-5-methylphenyl)trimethylsilane

[0250] Prepared according to GP from the corresponding diazene a (158.3 mg, 1.0 mmol, 2.0 eq.), sodium tert-butoxide (4.8 mg, 0.05 mmol, 10 mol%) and 2-bromo-1 -methoxy-4- methylbenzene (100.5 mg, 0.50 mmol, 1.0 eq.). The reaction mixture was stirred for 1 h at room temperature. Purification by column chromatography on silica gel using petroleum ether / ethyl acetate (100:0— >100:1 ) as eluent afforded the title compound 24a (77.1 mg, 0.40 mmol, 79 %) as a clear liquid.

[0251] Rf (PE / AcOEt 100:2) = 0.73.1H NMR (400 MHz, CDCI3): δ / ppm = 7.22 (s, 1 H), 7.18 (dd, J = 8.2, 2.3 Hz, 1 H), 6.78 (d, J = 8.2 Hz, 1 H), 3.82 (s, 3H), 2.35 (s, 3H), 0.32 (s, 9H).13C{1H} NMR (101 MHz, CDCI3): δ / ppm = 162.6, 135.7, 131.1 , 129.4, 127.9, 109.7, 55.3, 20.7, -0.8.1H / 29Si HMQC NMR (400 / 79 MHz, CDCI3): δ / ppm = 0.32 / -5.3. HRMS (APCI) m / z: [M+H]+Calcd for CnHisOSiH 195.1200. Found 195.1198.

[0252] (4-(allyloxy)phenyl)trimethylsilane Prepared according to GP from the corresponding diazene a (158.3 mg, 1.0 mmol, 2.0 eq.), sodium tert-butoxide (4.8 mg, 0.05 mmol, 10 mol%) and 1 -(allyloxy)-4-bromobenzene (106.5 mg, 0.50 mmol, 1.0 eq.). The reaction mixture was stirred for 30 min at room temperature. Purification by filtration on a pad of silica gel using petroleum ether (250 mL) as eluent afforded the title compound 25a (99.2 mg, 0.48 mmol, 96 %) as a yellow oil.

[0253] 1H NMR (300 MHz, CDCl3): δ / ppm = 7.51 (d, J = 8.6 Hz, 2H), 6.99 (d, J = 8.5 Hz, 2H), 6.12 (ddt, J = 17.3, 10.5, 5.3 Hz, 1 H), 5.47 (ddt, J = 17.3, 1.6, 0.3 Hz, 1 H), 5.34 (ddt, J = 10.5, 1.5, 1.5 Hz, 1 H), 4.60 (ddd, J = 5.3, 1.5, 1.5 Hz, 2H), 0.32 (s, 9H).13C{1H} NMR (75 MHz, CDCI3): δ / ppm = 159.4, 134.8, 133.5, 131.6, 117.7, 114.4, 68.7, -0.8.1H / 29Si HMQC NMR (300 / 60 MHz, CDCI3): δ / ppm = 0.33 / -4.7. The spectroscopic data match the literature report (Chem. Asian J. 2010, 5 (11 ), 2346-2350).

[0254] 4-(3-chloropyridin-2-yl)-N-methyl-N-(4-(trimethylsilyl)phenyl)piperazine-1- carboxamide mw: 403.00 g / mol

[0255] Prepared according to GP from the corresponding diazene a (94.9 mg, 0.6 mmol, 2.0 eq.), sodium tert-butoxide (8.6 mg, 0.09 mmol, 30 mol%) and N-(4-bromophenyl)-4-(3- chloropyridin-2-yl)-N-methylpiperazine-1 -carboxamide (122.9 mg, 0.3 mmol, 1.0 eq.). The reaction mixture was stirred for 20 min at room temperature. Purification by column chromatography on silica gel using toluene / ethyl acetate (100:0— >98.5:1.5— >97:3— >93:7— >85:15— >70:30) as eluent afforded the title compound 26a (55.0 mg, 0.14 mmol, 45 %) as a pale-yellow oil.

[0256] R / (Toluene / AcOEt 1 :1 ) = 0.46.1H NMR (300 MHz, CDCI3): δ / ppm = 8.13 (dd, J = 4.8, 1.7 Hz, 1 H), 7.55 (dd, J = 7.7, 1.7 Hz, 1 H), 7.47 (d, J = 8.3 Hz, 1 H), 7.10 (d, J = 8.3 Hz, 1 H), 6.82 (dd, J = 7.7, 4.8 Hz, 1 H), 3.42 - 3.35 (m, 4H), 3.25 (s, 3H), 3.22 - 3.14 (m, 4H), 0.25 (s, 9H).13C{1H} NMR (75 MHz, CDCI3): d / ppm = 161.1 , 158.3, 147.2, 145.9, 138.9, 136.3, 134.7, 122.81 , 122.78, 118.3, 48.7, 45.7, 39.5, -0.9.1H / 29Si HMQC NMR (300 / 60 MHz, CDCI3): d / ppm = 0.25 / -4.1. HRMS (ESI) m / z: [M+H]+ Calcd for C20H27ClN4OSiH 403.1715. Found 403.1717. 2-methyl-6-(trimethylsilyl)pyridine

[0257] 27a

[0258] C9H15NSi mw: 165.31 g / mol

[0259] Prepared according to GP from the corresponding diazene a (158.3 mg, 1.0 mmol, 2.0 eq.), sodium tert-butoxide (14.4 mg, 0.15 mmol, 30 mol%) and 2-bromo-6-methylpyridine (86.0 mg, 0.50 mmol, 1.0 eq.). The reaction mixture was stirred for 1 h at room temperature. Purification by column chromatography on silica gel using petroleum ether / ethyl acetate (100:1 — >100:2— >100:3) as eluent afforded the title compound 27a (50.3. mg, 0.30 mmol, 61 %) as a yellow oil. Note: 27a is volatile and should be dried carefully under vacuum.

[0260] Rf (PE / AcOEt 90:10) = 0.39.1H NMR (400 MHz, CDCl3): δ / ppm = 7.45 (t, J = 7.6 Hz, 1 H), 7.30 (d, J = 7.5 Hz, 1 H), 7.03 (d, J = 7.7 Hz, 1 H), 2.58 (s, 3H), 0.31 (s, 9H).13C{1H} NMR (101 MHz, CDCI3): δ / ppm = 167.7, 158.5, 134.1 , 125.8, 122.4, 25.1 , -1.6.1H / 29Si HMQC NMR (400 / 79 MHz, CDCI3): 6 / ppm = 0.30. / -6.1. The spectroscopic data match the literature report (Chem. - Eur. J. 2016, 22 (9), 2930-2934).

[0261] 5-(trimethylsilyl)-2,2'-bipyridine mw: 228.37 g / mol

[0262] Prepared according to GP from the corresponding diazene a (158.3 mg, 1.0 mmol, 2.0 eq.), sodium tert-butoxide (14.4 mg, 0.15 mmol, 30 mol%) and 5-bromo-2,2'-bipyridine (117.5 mg, 0.50 mmol, 1.0 eq.). The reaction mixture was stirred for 1 h at room temperature. Purification by column chromatography on silica gel using petroleum ether / ethyl acetate (100:10^100:20) as eluent afforded the title compound 28a (70.4 mg, 0.31 mmol, 62 %) as a yellow oil.

[0263] Rf (PE / AcOEt 100:2) = 0.36.1H NMR (400 MHz, CDCI3): δ / ppm = 8.80 (dd, J = 1.9, 1.0 Hz, 1 H), 8.71 (ddd, J = 4.8, 1.8, 0.9 Hz, 1 H), 8.44 (dt, J = 7.9, 1.1 Hz, 1 H), 8.39 (dd, J = 7.8, 1.0 Hz, 1 H), 7.95 (dd, J = 7.8, 1.9 Hz, 1 H), 7.82 (td, J = 7.7, 1.8 Hz, 1 H), 7.34 - 7.27 (m, 1 H), 0.36 (s, 9H).13C{1H} NMR (101 MHz, CDCI3): δ / ppm = 156.4, 156.2, 153.4, 149.3, 142.2,

[0264] 136.9, 135.3, 123.8, 121.1 , 120.3, -1.2.1H / 29Si HMQC NMR (400 / 79 MHz, CDCI3): δ / ppm = 0.35 / -3.9. HRMS (ESI) m / z: [M+H]+ Calcd for Ci3H16N2SiH 229.1156. Found 229.1161. tert-butyl 4-(5-(trimethylsilyl)pyrimidin-2-yl)piperazine-1 -carboxylate mw: 336.51 g / mol

[0265] Prepared according to GP from the corresponding diazene a (158.3 mg, 1.0 mmol, 2.0 eq.), sodium tert-butoxide (14.4 mg, 0.15 mmol, 30 mol%) and tert-butyl 4-(5-bromopyrimidin-2- yl)piperazine-1 -carboxylate (171.6 mg, 0.50 mmol, 1.0 eq.). The reaction mixture was stirred for 4.5 h at room temperature. Purification by column chromatography on silica gel using petroleum ether / diethyl ether (100:0^100:10^100:20^100:30) as eluent afforded the title compound 29a (135.8 mg, 0.40 mmol, 81 %) as a white solid. fy (PE / Et2O 100:40) = 0.29.1H NMR (300 MHz, CDCI3): δ / ppm = 8.33 (s, 2H), 3.80 (t, 4H), 3.47 (t, 4H), 1.47 (s, 9H), 0.23 (s, 9H).13C{1H} NMR (75 MHz, CDCI3): δ / ppm = 162.5, 161.8, 155.0, 118.0, 80.1 , 43.5 (bs), 28.6, -1.1.1H / 29Si HMQC NMR (300 / 60 MHz, CDCI3): δ / ppm = 0.23 / -5.7. The spectroscopic data match the literature report (ACS Catal. 2021 , 11 (16), 10095-10103).

[0266] 1-phenyl-4-(trimethylsilyl)-1H-pyrazole

[0267] 30a

[0268] C12H16N2Si mw: 216.36 g / mol

[0269] Prepared according to GP from the corresponding diazene a (63.3 mg, 0.4 mmol, 2.0 eq.), sodium tert-butoxide (3.8 mg, 0.04 mmol, 20 mol%) and 4-bromo-1 -phenyl-1H-pyrazole (44.6 mg, 0.20 mmol, 1 .0 eq.). The reaction mixture was stirred for 20 min at room temperature. Purification by column chromatography on silica gel using petroleum ether / diethyl ether (100:0^97.5:2.5 -^95:5^90:10) as eluent afforded the title compound 30a (24.0 mg, 0.11 mmol, 55 %) as a clear oil. Rz(PE) = 0.11 .1H NMR (300 MHz, CDCl3): δ / ppm = 7.85 (d, J = 0.7 Hz, 1 H), 7.73 - 7.71 (m, 1 H), 7.71 - 7.68 (m, 2H), 7.51 - 7.39 (m, 2H), 7.28 (t, J = 7.4 Hz, 1 H), 0.29 (s, 9H).13C{1H} NMR (75 MHz, CDCI3): δ / ppm = 145.8, 140.2, 131.4, 129.5, 126.5, 119.5, 117.2, -0.2.1H / 29Si HMQC NMR (300 / 60 MHz, CDCI3): δ / ppm = 0.29 / -10.4. HRMS (APCI) m / z: [M+H]+Calcd for C12H16N2S1H 217.1156. Found 217.1155. trans-trimethyl(2-phenylcyclopropyl)silane mw: 190.36 g / mol

[0270] Prepared according to GP from the corresponding diazene a (158.3 mg, 1.0 mmol, 2.0 eq.), sodium tert-butoxide (14.4 mg, 0.15 mmol, 30 mol%) and trans-(2- bromocyclopropyl)benzene (98.5 mg, 0. mmol, 1.0 eq.). The reaction mixture was stirred for 40 min at room temperature. Purification by column chromatography on silica gel using petroleum ether as eluent afforded the title compound 31a in an inseparable mixture with the protodebrominated product (58.2 mg, 0.26 mmol, 77% purity, yield based on purity: 52 %) as a clear oil.

[0271] R / (PE) = 0.78.1H NMR (400 MHz, CDCI3): δ / ppm = 7.23 (td, J = 7.6, 2.0 Hz, 2H), 7.15 - 7.08 (m, 1 H), 7.08 - 7.03 (m, 2H), 1 .76 (ddd, J = 7.5, 6.3, 4.6 Hz, 1 H), 0.95 (dt, J = 10.3, 4.3 Hz, 1 H), 0.86 (td, J = 7.7, 4.0 Hz, 1 H), 0.09 - 0.02 (m, 1 H), 0.00 (s, 9H).13C{1H} NMR (101 MHz, CDCI3): d / ppm = 144.7, 128.4, 125.7, 125.4, 19.9, 13.2, 10.7, -2.3.1H / 29Si HMQC NMR (300 / 60 MHz, CDCI3): δ / ppm = 0.0 / 1.5. The spectroscopic data match the literature report (J. Or%. Chem. 2023, 88 (3), 1515-1521 ). triisopropyl((trimethylsilyl)ethynyl)silane mw: 254.56 g / mol

[0272] Prepared according to GP from the corresponding diazene a (158.3 mg, 1.0 mmol, 2.0 eq.), sodium tert-butoxide (9.6 mg, 0.10 mmol, 20 mol%) and (bromoethynyl)triisopropylsilane (130.6 mg, 0.5 mmol, 1.0 eq.). The reaction mixture was stirred for 20 min at room temperature. Purification by column chromatography on silica gel using petroleum ether as eluent afforded the title compound 32a (106.3 mg, 0.42 mmol, 84 %) as a clear oil.

[0273] R / (PE) = 0.85.1H NMR (300 MHz, CDCI3): δ / ppm = 1.10 - 1.03 (m, 21 H), 0.17 (s, 9H).13C{1H} NMR (75 MHz, CDCI3): δ / ppm = 116.4, 110.3, 18.7, 11.2, 0.2.1H / 29Si HMQC NMR (300 / 60 MHz, CDCI3): δ / ppm = 1.07 / -2.8 (Si(iPr)3), 0.17 / -19.4 (SiMes). The spectroscopic data match the literature report (ChemCatChem 2022, 14 (18), e202200794) poly(4-trimethylsilylstyrene)

[0274] Prepared according to GP from the corresponding diazene a (189.9 mg, 1.2 mmol, 2.0 eq.), sodium tert-butoxide (5.8 mg, 0.06 mmol, 10 mol%) and poly(4-bromostyrene) (109.8 mg, 0.6 mmol, 1.0 eq.). The reaction mixture was stirred for 20 min at room temperature. The crude mixture was diluted with DCM, washed with water and brine, dried over MgSCU, filtered and concentrated under reduced pressure to afford poly(4-trimethylsilylstyrene) (100 mg, 0.56 mmol, 94%) as an off-white solid.

[0275] SEC (vs. polystyrene standards in THF): Mn= 33 656 g.mol'1, Mw= 61 591 g.mol'1, Mw / Mn= 1.830.1H NMR (400 MHz, CDCl3): δ / ppm = 7.33 - 7.05 (br, m, 2H per (4-TMS)S repeat unit), 6.61 - 6.32 (br, m, 2H per (4-TMS)S repeat unit), 1.91 - 1.26 (br, m, 4H per (4-TMS)S repeat unit), 0.28 (bs, 9H per (4-TMS)S repeat unit).13C{1H} NMR (101 MHz, CDCI3): d / ppm = 146.2,137.1 , 133.1 , 127.2, 40.4, 29.8, 0.9.1H / 29Si HMQC NMR (300 / 60 MHz, CDCI3): δ / ppm = 0.28 / -4.7. trimethylsilylferrocene mw: 258.22 g / mol

[0276] Prepared according to GP from the corresponding diazene a (158.3 mg, 1.0 mmol, 2.0 eq.), sodium tert-butoxide (4.8 mg, 0.05 mmol, 10 mol%) and bromoferrocene (132.5 mg, 0.50 mmol, 1.0 eq.). The reaction mixture was stirred for 20 min at room temperature. Purification by filtration on a pad of silica gel using petroleum ether (250 mL) as eluent afforded trimethylsilylferrocene (117.1 mg, 0.45 mmol, 91 %) as a dark orange oil. Rf (PE) = 0.58.1H NMR (400 MHz, CDCl3): δ / ppm = 4.34 (t, J = 1.6 Hz, 2H), 4.14 (s, 5H), 4.10 (t, J = 1.6 Hz, 2H), 0.23 (s, 9H).13C{1H} NMR (101 MHz, CDCI3): δ / ppm = 73.0, 72.2, 70.8, 68.3, -0.1.1H / 29Si HMQC NMR (300 / 60 MHz, CDCI3): δ / ppm = 0.24 / -3.8. The spectroscopic data match the literature report (J. Am. Chem. Soc. 2008, 130 (47), 15982-15989)

Claims

CLAIMS1. A method for forming a silylated compound comprising the step of reacting an organic substrate comprising at least one C-X bond, X being Br or I, with a mixture comprising:(a) a silylated diazene of formula (I)whereinR is selected in the group consisting of C1-C18 alkyl, C2-C18 alkenyl, C2-C18 alkynyl, aryl, heteroaryl, heterocycloalkyl, C3-C7 cycloalkyl, Si(CrC6alkyl)3 and Si(0-CrC6 alkyl)3, said alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocycloalkyl and cycloalkyl being optionally substituted, andR1, R2and R3are each independently selected in the group consisting of H, C1-C12 alkyl, C2- C12 alkenyl, C2-C12 alkynyl, C1-C12 alkoxy, aryl, aryloxy, heteroaryl, heteroaryloxy, heterocycloalkyl, C3-C7 cycloalkyl, halogen and siloxy, said alkyl, alkenyl, alkynyl, alkoxy, aryl, aryloxy heteroaryl, heteroaryloxy, siloxy, heterocycloalkyl and cycloalkyl being optionally substituted, and(b) a catalyst.

2. The method of claim 1 , wherein in the diazene of formula (I), R is a C4-C12 alkyl, preferably a tert-butyl.

3. The method of claims 1 or 2, wherein in the diazene of formula (I), R1, R2and R3are each independently selected in the group consisting of H, C1-C6 alkyl and aryl.

4. The method of any one of claims 1 to 3, wherein the diazene of formula (I) is selected in the group consisting of the following compounds:

5. The method of any one of claims 1 to 4, wherein in the organic substrate, X is Br.

6. The method of any one of claims 1 to 5, wherein the organic substrate responds to one of the following formulae:wherein• X is Br or I,• Y1is N or CR5, Y2is N or CR7and Y3is N or CR9,• R4, R5, R6, R7, R8and R9are independently selected in the group consisting of H, halogen, aryl, cycloalkyl, heteroaryl, heterocycloalkyl, OH, CN, NO2, and a C1-C12 aliphatic chain wherein one or more, preferably 1 to 4, methylene unit(s) is eventually replaced by -O-, - C(O)-, -N-, NR’-, -S-, -S(O)-, -S(O)2-, -P-, -B- or -Si-, said aliphatic chain, cycloalkyl, aryl, heterocycloalkyl or heteroaryl being optionally substituted, or two or more of R4, R5, R6, R7, R8and R9, together with the atoms to which they are bonded, form an aryl, a heteroaryl, a cycloalkyl, a cycloalkenyl or a heterocycloalkyl, said aryl, heteroaryl, cycloalkyl, cycloalkenyl and heterocycloalkyl being optionally substituted, provided that at least one of R4, R5, R6, R7, R8and R9is X, . Z1is CR12R13, N-R”, 0 or S, . Z2is CR14or N, . Z3is CR15or N,• R” is selected in the group consisting of H, aryl or a C1-C12 aliphatic chain wherein one or more, preferably 1 to 4, methylene unit(s) is eventually replaced by -O-, -C(O)-, -N-, NR’-, -S-, -S(O)- or-S(O)2-,• R10, R11, R12and R13, are independently selected in the group consisting of H, halogen, aryl, cycloalkyl, heteroaryl, heterocycloalkyl, OH, CN, NO2, and a C1-C12 aliphatic chain wherein one or more, preferably 1 to 4, methylene unit(s) is eventually replaced by -O-, -C(O)-, -N- , NR’-, -S-, -S(O)-, -S(O)2-, -P-, -B- or -Si-, said aliphatic chain, cycloalkyl, aryl, heterocycloalkyl or heteroaryl being optionally substituted,R14and R15are independently selected in the group consisting of H, aryl or a C1-C12 aliphatic chain wherein one or more, preferably 1 to 4, methylene unit(s) is eventually replaced by - O-, -C(O)-, -N-, NR’-, -S-, -S(O)- or-S(O)2-, orR10and R11or R11and R15or R14and R15or R12and R14, together with the atoms to which they are bonded, form a fused aryl, heteroaryl, cycloalkyl, cycloalkenyl or heterocycloalkyl, said aryl, heteroaryl, cycloalkyl, cycloalkenyl and heterocycloalkyl being optionally substituted, provided that at least one of R10, R11, R12, R13, R14and R15is X,• R’ is H, C1-C12 alkyl, aryl or heteroaryl, said alkyl, aryl or heteroaryl being optionally substituted,• R16, R17and R18are independently selected in the group consisting of H, halogen, cycloalkyl, aryl, heteroaryl, heterocycloalkyl, OH, CN, and a Ci -C12 aliphatic chain wherein one or more, preferably 1 to 4, methylene unit(s) is eventually replaced by -O-, -C(O)-, -N-, NR’-, -S-, - S(O)-, -S(O)2-, -P-, -B- or -Si-, said aliphatic chain, cycloalkyl, aryl, heterocycloalkyl or heteroaryl being optionally substituted, orR16and R17or R16and R18or R17and R18, together with the atoms to which they are bonded, form a fused cycloalkyl, cycloalkenyl or heterocycloalkyl, said cycloalkyl, cycloalkenyl and heterocycloalkyl being optionally substituted, provided that at least one of R16, R17and R18is X,• R19, R20, R21, are independently selected in the group consisting of H, halogen, cycloalkyl, aryl, heteroaryl, heterocycloalkyl and a C1-C12 aliphatic chain wherein one or more, preferably 1 to 4, methylene unit(s) is eventually replaced by -O-, -C(O)-, -N-, NR’-, -S-, - S(O)-, -S(O)2-, -P-, -B- or -Si-, said aliphatic chain, cycloalkyl, aryl, heterocycloalkyl or heteroaryl being optionally substituted, orR19and R20or R20and R21, together with the atoms to which they are bonded, form a cycloalkyl, a cycloalkenyl or heterocycloalkyl, said cycloalkyl, cycloalkenyl and heterocycloalkyl being optionally substituted,• R23is independently selected in the group consisting of H, aryl, heteroaryl and a C1-C12 aliphatic chain wherein one or more, preferably 1 to 4, methylene unit(s) is eventually replaced by -O-, -C(O)-, -N-, NR’-, -S-, -S(O)-, -S(O)2-, -P-, -B- or -Si-, said aliphatic chain, aryl or heteroaryl being optionally substituted.

7. The method of any one of claims 1 to 6, wherein the catalyst is a hydroxide of an alkali metal or alkaline earth metal, or a salt of an ammonium, a phosphonium, an alkali metal, an alkaline earth metal or mixtures thereof, preferably selected in the group consisting of tBuOLi, tBuOK, tBuONa, MeONa, NaOH, KOH, and mixtures thereof.

8. The method according to any one of claims 1 to 7, characterized in that the mixture comprises one or more additives, preferably selected in the group consisting of crown ethers such as 18-crown-6, 15-crown-5, 12-crown-4, cryptands, polyamino compounds such asN,N,N’,N’-tetramethylenediamine (TMEDA) and nitrogen heterocycles such as pyridine, bipyridine or phenantroline.

9. The method according to any one of claims 1 to 8, characterized in that the mixture is substantially free of a transition-metal.

10. The method according to any one of claims 1 to 9, further comprising the steps of(i) preparing the silylated diazene of formula (I) as defined in any one of claims 1 to 4 by oxidation of the corresponding hydrazine,(ii) reacting the organic substrate as defined in any one of claims 1 , 5 and 6, with a mixture comprising said silylated diazene of formula (I) and the catalyst as defined in any one of claims 1 and 7.11 . The method according to claim 10, characterized in that step (ii) comprises the following sub-steps:(ii - 1 ) charging a reactor with a reaction medium comprising the organic substrate comprising at least one C-X bond, and a solvent,(ii-2) adding the catalyst to the reaction medium,(ii-3) adding the diazene of formula (I) to the reaction medium,(ii-4) recovering the silylated compound.

12. A composition comprising:(a) a silylated diazene of formula (I) as defined in any one of claims 1 to 4,(b) a catalyst, preferably as defined in claim 7, and(c) an organic substrate comprising at least one C-X bond, preferably as defined in claims 5 and 6.

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