Cyclisation of unsaturated aldehydes or ketones in the presence of light

Abstract

The present invention relates to a process of photoredox catalysed cyclisation of unsaturated aldehyde or ketone of the formula (I) to a cyclic unsaturated aldehyde or ketone of the formula (II) in the presence of - at least one cobalt complex (CC); - at least one photocatalyst (PC) being an organic photocatalyst, preferably a cyanoarene polyaromatic photocatalyst, or an iridium complex; - at least one secondary amine (SA) or an ammonium salt (ASSA) of the at least one secondary amine (SA) and an organic or inorganic acid; - light. It has been shown that by said process cyclic unsaturated aldehydes or ketones of the formula (II) can be obtained at high conversion in high yields and selectivity.

Description

[0001] CYCLISATION OF UNSATURATED ALDEHYDES OR KETONES IN THE PRESENCE OF LIGHT

[0002] Technical Field

[0003] The present invention relates to the field of cyclisation of unsaturated aldehydes or ketones.

[0004] Background of the invention

[0005] Cyclic unsaturated aldehydes and ketones are important intermediates in the field of flavours and fragrances.

[0006] Comito R. J. et al., J. Am. Chem. Soc. 2013, 135, 9358-9361 disclose a thermal cyclisation of unsaturated aldehydes to yield cyclic unsaturated aldehydes by treating the unsaturated aldehydes with base and a Fe(lll) trisphenanthroline complex and 20 mol% of an imidazolidinone. This method is disadvantageous in that stoechiometric amounts of oxidants (Fe(lll) trisphenanthroline complex).

[0007] Capacci A. G. et al., Nature Chemistry 2017, 9, 1073-1077 discloses a direct, enantioselective alpha-alkylation of aldehydes using simple olefins. It furthermore, discloses an intramolecular alpha-alkylation of unsaturated aldehydes in the presence of chiral imidazolidinones or prolinols, in combination with a thiophenol and iridium photoredox catalyst and visible light.

[0008] This, however, does not lead to the desired cyclic unsaturated aldehydes but to cyclic saturated aldehydes.

[0009] Therefore, a method of synthesis of cyclic aldehydes and ketones which uses catalytical amounts of a catalyst would be highly appreciated.

[0010] Summary of the invention

[0011] Therefore, the problem to be solved by the present invention is to offer a process for the synthesis of cyclic unsaturated aldehydes or ketones by a catalytic process.

[0012] Surprisingly, it has been found that the process according to claim 1 offers a solution to this problem.

[0013] It has been found that the use of a cobalt complex in combination with photocatalyst (PC) being an organic photocatalyst or an iridium complex and a secondary amine (SA) or an ammonium salt (ASSA) in the presence of light canyield a cyclic unsaturated aldehyde or ketone of the formula (II) from an unsaturated aldehyde or ketone of the formula (I).

[0014] It has been particularly found that this process yields the desired cyclic unsaturated aldehyde or ketones in a high yield and selectivity at high conversion.

[0015] Further aspects of the invention are subject of further independent claims. Particularly preferred embodiments are subject of dependent claims.

[0016] Detailed description of the invention

[0017] In a first aspect the present invention relates to a process of photoredox catalysed cyclisation of unsaturated aldehyde or ketone of the formula (I) to a cyclic unsaturated aldehyde or ketone of the formula (II) in the presence of

[0018] - at least one cobalt complex (CC);

[0019] - at least one photocatalyst (PC) being an organic photocatalyst or an iridium complex;

[0020] - at least one secondary amine (SA) or an ammonium salt (ASSA) of the at least one secondary amine (SA) and an organic or inorganic acid;

[0021] - light;

[0022]

[0023] whereinW represents 0

[0024]

[0025] , S, NR, or R3R3; and

[0026] R4R4

[0027] W represents 0

[0028]

[0029] , S, NR, or > '»

[0030] wherein R represents a Ci-10-alkyl group or Ce-12-aryl group or C6-12- aralkyl group o

[0031]

[0032] r a """s°2 Ar

[0033] with Ar being a Ce-12-aryl group, preferably a p-tolyl group;

[0034] with the proviso, that either W or W, are different from 0, S, or NR;

[0035] X represents either H or a C1-10-alkyl group or a C6-12-cycloalkyl group or a C6-12-aryl group;

[0036] W represents 0, S, N

[0037] R1, R1, R2, R2', R3, R3', R4, R4', R5, R5', R6, R6, R7, R7, R8, R9and R9', either, independently from each other, represents H, a C1-10-alkyl group or a C6-12-aryl group; particularly H or CH3;

[0038] or

[0039] at least two substituents of the group consisting of R1, R1', R2, R2', R3, R4, R4', R5, R5', R6, R6', R7, R7', R8, R9and R9', form together an alkylene group yielding a 5- to 12-membered ring,

[0040] n1, n2 and n3, independently from each other, represent each a value of 0 or 1; and wherein any wavy line represents a carbon-carbon bond which when linked to the carbon-carbon double bond is either in the Z- or in the E-configuration.

[0041] In an embodiment, the process of photoredox catalysed cyclisation of unsaturated aldehyde or ketone of the formula (I) to a cyclic unsaturated aldehyde or ketone of the formula (II) is in the presence of

[0042] - at least one cobalt complex (CC);

[0043] - at least one photocatalyst (PC) being an organic photocatalyst or an iridium complex;- at least one secondary amine (SA) or an ammonium salt (ASSA) of the at least one secondary amine (SA) and an organic or inorganic acid;

[0044] W represents R3R3; and

[0045]

[0046] W represents

[0047] X represents either H or a C1-10-alkyl group or a C6-12-cycloalkyl group or a C6-12-aryl group;

[0048] R1, R1, R2, R2', R3, R3', R4, R4', R5, R5', R6, R6, R7, R7, R8, R9and R9', either, independently from each other, represents H, a C1-10-alkyl group or a C6-12-aryl group; particularly H or CH3;

[0049] orat least two substituents of the group consisting of R1, R1', R2, R2', R3, R4, R4', R5, R5', R6, R6', R7, R7', R8, R9and R9', form together an alkylene group yielding a 5- to 12-membered ring,

[0050] n1, n2 and n3, independently from each other, represent each a value of 0 or 1; and wherein any wavy line represents a carbon-carbon bond which when linked to the carbon-carbon double bond is either in the Z- or in the E-configuration.

[0051] In a preferred embodiment, the at least one secondary amine (SA) or an ammonium salt (ASSA) of the at least one secondary amine (SA) and an organic or inorganic acid is an ammonium salt (ASSA) of the at least one secondary amine (SA) and an organic or inorganic acid.

[0052] In an embodiment, the process of photoredox catalysed cyclisation of unsaturated aldehyde or ketone of the formula (I) to a cyclic unsaturated aldehyde or ketone of the formula (II) is in the presence of

[0053] - at least one cobalt complex (CC);

[0054] - at least one photocatalyst (PC) being an organic photocatalyst or an iridium complex;

[0055] - an ammonium salt (ASSA) of at least one secondary amine (SA) and an organic or inorganic acid;

[0056]

[0057]

[0058] W represents

[0059] X represents either H or a C1-10-alkyl group or a C6-12-cycloalkyl group or a C6-12-aryl group;

[0060] R1, R1, R2, R2', R3, R3', R4, R4', R5, R5', R6, R6, R7, R7, R8, R9and R9', either, independently from each other, represents H, a C1-10-alkyl group or a C6-12-aryl group; particularly H or CH3;

[0061] or

[0062] at least two substituents of the group consisting of R1, R1', R2, R2', R3, R4, R4', R5, R5', R6, R6', R7, R7', R8, R9and R9', form together an alkylene group yielding a 5- to 12-membered ring,

[0063] n1, n2 and n3, independently from each other, represent each a value of 0 or 1; and wherein any wavy line represents a carbon-carbon bond which when linked to the carbon-carbon double bond is either in the Z- or in the E-configuration.

[0064] In a preferred embodiment, the unsaturated aldehyde or ketone of formula (I) is an aldehyde of formula (I).

[0065] In a preferred embodiment, the unsaturated aldehyde or ketone of formula (II) is an aldehyde of formula (II).In an embodiment, the process of photoredox catalysed cyclisation of unsaturated aldehyde of the formula (I) to a cyclic unsaturated aldehyde of the formula (II) is in the presence of

[0066] - at least one cobalt complex (CC);

[0067] - at least one photocatalyst (PC) being an organic photocatalyst or an iridium complex;

[0068] - an ammonium salt (ASSA) of at least one secondary amine (SA) and an organic or inorganic acid;

[0069] W represents R3R3; and

[0070]

[0071] W represents

[0072] X represents either H or a C1-10-alkyl group or a C6-12-cycloalkyl group or a C6-12-aryl group;

[0073] R1, R1, R2, R2', R3, R3', R4, R4', R5, R5', R6, R6, R7, R7, R8, R9and R9', either,independently from each other, represents H, a C1-10-alkyl group or a C6-12-aryl group; particularly H or CH3;

[0074] or

[0075] at least two substituents of the group consisting of R1, R1', R2, R2', R3, R4, R4', R5, R5', R6, R6', R7, R7', R8, R9and R9', form together an alkylene group yielding a 5- to 12-membered ring,

[0076] n1, n2 and n3, independently from each other, represent each a value of 0 or 1; and wherein any wavy line represents a carbon-carbon bond which when linked to the carbon-carbon double bond is either in the Z- or in the E- configuration.

[0077] For sake of clarity, some terms used in the present document are defined as follows:

[0078] In the present document, a “Cx-y-alkyl” group is an alkyl group comprising x to y carbon atoms, i.e., for example, a Ci-3-alkyl group is an alkyl group comprising 1 to 3 carbon atoms. The alkyl group can be linear or branched. For example -CH(CH3)-CH2-CH3 is considered as a C4-alkyl group.

[0079] The term “cycloalkyl group” is understood as comprising a monocyclic or fused, spiro and / or bridged bicyclic or tricyclic cycloalkyl group. Preferably, the cycloalkyl group is a monocyclic cycloalkyl group.

[0080] A “Cx-y aryl” group is an aryl group comprising x to y carbon atoms. An aryl group designates the normal meaning in the art, i.e., an aromatic hydrocarbyl group such as phenyl, pyridine, biphenyl, anthryl or naphthyl group, which may be optionally substituted. Non-limiting examples of the optional substituent of the aryl group include a C1-4 alkyl or alkoxy group, a hydroxy group or a halogen atom.

[0081] A “Cx-y-alkylene” group is an alkylene group comprising x to y carbon atoms. An alkylene is a substituent which, formally, is obtained from an alkane by removal of 2 H atoms and forms a carbon-carbon bond with each of the two rests of the molecule the alkylene group is bound to. For example, a Ci-3-alkylene group is an alkylene group comprising 1 to 3 carbon atoms. The alkylene group can be linear or branched. For example, -CH2-CH2-CH2- and -CH(CH3)-CH2- and -C(CH2-CH3)- and -C(CH3)2- are all considered as a C3-alkylene group.In the present document, “aralkyl” group is an alkyl group of which at least one H is substituted by an aryl group. Hence, for example, benzyl (= C6H5-CH2-) is a C7-aralkyl group.

[0082] In case identical labels for symbols or groups are present in several formulae, in the present document, the definition of said group or symbol made in the context of one specific formula applies also to other formulae which comprises the same said label.

[0083] The term “independently from each other” in this document means, in the context of substituents, moieties, or groups, that identically designated substituents, moieties, or groups can occur simultaneously with a different meaning in the same molecule.

[0084] Any single dotted line in any formulae represents the bond by which said substituent is bound to the rest of a molecule.

[0085] The term “olefinically unsaturated" means in this document that an olefinic unsaturation (C=C) is present. This is used to contrast to unsaturations which are present in alkynes (C-C triple bonds) or double bonds of carbon atoms to hetero atoms such as C=O, or C=N or aromatic C-C bonds.

[0086] Unsaturated aldehyde or ketone

[0087] The aldehyde or ketone of the formula (I) is an unsaturated aldehyde or ketone.

[0088]

[0089] The carbon-carbon double bond is situated so that, depending on the values of n1, n2 and n3, 4 (n1 =n2=n3=0) to 7 (n1 =n2=n3=1 ) carbon atoms are located between the carbon-carbon double bond and the carbon-oxygen double bond of the carbonyl group.

[0090] It is particularly preferred that n1 +n2+n3 = 0 or 1.The unsaturated aldehydes or ketones are olefinically unsaturated aldehydes or ketones. Particularly, said unsaturated aldehydes or ketones do not have any cumulative and / or conjugated carbon-carbon double bonds.

[0091] In one of the embodiments, the substituents R1, R1', R2, R2', R3, R3', R4, R4', R5, R5', R6, R6', R7, R7', R8, R9and R9' independently from each other, represents H, a Ci- -alkyl group or a Ce-12-aryl group; particularly H or CH3.

[0092] In this embodiment, the unsaturated aldehyde or ketone is a linear or branched aldehyde or ketone.

[0093] The unsaturated aldehyde or ketone of formula (I) is preferably a compound of the formula (l-A) or (l-B) or (l-C) or (l-D), particularly (l-AR) or (l-BS) or (l-CS), preferably (l-A), more preferably (l-AR)

[0094] (l-B)

[0095] (l-C)

[0096] (l-D)

[0097] (l-AR)

[0098] (l-BS)

[0099]

[0100]

[0101] In another embodiment, at least two substituents of the group consisting of R1, R1, R2, R2', R3, R4, R4', R5, R5', R6, R6', R7, R7, R8, R9and R9, form together an alkylene group yielding a 5- to 12-membered ring.

[0102] In this embodiment, the unsaturated aldehyde or ketone has at least one cyclic structure of ring size 5 to 12. The process of cyclisation then leads to a cyclic unsaturated aldehyde or ketone of the formula (II) having at least 2 cycles in its structure.

[0103] Non limiting examples for an unsaturated aldehydes or ketones of formula (I) for this embodiment are the following ones of the formulas

[0104]

[0105] In case X represents H, the compound of the formula (I) and accordingly also the compound of the formula (II) are aldehydes.

[0106] In case X represents a C1-10-alkyl group or a C6-12-cycloalkyl group or a C6-12-aryl group, the compound of the formula (I) and accordingly also the compound of the formula (II) are ketones.

[0107] It is particularly preferred that X represents H.

[0108] It is preferred that in formula (I) R1' = R2' = R3' = R4' = R5' = R6' = R7' = H; and that R1, R2, R3, R4, R5, R6, R7, R8, R9and R9', independently from each other, represents H or CH3; particularly so that 1 to 3 of the groups R1, R2, R3, R4, R5, R7, R8, R9and R9' represent CH3.

[0109] Cobalt complex

[0110] The process of the present invention is performed in the presence of at least one cobalt complex (CC).

[0111] The cobalt complex is a complex of Co(ll) or Co(lll). It is preferred that preferably that the cobalt complex at least one organic ligand, preferably a chelating ligand, particularly ligands having the structural element of C=N, more preferably an oxime, which is bound via nitrogen atom to the cobalt.

[0112] It is particularly preferred that the cobalt complex is a complex of Co(lll). It is particularly preferred that the cobalt complex (CC) is a cobalt complex selected from the group consisting of the cobalt complexes of the formula (CC1 ), (CC2), (CC3), (CC4), (CC5), (CC5), (CC6), (CC7), (CC8), (CC9), (CC10), (CC11), (CC12), (CC13), (CC14), and (CC15)

[0113]

[0114] (CC1) (CC2) (CC3)(CC4)

[0115] (CC7) (CC9)

[0116] (CC10) (CC11) (CC12)

[0117]

[0118] (CC14). (CC15)It is particularly preferred that the cobalt complex (CC) is a cobalt complex selected from the group consisting of the cobalt complexes of the formula (CC1 ), (CC2), (CC3), (CC4), (CC5), (CC5), (CC6), (CC7), (CC8), (CC9), (CC10), (CC11), (CC12), (CC13), and (CC14)

[0119]

[0120] (CC7) (CC8) (CC9)

[0121]

[0122] (CC13) (CC14).

[0123] Photocatalyst

[0124] The process of the present invention is performed in the presence of at least one photocatalyst (PC), which is either an organic photocatalyst or an iridium complex.

[0125] In one embodiment, the photocatalyst (PC) is an iridium complex.

[0126] It is preferred that the photocatalyst (PC) is an iridium complex which comprises at least a ligand from the group consisting of

[0127]

[0128] wherein

[0129] Y1, Y1', Y2, Y2', Y and Y3', independently from each other, represents H, a Ci -4-alkyl group or a halogenated Ci -4-alkyl group or a halide or a C1-4 alkoxy group;

[0130] and wherein * marks the atom of the ligand which is bound to the iridium center.

[0131] It is particularly preferred that the iridium complex is an iridium complex which is selected from the group consisting of the compounds of the formula (PC1), (PC2), (PC3), (PC4), (PC5), (PC6), (PC7) and (PC8)

[0132]

[0133] (PC4)

[0134] (PC5) (PC6)

[0135] (PC7) (PC8)

[0136]

[0137] In another embodiment, the photocatalyst (PC) is an organic photocatalyst.

[0138] There exist a broad variety of organic photocatalysts as disclosed by Romero N. A. et al. in Chem. Rev. 2016, 116, 10075-10166, which is herewith incorporated by reference. The organic photocatalyst is particularly selected from the group consisting of cyanoarenes, benzophenones, quinones, pyryliums, thiapyryliums, quinoliniums, acridiniums, xanthene dyes, rhodamines, phenothiazines and polyaromatic photocatalysts.

[0139] More preferably, the organic photocatalyst is a cyanoarene polyaromatic photocatalyst.

[0140] It is preferred that the organic photocatalyst is a cyanoarene polyaromatic photocatalyst which is a compound of the formula (PC0)(PC0)

[0141]

[0142] wherein A1, A2, A3, A4and A5, independently from each other, represents either a halide, CN or an aromatic secondary amino group, particularly of the formula (B1), particularly of the formula (B2)

[0143] (B1) (B2) Ar1' ^Ar2

[0144]

[0145] Z' wherein Ar1and Ar2represent either a phenyl or a substituted phenyl groups or form together a bridged di-phenylic group;

[0146] Z1and Z2, independently from each other, represents represent either H, a halide or a Ci-4-alkyl group or a Ci-4-alkoxy group;

[0147] and any dotted single line in any formulae represents the bond by which said substituent is bound to the rest of a molecule;

[0148] with the proviso, that

[0149] at least one of the substituents A1, A2, A3, A4and A5is an aromatic secondary amino group;

[0150] and not more than two of the substituents A1, A2, A3, A4and A5are halides.

[0151] It is particularly preferred that this cyanoarene polyaromatic photocatalyst is a cyanoarene polyaromatic photocatalyst, which is selected from the group consisting of the compounds of the formula (PC9), (PC10), (PC11), (PC12), (PC13), (PC14), (PC15), (PC16) and (PC17)

[0152]

[0153]

[0154] It is preferred that the photocatalyst (PC) is an organic photocatalyst, particularly selected from the group consisting of cyanoarenes, benzophenones, quinones, pyryliums, thiapyryliums, quinoliniums, acridiniums, xanthene dyes, rhodamines, phenothiazines and polyaromatic photocatalysts.

[0155] It is most preferred that the photocatalyst (PC) is a cyanoarene polyaromatic photocatalyst.

[0156] In a preferred embodiment, the photocatalyst (PC) is a cyanoarene polyaromatic photocatalyst selected from the group consisting of the compounds of the formula (PC9), (PC10), (PC11), (PC12), (PC13), (PC14), and (PC15).

[0157] Secondary amine or ammoniums salt of secondary amine and organic or inorganic acid

[0158] The process of the present invention is performed in the presence of at least one secondary amine (SA) or an ammonium salt (ASSA) of the at least one secondary amine (SA) and an organic or inorganic acid.

[0159] It is preferred that the secondary amine (SA) or an ammonium salt (ASSA) of the at least one secondary amine (SA) and an organic or inorganic acid is a cyclic secondary amine or an ammonium salt of a cyclic secondary amine and an organic or inorganic acid.

[0160] Principally, any secondary amine is suitable for this purpose.

[0161] Preferably the cyclic secondary amine or an ammonium salt of a cyclic secondary amine and an organic or inorganic acid is selected from the group consisting of the formula (SAi) or (SAii)(SAii)

[0162]

[0163] Q represents CH2 or CH2CH2 or 0 or S or NQ3;

[0164] Q1, Q1', Q2and Q2', independently from each other, represents H, or a C1-4- alkyl group or a carboxyl group;

[0165] Q3represents H or a Ci-4-alkyl group, preferably a methyl group;

[0166] or an ammonium salt of said secondary amine (SAi) or (SAii) and an organic or inorganic acid.

[0167] In a preferred embodiment the secondary amine (SA) or an ammonium salt (ASSA) of the at least one secondary amine (SA) and an organic or inorganic acid is a secondary amine (SA) selected from the group consisting of pyrrolidine, piperidine, piperazine, methyl piperazine, morpholine, thiomorpholine and proline; or an ammonium salt of said secondary amine, selected from the group consisting of pyrrolidine, piperidine, piperazine, methyl piperazine, morpholine, thiomorpholine and proline, and an organic or inorganic acid

[0168] The organic or inorganic acid suitable for the formation of an ammonium salt (ASSA) of the at least one secondary amine is preferably a carboxylic acid or a sulfonic acid, particularly an aromatic sulfonic acid.

[0169] In one of the embodiments, said organic or inorganic acid is preferably a carboxylic acid having 1 to 6 carbon atoms, particularly acetic acid or trifluoroacetic acid or trichloroacetic acid.

[0170] In another embodiment, said organic or inorganic acid is preferably a sulfonic acid, particularly an aromatic sulfonic acid, or a halogenated alkylsulfonic acid. Preferably said sulfonic acid is trifluoromethanesulfonic acid (= triflic acid) or p-toluenesulfonic acid (=pTSA).

[0171] It is preferred that ammonium salt (ASSA) of the at least one secondary amine and an organic or inorganic acid, is an ammonium salt of the at least one secondary amine and an organic acid.It is particularly preferred that the secondary amine (SA) or an ammonium salt (ASSA) of the at least one secondary amine (SA) and an organic or inorganic acid is an ammonium salt (ASSA) of a secondary amine (SA) and an organic or inorganic acid.

[0172] Particularly preferred as ammonium salt (ASSA) of a secondary amine is an ammonium salt (ASSA) of morpholine or methyl piperazine and an organic or inorganic acid. Even more preferred is an ammonium salt (ASSA) of a secondary amine which is selected from the group consisting of the compounds of the formula (ASSA1), (ASSA2), (ASSA3), (ASSA4), (ASSA5), and (ASSA6).

[0173] (ASSA1 ) (ASSA2)

[0174] (ASS3) (ASSA4)

[0175] (ASSA5) (ASSA6)

[0176]

[0177] Light

[0178] The process of the present invention is performed in the presence of light. Different light sources for the light can be chosen by the person skilled in the art. Particularly Xe high pressure arc lamps, mercury vapor lamps, laser or LED lamps can be used as suitable light sources. These lamps can provide light with different wavelengths form ultraviolet to infrared light.

[0179] It is preferred that the light used for the process is a light of the wavelengths of between 300 and 800 nm, particularly between 300 and 500 nm, preferably between 385 and 460 nm.

[0180] In one embodiment, the light which is used can be realized by filtering the undesired light wavelengths from a light source. For example, a light source having a multichromatic or white emission can be filtered by a filter which blocks off the undesired wavelength.There are different possibilities of such filters known and commercially available such as absorption, dichroic, monochromatic, band-pass, short-pass or wedge filters, using different physical methods for filtration of light.

[0181] In another embodiment, a light source is chosen which has the emission in the range of the desired range of wavelength. In a very specific embodiment, the light sources emit monochromatic or quasi-monochromatic light of the desired wavelength. Such light sources can be chosen by the person skilled in the art.

[0182] Particularly preferred are LED lamps, particularly LED lamps emitting a light of 420 nm.

[0183] There exist different possibilities how the light source is arranged to allow the emitted light to the reaction mixture.

[0184] Suitable arrangements are known as photoreactors to the person skilled in the art.

[0185] In one of the embodiments, the light source is inserted in the reaction vessel. In another embodiment the light source is arranged in or outside the wall of the reactor, in which case the walls need to be transparent to light of the desired wavelength.

[0186] In an even further embodiment, the reaction medium is in contact with light source in form of a thin film.

[0187] It also can be advantageous to use helical arrangements of light sources or reaction vessel, respectively, to optimize optimal photo absorption.

[0188] Solvents might be used for the process of the invention. It is obvious that for the choice of solvent it is advantageous that said solvent does not absorb or does not absorb much of the light of the desired wavelength to assure to avoid the reaction to occur quantitatively.

[0189] The use of a solvent is advantageous to adjust the concentration of the ingredients allowing an optimal absorption of the light by the absorbing species in the reaction mixture assuring optimal conversion and yield.

[0190] It is preferred that the solvent is selected from the group consisting of alcohols, aliphatic ketones, alkylnitriles, ethers, halogenated hydrocarbons and dialkylsulfoxydes.Particularly suitable are organic solvents selected from the group consisting of methanol, ethanol, acetonitrile, acetone, a,a,a-trifluorotoluene, 1,2-dichloroethane and dimethylsulfoxyde, in particular acetonitrile.

[0191] It is preferred that the unsaturated aldehyde or ketone of the formula (I) is present in the range 0.05 - 2 mol / Liter, preferably in the range of 0.1 - 1 mol / Liter, in respect to the reaction mixture.

[0192] It is further preferred that the cobalt complex (CC) is present in the reaction mixture in an amount that the molar ratio of cobalt complex (CC) I compound of the formula (I) is in the range of 0.1 to 5 mol% preferably in the range of 0.25 to 1 mol%.

[0193] It is further preferred that the photocatalyst (PC) is present in the reaction mixture in an amount that the molar ratio of photocatalyst (PC) I compound of the formula (I) is in the range of 0.1 to 5 mol%, preferably in the range of 0.25 to 1 mol%.

[0194] It is further preferred that secondary amine (SA) or an ammonium salt (ASSA) of the at least one secondary amine (SA) and an organic or inorganic acid is present in the reaction mixture in an amount that the molar ratio of secondary amine (SA) or an ammonium salt (ASSA) I compound of the formula (I) is in the range of 5 - 20 mol%, preferably in the range of 10 - 15 mol%.

[0195] The process can be performed at a temperature of preferably between 0°C and 60°C, particularly between 10°C and 40°C, most preferably between 20 and 30°C.

[0196] It is preferred that the process is performed in inert atmosphere, particularly under nitrogen or argon.

[0197] Cyclic aldehyde or ketone

[0198] The process leads to a cyclic aldehyde or ketone of the formula (II).O

[0199]

[0200] Said cyclic aldehyde or ketone has, depending on the values of n1, n2 and n3, a ring size of 5 (n1=n2=n3=0) to 8 (n1=n2=n3=1) carbon atoms. It is particularly preferred that compound of the formula (II) has a ring size of 5 or 6, i.e. that n1+n2+n3 = 0 or 1.

[0201] It is particularly preferred that the above process leads to a cyclic unsaturated aldehyde or ketone of the formula ( I l-A) or ( I l-B) or ( I l-C) or ( I l-D), particularly (ll-AA) or (ll-BB) or (ll-BC) or (ll-BD) or (ll-CC) or (ll-DD), more particularly (ll-AAR) or (ll-BBS), or (ll-BCS) or (ll-BDS), preferably (ll-AA), more preferably (ll-AAS)

[0202]

[0203] (ll-BBS)

[0204]

[0205] wherein R9represents a C1-10-alkylene group, particularly CH2.The cyclic unsaturated aldehydes or ketones of the formula (II) can be obtained at high conversion in significantly high yields and selectivity.

[0206] As shown above the combination of cobalt complex (CC); photocatalyst (PC), secondary amine (SA) or an ammonium salt (ASSA) and unsaturated aldehyde or ketone of the formula (I) can advantageously yield by the above process in the presence of light to the cyclic unsaturated aldehyde or ketone of the formula (II).

[0207] Hence, the present invention relates in a further aspect to a composition for comprising at least

[0208] a) a cobalt complex (CC);

[0209] b) a photocatalyst (PC) being an organic photocatalyst, particularly a cyanoarene polyaromatic photocatalyst, or an iridium complex; and c) a secondary amine (SA) or an ammonium salt (ASSA) of the secondary amine (SA) and an organic or inorganic acid; d) an unsaturated aldehyde or ketone of the formula (I).

[0210] Details for these ingredients, such as their preferred embodiments and concentrations, ratios are described above in great details.

[0211] As shown above the combination of cobalt complex (CC); photocatalyst (PC) and secondary amine (SA) or an ammonium salt (ASSA) can be used for the photoredox catalysed cyclisation of an unsaturated aldehyde or ketone of the formula (I).

[0212] Hence, the present invention relates in a further aspect to the use of a composition comprising at least

[0213] a) a cobalt complex (CC);

[0214] b) a photocatalyst (PC) being an organic photocatalyst, preferably a cyanoarene polyaromatic photocatalyst, or an iridium complex; and c) a secondary amine (SA) or an ammonium salt (ASSA) of the secondary amine (SA) and an organic or inorganic acid;- 28 - 2024P00184WC for the photoredox catalysed cyclisation of an unsaturated aldehyde or ketone of the formula (I).

[0215] Details for these ingredients, such as their preferred embodiments and concentrations, ratios are described above in great details.

[0216] Examples

[0217] The following examples are provided to further illustrate the compositions and effects of the present invention. These examples are illustrative only and are not intended to limit the scope of the invention in any way.

[0218] General procedure of

[0219]

[0220] A 20 mL glass reactor was charged under argon with (R)-3,7-dimethyloct-6-enal (154 mg, 1 mmol) followed by photocatalyst (PC) as indicated in the respective tables (0.01 mmol, 1 mol%), followed by the cobalt catalyst (CC) as indicated in the respective tables in the concentration as indicated in the respective tables, followed by the secondary amine (SA) or the ammonium salt (ASSA) of the secondary amine as indicated in the respective tables in the concentration as indicated in the respective tables dissolved in acetonitrile. The reaction mixture was irradiated at 460 nm under inert atmosphere at 25°C. After 23h the irradiation was stopped, and the reaction mixture was analysed. The colourless liquid product of the reaction was identified as 7S;2R;5S)-2-methyl-5-(prop-1 -en-2-yl)cyclopentane-1 -carbaldehyde:

[0221] 1H NMR (500 MHz, CD2Cl2): 6 = 9.5 (d, 1H), 4.73 (t, 1H), 4.71 (t, 1H), 2.80 (q, 1H), 2.26-2.16 (m, 2H), 1.96-1.88 (m, 2H), 1.7 (s, 3H),1.68-1.60 (m, 1 H), 1.4-1.33 (m, 1 H), 1.05 (d,3H) ppm.

[0222] 13C NMR (125 MHz, CD2Cl2): 6 = 204.1 (CH), 146.8 (C), 110 (CH2), 64.1 (CH), 49.5 (CH), 36.6 (CH), 33.9 (CH2), 30.7 (CH2), 20.6 (CH3), 19.6 (CH3) ppm.

[0223] The conversion and yield are reported in the respective tables.- 29 - 2024P00184WC First series: cyclisation using different photocatalysts (PC)

[0224] The cyclisation has been performed using the described general procedure conversion and yield are reported in table 1.

[0225] Example. PC1Conversion2[%] Yield2[%]

[0226] 1 (PC1) 88 64

[0227] 2 (PC2) 86 51

[0228] 3 (PC3) 87 60

[0229] 4 (PC4) 88 43

[0230] 5 (PC5) 85 58

[0231] 6 (PC6) 86 57

[0232] 7 (PC7) 86 59

[0233] 8 (PC9) 88 63

[0234]

[0235] Table 1. Cyclisation of (R)-3,7-c imethyloct-6-enal in 0.1 M acetonitrile using different photocatalysts, cobalt complex (CC) of the formula (CC3), and ammonium salt (ASSA) of the formula (ASSA1 ) with a molar ratio in ppm relative to the substrate of PC / CC / ASSA = 10'000 / 50'000 / 100'000.1PC: Photocatalyst of the formula determined by GC, relative to (R)-3,7-dimethyloct-6-enal.

[0236] Second series: cyclisation using different photocatalysts (PC)

[0237] The cyclisation has been performed using the described general procedure conversion and yield are reported in table 2.

[0238] Example. PC1Conversion2[%] Yield2[%]

[0239] 9 (PC9) 97 85

[0240] 10 (PC10) 94 80

[0241] 11 (PC11) 92 73

[0242] 12 (PC12) 94 81

[0243] 13 (PC13) 95 77

[0244] 14 (PC14) 94 77

[0245] 15 (PC15) 95 75

[0246] 16 (PC16) 54 17

[0247]

[0248] Table 2. Cyclisation of (R)-3,7-c imethyloct-6-enal in 0.05 M acetonitrile using different photocatalysts, cobalt complex (CC) of the formula (CC12), and ammonium salt (ASSA) of the formula (ASSA6) with a molar ratio in ppm relative to the substrate of PC / CC / ASSA = 10'000 / 10'000 / 150'000.1PC: Photocatalyst of the formula determined by GC, relative to (R)-3,7-dimethyloct-6-enal.As can be seen from Table 2, high conversion and yield are achieved by the process of the invention with a range of organic photocatalysts. Comparatively lower conversion and yield was obtained PC16 under these conditions due to low solubility of PC16 in acetonitrile.

[0249] Third series: cyclisation using different cobalt complexes (CC)

[0250] The cyclisation has been performed using the described general procedure conversion and yield are reported in table 3.

[0251] Example. CC1Conversion2[%] Yield2[%]

[0252] 17 (CC1) 20 47

[0253] 18 (CC2) 17 56

[0254] 19 (CC3) 87 63

[0255] 20 (CC4) 14 59

[0256] 21 (CC5) 26 45

[0257] 22 (CC6) 25 48

[0258] 23 (CC7) 20 47

[0259] 24 (CC8) 22 57

[0260] 25 (CC9) 20 53

[0261]

[0262] Table 3. Cyclisation of (R)-3,7-d imethyloct-6-enal in 0.1 M acetonitrile using different cobalt complexes, photocatalyst (PC) of the formula (PC9) and ammonium salt (ASSA) of the formula (ASSA1 ) with a molar ratio in ppm relative to the substrate of PC / CC / ASSA = 10 000 I 50 0001 100000.1CC: Cobalt complex of formula determined by GC, relative to (R)-3,7-dimethyloct-6-enal.

[0263] Fourth series: cyclisation using different cobalt complexes (CC)

[0264] The cyclisation has been performed using the described general procedure conversion and yield are reported in table 4.

[0265] Example. CC1Conversion2[%] Yield2[%]

[0266] 26 (CC3) 92 81

[0267] 27 (CC10) 93 82

[0268] 28 (CC11) 95 84

[0269] 29 (CC12) 94 86

[0270]

[0271] Table 4. Cyclisation of (R)-3,7-d imethyloct-6-enal in 0.05 M acetonitrile using different cobalt complexes, and photocatalyst (PC9) of the formula (PC9) and ammonium salt (ASSA) of the formula (ASSA6) with a molar ratio in- 31 - 2024P00184WC ppm relative to the substrate of PC / CC / ASSA =

[0272] 10 000 / 10 000 / 150000.

[0273] 1CC: Cobalt complex of formula determined by GC, relative to (?)-3,7-dimethyloct-6-enal

[0274] Fifth series: cyclisation using different secondary amine (SA) or ammonium salts (ASSA)

[0275] The cyclisation has been performed using the described general procedure conversion and yield are reported in table 5.

[0276] Example. ASSA1Conversion2[%] Yield2[%] 30 (ASSA1 ) 93 73

[0277] 31 (ASSA2) 59 45

[0278] 32 (ASSA3) 78 61

[0279] 33 (ASSA4) 46 6

[0280] 34 (ASSA5) 23 5

[0281] 35 (ASSA6) 94 79

[0282]

[0283] Table 5. Cyclisation of (R -3,7-dimethyloct-6-enal in 0.1 M acetonitrile using different secondary amines (SA) or ammonium salts (ASSA) of secondary amines and organic acids, photocatalyst (PC) of the formula (PC9) and cobalt complex (CC) of the formula (CC3) with a molar ratio in ppm relative to the substrate of PC / CC / ASSA = 10'000 / 10'000 / 100'000)1ASSA: ammonium salts of secondary amine and organic acid of formula determined by GC, relative to (RJ-3,7-dimethyloct-6-enal.

[0284] Sixth series: cyclisation using different solvents

[0285] The cyclisation has been performed using the described general procedure conversion and yield are reported in table 6.

[0286] Example. Solvents Conversion1[%] Yield1[%] 36 Acetonitrile 87 63

[0287] 37 Acetone 55 20

[0288] 38 Methanol 77 50

[0289] 39 Dimethoxyethane 27 4

[0290] 40 a,a,a-Triflurotoluene 24 3

[0291] 41 Dimethylsulfoxyde 49 33

[0292] 42 1,2-Dichloroethane 30 6

[0293] 43 Ethanol 80 8

[0294]

[0295] Table 6. Cyclisation of (R -3,7-dimethyloct-6-enal in 0.1 M concentration in different solvents, photocatalyst (PC) of formula (PC9), cobalt complex(CC) of formula (CC3) and ammonium salt (ASSA) of formula (ASSA1) and with a molar ratio in ppm relative to the substrate of PC / CC / ASSA = 10 000 / 50 000 / 100 000. determined by GC, relative to / ?-3,7-dimethyloct-6-enal.

[0296] Seventh series: cyclisation using different wavelengths of light

[0297] A 400 mL glass reactor was charged under argon with (R)-3,7-dimethyloct-6-enal (2.3 g, 15 mmol) followed by photocatalyst (PC) of the formula (PC9)(0.15 mmol, 1 mol%), followed by the cobalt complex (CC) of the formula (CC12) (0.15 mmol, 1 mol%), followed by the ammonium salt (ASSA) of the formula (ASSA6) (2.25 mmol, 15 mol%) dissolved in 300 ml of acetonitrile. The reaction mixture was irradiated with LED light of a wavelength as indicated in table 7 under inert atmosphere. After 23h the irradiation was stop, and the reaction mixture was analyzed for the formation of (TS,2R,5S)-2-methyl-5-(prop-1-en-2-yl)cyclopentane-1-carbaldehyde and the results are shown in table 7.

[0298] Example. Wavelength of light [nm] Conversion1[%] Yield1[%]

[0299] 44 385 97 75

[0300] 45 420 95 76

[0301] 46 460 97 74

[0302]

[0303] Table 7. Cyclisation of (R)-3,7-dimethyloct-6-enal at 45°C at different wavelengths in 0.05 M acetonitrile, photocatalyst (PC) of the formula (PC9), cobalt complex (CC) of the formula (CC12) and ammonium salt (ASSA) of the formula (ASSA6).

[0304] determined by GC, relative to (R)-3,7-dimethyloct-6-enal.

[0305] Eighth series: cyclisation using different temperatures

[0306] The procedure as indicate above for the seventh series has been repeated using a wavelength of 420 nm at a temperature of 25° C and 45 °C. The results are shown in table 8 and 9.

[0307] Example. Temperature [°C] Conversion1[%] Yield1[%]

[0308] 47 45 95 76

[0309] 48 25 97 77

[0310]

[0311] Table 8. Cyclisation of (R)-3,7-dimethyloct-6-enal at a wavelength of 420 nm in 0.05 M acetonitrile, photocatalyst (PC) of the formula (PC9), cobalt complex (CC) of the formula (CC12) and ammonium salt (ASSA) of the formula (ASSA6).

[0312] determined by GC, relative to (R)-3,7-dimethyloct-6-enal.

[0313] Ninth series: cyclisation using different temperatures- 33 - 2024P00184WC Example. Temperature [°C] Conversion1[%] Yield1[%] 49 50 82 46 50 25 94 71 51 10 93 70 52 0 94 72

[0314]

[0315] Table 9. Cyclisation of (R)-3,7-dimethyloct-6-enal at a wavelength of 420 nm in 0.5 M acetonitrile, photocatalyst (PC) of the formula (PC9), cobalt complex (CC) of the formula (CC12) and ammonium salt (ASSA) of the formula (ASSA6). determined by GC, relative to (R)-3,7-dimethyloct-6-enal.

[0316] Tenth series: cyclisation using different loadings and concentrations

[0317] The cyclisation has been performed using the described general procedure conversion and yield are reported in table 10.

[0318] Concentration Conversion2Yield2Example PC / CC / ASSA1

[0319] [M] [%] [%] 53 alk0.05 10 000 / 10 000 / 150 000 95 85 54 0.05 5 000 / 10 000 / 150 000 95 82 55 0.1 5 000 / 10 000 / 150 000 95 83 56 0.1 2 500 / 10 000 / 150 000 95 77 57 0.2 2 500 / 10 000 / 150 000 93 77 58 0.1 2 500 / 10 000 / 100 000 93 76 59 0.5 1 000 / 1 000 / 15 000 30 21 60 0.5 1 000 / 1 000 / 150 000 64 32 61 0.5 1 000 / 2 500 / 150 000 89 65 62 0.5 1 000 / 5 000 / 150 000 91 68 63 0.5 2 500 / 2 500 / 150 000 94 73 64 1 2 500 / 2 500 / 150 000 94 67 65 0.5 3 000 / 3 000 / 150 000 93 75

[0320]

[0321] Table 10. Cyclisation of (R)-3,7-dimethyloct-6-enal at a wavelength of 420 nm and 25°C in a concentration in acetonitrile as indicated, photocatalyst (PC) of the formula (PC9), cobalt complex (CC) of the formula (CC12) and ammonium salt (ASSA) of the formula (ASSA6).

[0322] 1molar ratio in ppm relative to the substrate of PC / CC / ASSA, relative to (R)-3,7-dimethyloct-6-enal.

[0323] 2determined by GC, relative to (R)-3,7-dimethyloct-6-enal. Eleventh series: Cyclisation using different reaction conditionsA 20-mL glass reactor was charged under argon with the corresponding aldehyde followed by photocatalyst (PC) as indicated in Table 11, by the cobalt catalyst (CC) as indicated in Table 11, and by the secondary amine (SA) or the ammonium salt (ASSA) of the secondary amine as indicated in Table 11. It was dissolved in acetonitrile at concentrations indicated in Table 11. The reaction mixture was irradiated at a wavelength specified in Table 11 under inert atmosphere at a temperature specified in Table 11. After 23h, the irradiation was stopped, and the reaction mixture was analysed. The conversion and yield are reported in Table 11.

[0324] Ex. Substrate PC CC SA ASSA Conversion Yield [%]la] [%]la] 66 (S)-6,8- PC9 CC7 - ASSA6 98 96 dimethylnon- 7-enal[b]

[0325] 67 (S)-6,8- PC6 CC15 Morpholine - 52 27 dimethylnon- 7-enal[c]

[0326] 68 (S)-4,8- PC9 CC13 - ASSA6 86 78 dimethylnon- 7-enal[d]

[0327] 69 (S)-4,8- PC6 CC15 Morpholine - 82 50 dimethylnon- 7-enal[c]

[0328] 70 (R)-3,7- PC9 CC12 - ASSA6 94 73 dimethyloct- 6-enal[e]

[0329] 71 (R)-3,7- PC6 CC15 Morpholine - 73 28 dimethyloct- 6-enal[c]

[0330] 72 (S)-6,8- PC9 CC15 Methyl- 27 7 dimethylnon- piperazine

[0331] 7-enal[f]

[0332] (S)-6,8- PC9 CC15 - ASSA6 100 70 dimethylnon-

[0333]

[0334] 7-enal[g]

[0335] Table 11. Cyclisation of corresponding aldehydes in different conditions

[0336] adetermined by GC, relative to the substrate.

[0337] bA(irr) = 420 nm, T = 25°C, MeCN (0.1 M), PC / CC / ASSA = 4000 / 4000 / 150000, molar ratio in ppm relative to the substrate.

[0338] cA(irr) = 427 nm, T = 25°C, DMSO (0.1 M), PC / CC / SA = 25000 / 50000 / 200 000, molar ratio in ppm relative to the substrate.- 35 - 2024P00184WCdA(irr) = 420 nm, T = 25°C, MeCN (0.5 M), PC / CC / ASSA = 2500 / 2500 / 100000, molar ratio in ppm relative to the substrate.

[0339] eA(irr) = 420 nm, T = 25°C, MeCN (0.5 M), PC / CC / ASSA = 2500 / 2500 / 150000, molar ratio in ppm relative to the substrate.

[0340] fA(irr) = 427 nm, T = 35°C, MeCN (0.2 M), PC / CC / SA = 6000 I 3000 I 250 000, molar ratio in ppm relative to the substrate.

[0341] gA(irr) = 427 nm, T = 35°C, MeCN (0.2 M), PC / CC / ASSA = 6000 / 3000 / 250 000, molar ratio in ppm relative to the substrate.

[0342] As seen from Table 11, the cyclisation reactions in the presence of an ammonium salt of a secondary amine (ASSA) led to higher substrate conversion and yield, compared to the conversion and yield of the cyclisation reactions in the presence of a secondary amine.

[0343] Examples of cyclisation of further unsaturated aldehyde or ketone of the formula (I) according to the process of the invention

[0344] Cyclization of (R)-3,7-dimethyloct-6-enal

[0345]

[0346] To a solution of (R)-3,7-dimethyloct-6-enal (ee = 79%) in acetonitrile (0.5M) was added the photocatalyst (PC) of the formula (PC9) (2,4,5,6-tetrakis(9 / - / -carbazol-9-yl) isophthalonitrile) (0.25 mol%), followed by the cobalt complex (CC) of the formula (CC12) (0.25 mol%), and the ammonium salt (ASSA) of secondary amine and organic acid of the formula (ASSA6) (methyl piperazinium trifluoroacetic acid salt) (15 mol%). The reaction mixture was irradiated with LED at 420 nm under nitrogen atmosphere at 25°C. After 23h the reaction was stopped, concentrated and distilled under vacuum to afford (+)-(1 S,2R,5S)-2-methyl-5-(prop-1-en-2-yl)cyclopentane-1-carbaldehyde (GC: 89 % of desired product, ee = 79%) as a colourless liquid.

[0347] Cyclization of (S)-4,8-dimethylnon-7-enal

[0348] To a solution of (+)-(S)-4,8-dimethylnon-7-enal (ee 35%) dissolved in acetonitrile (0.5M) was added the photocatalyst (PC) of the formula (PC9) (1,2,3,5-Tetrakis(carbazol-9-yl)-4,6-dicyanobenzene, 2,4,5,6-tetrakis(9 / - / -carbazol-9-yl) isophthalonitrile) (0.25 mol%), the cobalt complex (CC) of the formula (CC13) (Co(dmgBF2)2.2H2O) (0.25 mol%) and the ammonium salt (ASSA) of secondaryamine and organic acid of the formula (ASSA6) (methyl piperazinium trifluoroacetic acid salt) (15 mol% ). The reaction mixture was irradiated at 420 nm under nitrogen atmosphere at 25°C. After 28h the reaction was stopped. The crude reaction mixture was concentrated and distilled under vacuum () to afford the desired aldehyde (+)-(7S,2S,5S)-5-methyl-2-(prop-1-en-2-yl)cyclohexane-1- carbaldehyde (GC: 99% of desired product, ee 35%,) as a colourless liquid.

[0349] 1H NMR (500 MHz, CD2Cl2): 6 = 9.5 (d, 1H), 4.73 (t, 1H), 4.71 (t, 1H), 2.80 (q, 1H), 2.26-2.16 (m, 2H), 1.96-1.88 (m, 2H), 1.7 (s, 3H),1.68-1.60 (m, 1 H), 1.4-1.33 (m, 1 H), 1.05 (d,3H) ppm.

[0350] 13C NMR (125 MHz, CD2Cl2): 6 = 204.1 (CH), 146.8 (C), 110 (CH2), 64.1 (CH), 49.5 (CH), 36.6 (CH), 33.9 (CH2), 30.7 (CH2), 20.6 (CH3), 19.6 (CH3) ppm.

[0351]

[0352] Cyclization of (+)-(S)-6,8-dimethylnon-7-enal

[0353] To a solution of (+)-(S)-6,8-dimethylnon-7-enal (ee 31%) dissolved in acetonitrile (0.1 M) was added the photocatalyst (PC) of the formula (PC9) (1,2,3,5- Tetrakis(carbazol-9-yl)-4,6-dicyanobenzene, 2,4,5,6-tetrakis(9 / - / -carbazol-9-yl) isophthalonitrile) (0.4 mol%), the cobalt complex (CC) of the formula (CC7) (Co(dmgH)2(Methyl Benzymidazol)CI) (0.4 mol%) and the ammonium salt (ASSA) of secondary amine and organic acid of the formula (ASSA6) (methyl piperazinium trifluoroacetic acid salt) (15 mol%). The reaction mixture was irradiated at 420 nm under nitrogen atmosphere at 25°C. After 21 h, the reaction was stopped. The crude reaction mixture was concentrated and distilled under vacuum to afford the desired aldehyde (-)-(1 R,2R,3S)-3-methyl-2-(prop-1 -en-2-yl)cyclohexane-1 - carbaldehyde (GC: 98% of desired product, ee 31%,) as a colourless liquid.

[0354] 1H-NMR (600 MHz, CDCl3): d = 9.42 (d, J= 4.6 Hz, 1H, CHO), 4.8 (brs, 1H, C=CH), 4,76 (brs, 1 H, C=CH) 2.27 (m, 1 H, CH-CHO), 1.89 (t, J = 22 Hz, 1H, CH2), 1.82 (m, 1H, CH2), 1.78 (m, 1H, CH2), 1.77 (m, 1H, CH2), 1.64 (s, 3H, CH3), 1.42 (m, 1H. CH), 1.35 (ap. t, 2H, CH2), 1.01 (m, 1H, CH2), 0.82 (d, J =6.3 Hz, 3H, CH3) ppm.- 37 - 2024P00184WC C-NMR (151 MHz, CDCl3): d = 204.83 (CHO), 144.99 (C, C=CH), 113.76 (CH2, C=CH2), 53.67 (CH), 52.72 (CH, CH-CHO), 34.48 (CH2), 33.64 (CH), 26.26 (CH2), 24.77 (CH2), 19.77 (CH3), 18.58 (CH3) ppm.

Claims

Claims1. A process of photoredox catalysed cyclisation of unsaturated aldehyde or ketone of the formula (I) to a cyclic unsaturated aldehyde or ketone of the formula (II) in the presence of- at least one cobalt complex (CC);- at least one photocatalyst (PC) being an organic photocatalyst or an iridium complex;- at least one secondary amine (SA) or an ammonium salt (ASSA) of the at least one secondary amine (SA) and an organic or inorganic acid;W represents 0, S, NR, or R3R3; and R4R4W represents 0, S, NR, orwherein R represents a Ci- -alkyl group or Ce-12-aryl group or Ce-12- aralkyl group or a """s°2 Arwith Ar being a Ce-12-aryl group, preferably a p-tolyl group;with the proviso, that either W or W, are different from 0, S, or NR;X represents either H or a Ci-w-alkyl group or a C6-i2-cycloalkyl group or a Ce-12-aryl group;R1, R1, R2, R2, R3, R3, R4, R4, R5, R5, R6, R6, R7, R7, R8, R9and R9, either, independently from each other, represents H, a C1-10-alkyl group or a C6-12-aryl group; particularly H or CH3;orat least two substituents of the group consisting of R1, R1', R2, R2', R3, R4, R4', R5, R5', R6, R6', R7, R7', R8, R9and R9', form together an alkylene group yielding a 5- to 12-membered ring,n1, n2 and n3, independently from each other, represent each a value of 0 or 1; and wherein any wavy line represents a carbon-carbon bond which when linked to the carbon-carbon double bond is either in the Z- or in the E- configuration.

2. The process according to claim 1 characterized in that R1' = R2' = R3' = R4' = R5' = R6' = R7' = HandR1, R2, R3, R4, R5, R6, R7, R8, R9and R9', independently from each other, represents H or CH3; particularly so that 1 to 3 of the groups R1, R2, R3, R4, R5, R7, R8, R9and R9' represent CH3.

3. The process according to claim 1 or 2, characterized in that the compound of the formula (I) is a compound of the formula (l-A) or (l-B) or (l-C) or (l-D), particularly (l-AR) or (l-BS) or (l-CS), preferably (l-A), more preferably (l-AR)(l-B)(l-D)(l-BS)(l-CS).

4. The process according to any of the preceding claims, characterized in that in that the compound of the formula (II) is a cyclic unsaturated aldehyde or ketone of the formula ( I l-A) or (I l-B) or ( I l-C) or (I l-D), particularly (ll-AA) or (ll-BB) or (ll-BC) or (ll-BD) or (ll-CC) or (ll-DD), more particularly (ll-AAR) or (ll-BBS) or (ll-BCS) or (I l-BDR), preferably (ll-AA), more preferably (ll-AAR)(II-BDR)wherein R9represents a C1-10-alkylene group, particularly CH2.

5. The process according to any of the preceding claims, characterized in that the cobalt complex (CC) is a Co(ll) or Co(lll) complex, preferably that the cobalt complex comprises at least one organic ligand, preferably a chelating ligand, particularly ligands having the structural element of C=N, more preferably an oxime, which is bound via nitrogen atom to the cobalt.

6. The process according to any of the preceding claims, characterized in that the cobalt complex (CC) is a cobalt complex selected from the group consisting of the cobalt complexes of the formula (CC1 ), (CC2), (CC3), (CC4), (CC5), (CC5), (CC6), (CC7), (CC8), (CC9), (CC10), (CC11), (CC12), (CC13), (CC14), and (CC15)OH OH (CC1) (CC3)(CC4)(CC7) (CC9)(CC10) (CC12)(CC13) (CC14). (CC15)7. The process according to any of the preceding claims, characterized in that photocatalyst (PC) is an iridium complex which comprises at least one ligand from the group consisting ofwhereinY1, Y1', Y2, Y2', Y and Y3', independently from each other, represents H, a Ci -4-alkyl group or a halogenated Ci -4-alkyl group or a halide or a C1-4 alkoxy group;and wherein * marks the atom of the ligand which is bound to the iridium center.

8. The process according to any of the preceding claims, characterized in that photocatalyst (PC) is an iridium complex which complex is selected from the group consisting of the compounds of the formula (PC1 ), (PC2), (PC3), (PC4), (PC5), (PC6), (PC7) and (PC8)(PC1)(PC3)(PC5)9. The process according to any of the preceding claims, characterized in that the photocatalyst (PC) is a cyanoarene polyaromatic photocatalyst, which is a compound of the formula (PCO)(PCO)wherein A1, A2, A3, A4and A5, independently from each other, represents either a halide, CN or an aromatic secondary amino group, particularly of the formula (B1 ), particularly of the formula (B2)(B1) (B2)Z' wherein Ar1and Ar2represent either a phenyl or a substituted phenyl groups or form together a bridged di-phenylic group;Z1and Z2, independently from each other, represents represent either H, a halide or a Ci-4-alkyl group or a Ci-4-alkoxy group;and any dotted single line in any formulae represents the bond by which said substituent is bound to the rest of a molecule;with the proviso, thatat least one of the substituents A1, A2, A3, A4and A5is an aromatic secondary amino group;and not more than two of the substituents A1, A2, A3, A4and A5are halides.

10. The process according to any of the preceding claims, characterized in that the photocatalyst (PC) is a cyanoarene polyaromatic photocatalyst, which is selected from the group consisting of the compounds of the formula (PC9), (PC10), (PC11), (PC12), (PC13), (PC14), (PC15), (PC16) and (PC17)11. The process according to any of the preceding claims, characterized in that the secondary amine (SA) is a cyclic secondary amine or an ammonium salt of a cyclic secondary amine and an organic or inorganic acid, preferably selected from the group consisting of the formula (SAi) or (SAii)Q2Q Q2(SAi) (SAii) Q1N Q11H whereinQ represents CH2 or CH2CH2 or 0 or S or NQ3;Q1, Q1', Q2and Q2', independently from each other, represents H, or a C1-4- alkyl group or a carboxyl group;Q3represents H or a Ci-4-alkyl group, preferably a methyl group;or an ammonium salt of said secondary amine (SAi) or (SAii) and an organic or inorganic acid.

12. The process according to any of the preceding claims, characterized in that secondary amine (SA) or an ammonium salt (ASSA) of the at least one secondary amine (SA) and an organic or inorganic acid isan ammonium salt (ASSA) of a secondary amine (SA) and an organic or inorganic acid;preferably an ammonium salt (ASSA) of morpholine or methyl piperazine and an organic or inorganic acid;more preferably an ammonium salt (ASSA) selected from the group consisting of the compounds of the formula (ASSA1), (ASSA2), (ASSA3), (ASSA4), (ASSA5), and (ASSA6)F(ASSA1 ) (ASSA2) F(ASSA3) (ASSA4)Cl -F (ASSA5) (ASSA6) Cl PF13. The process according to any of the preceding claims, characterized in that the light is a light of the wavelengths of between 300 and 500 nm, preferably between 385 and 460 nm.

14. A composition for comprising at leasta) a cobalt complex (CC);b) a photocatalyst (PC) being an organic photocatalyst, preferably a cyanoarene polyaromatic photocatalyst, or an iridium complex; and c) a secondary amine (SA) or an ammonium salt (ASSA) of the secondary amine (SA) and an organic or inorganic acid;d) an unsaturated aldehyde or ketone of the formula (I)X represents either H or a C1-10-alkyl group or a C6-12-cycloalkyl group or a C6-12-aryl group;R1, R1, R2, R2', R3, R3', R4, R4', R5, R5', R6, R6, R7, R7, R8, R9and R9', either, independently from each other, represents H, a C1-10-alkyl group or a C6-12-aryl group; particularly H or CH3;orat least two substituents of the group consisting of R1, R1', R2, R2', R3, R4, R4', R5, R5', R6, R6', R7, R7', R8, R9and R9', form together an alkylene group yielding a 5- to 12-membered ring,n1, n2 and n3, independently from each other, represent each a value of 0 or 1; and wherein any wavy line represents a carbon-carbon bond which when linked to the carbon-carbon double bond is either in the Z- or in the E- configuration.

15. The use of a composition comprising at leasta) a cobalt complex (CC);b) a photocatalyst (PC) being an organic photocatalyst, preferably a cyanoarene polyaromatic photocatalyst, or an iridium complex c) a secondary amine (SA) or an ammonium salt (ASSA) of the secondary amine (SA) and an organic or inorganic acid;for the photoredox catalysed cyclisation of an unsaturated aldehyde orX represents either H or a C1-10-alkyl group or a C6-12-cycloalkyl group or a C6-12-aryl group;R1, R1, R2, R2', R3, R3', R4, R4', R5, R5', R6, R6, R7, R7, R8, R9and R9', either, independently from each other, represents H, a C1-10-alkyl group or a C6-12-aryl group; particularly H or CH3;orat least two substituents of the group consisting of R1, R1', R2, R2', R3, R4, R4', R5, R5', R6, R6', R7, R7', R8, R9and R9', form together an alkylene group yielding a 5- to 12-membered ring,n1, n2 and n3, independently from each other, represent each a value of 0 or 1; and wherein any wavy line represents a carbon-carbon bond which when linked to the carbon-carbon double bond is either in the Z- or in the E-configuration.

Images