Use of Silylated Formiates as Hydrosilane Equivalents

Abstract

The present invention relates to a method for preparing organic compounds of formula (I) by reaction between a silylated formiate of formula (II) and an organic compound in the presence of a catalyst and optionally of an additive.

The invention also relates to use of the method for preparing organic compounds of formula (I) for the preparation of reagents for fine chemistry and for heavy chemistry, as well as in the production of vitamins, pharmaceutical products, adhesives, acrylic fibres, synthetic leathers, and pesticides.

Claims

1. A method for preparing compounds of formula (I) ##STR00157## where: independently from one another, R.sub.0, R.sub.1, and R.sub.2 are chosen from the group formed by an alkoxy group, an aryloxy group, an alkyl group, a carboxyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, a heterocyclic group, a silyl group, and a siloxy group, said alkyl, alkenyl, alkynyl, aryl, heteroaryl, alkoxy, aryloxy, silyl, siloxy, or heterocyclic groups optionally being substituted, or together with the silicon atom to which they are bonded, R.sub.0 and R.sub.1 form a silylated heterocycle that is optionally substituted and R.sub.2 is as defined above; n=0 or 1; m=0 or 1; when n=0 and m=1, Z is chosen from the group formed by —NR.sub.3R.sub.4 where: independently from each other, R.sub.3 and R.sub.4 are chosen from the group formed by a hydrogen atom, an alkyl group, a halogenoalkyl group, an alkenyl group, an alkynyl group, a silyl group, an aryl group, a heteroaryl group, and a heterocyclic group, said alkyl, alkenyl, alkynyl, aryl, heteroaryl, silyl, or heterocyclic groups optionally being substituted; or taken together with the nitrogen atom to which they are bonded, R.sub.3 and R.sub.4 form an optionally substituted heterocycle; when n=m=1, independently from one another, R.sub.3, R.sub.4 and R.sub.5 are chosen from the group formed by a hydrogen atom, an alkyl group, a halogenoalkyl group, an alkenyl group, a cyclic alkenyl group, an alkynyl group, a silyl group, an aryl group, a heteroaryl group, and a heterocyclic group, said alkyl, alkenyl, alkynyl, aryl, heteroaryl, silyl, or heterocyclic groups optionally being substituted; or together with the carbon atom to which they are bonded, R.sub.3, R.sub.4 and R.sub.5 form an optionally substituted aryl; or together with the carbon atom to which they are bonded, R.sub.3 and R.sub.4 form an optionally substituted cyclic alkyl and R.sub.5 is as defined above; or together with the carbon atom to which they are bonded, R.sub.3 and R.sub.4 form an optionally substituted cyclic alkenyl and R.sub.5 is as defined above; or together with the carbon atom to which they are bonded, R.sub.3, R.sub.4 and R.sub.5 form a cyclic alkenyl; and Z is chosen from the group formed by: X or Y as defined below; together with the carbon atom to which they are bonded, Z and R.sub.5 form a ##STR00158## group, where R.sub.3 is as defined above; or together with the carbon atom to which they are bonded, Z and R.sub.5 form a ##STR00159## group, where R.sub.7 is chosen from the group formed by a hydrogen atom, an alkyl group, or an aryl group, said alkyl and aryl groups optionally being substituted, where R.sub.3 is as defined above; when n=1 and m=0, Z is chosen from the group formed by —NR.sub.9R.sub.10 where: independently from each other, R.sub.9 and R.sub.10 represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, a heterocyclic group, and a silyl group, said alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclic, or silyl groups optionally being substituted; or taken together with the nitrogen atom to which they are bonded, R.sub.9 and R.sub.10 form an optionally substituted heterocycle; and R.sub.3, R.sub.4 and R.sub.5 are as defined above; characterised in that a silylated formiate of formula (II) ##STR00160## where R.sub.0, R.sub.1 and R.sub.2 are as defined above, is caused to react with an organic compound of formula (III), (IV), (V), (VI), (VII), (VIII) or (IX) ##STR00161## where: R.sub.3, R.sub.4, R.sub.5 R.sub.9 and R.sub.10 are as defined above; R.sub.7 is chosen from a group formed by a hydrogen atom, an alkyl group, or an aryl group, said alkyl and aryl groups optionally being substituted; R.sub.8 is chosen from the group formed by a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, and a heterocyclic group, said alkyl, alkenyl, alkynyl, aryl, heteroaryl, or heterocyclic groups optionally being substituted; X is chosen from the group formed by: an oxygen atom; a CR.sub.aR.sub.b group where, independently from each other, R.sub.a and R.sub.b represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, a silyl group, or a heterocyclic group, said alkyl, aryl, heteroaryl, silyl, or heterocyclic groups optionally being substituted; or an NR.sub.6 group where R.sub.6 represents a hydrogen atom, an alkyl group, a silyl group, or an aryl group, said alkyl, silyl and aryl groups optionally being substituted; and Y is chosen from a group formed by an oxygen atom or a sulphur atom; in the presence of a catalyst and optionally of an additive.

2. The method according to claim 1, wherein, when n=0 and m=1, the organic compound is of formula (IX); and in the compound of formula (I), Z is chosen from the group formed by —NR.sub.3R.sub.4; where independently from each other, R.sub.3 and R.sub.4 are chosen from the group formed by a hydrogen atom, an alkyl group, a halogenoalkyl group, an alkenyl group, an alkynyl group, a silyl group, an aryl group, a heteroaryl group, and a heterocyclic group, said alkyl, alkenyl, alkynyl, aryl, heteroaryl, silyl, or heterocyclic groups optionally being substituted.

3. The method according to claim 1, wherein, when n=0 and m=1, the organic compound is of formula (IX); and in the compound of formula (I), Z is chosen from the group formed by —NR.sub.3R.sub.4; where, taken together with the nitrogen atom to which they are bonded, R.sub.3 and R.sub.4 form an optionally substituted heterocycle.

4. The method according to claim 1, wherein, when n=m=1, the organic compound is of formula (III); and in the compound of formula (I), and together with the carbon atom to which they are bonded, Z and R.sub.5, form a ##STR00162## group, where R.sub.3 is chosen from the group formed by a hydrogen atom, an alkyl group, a silyl group, an aryl group, a heteroaryl group, and a heterocyclic group, said alkyl, aryl, heteroaryl, silyl, or heterocyclic groups optionally being substituted; R.sub.7 is chosen from a group formed by a hydrogen atom, an alkyl group, or an aryl group, said alkyl and aryl groups optionally being substituted.

5. The method according to claim 1, wherein, when n=m=1, the organic compound is of formula (IV); and in the compound of formula (I), and together with the carbon atom to which they are bonded, Z and R.sub.5 form a ##STR00163## group where: R.sub.3 is chosen from the group formed by a hydrogen atom, an alkyl group, a halogenoalkyl group, an alkenyl group, a cyclic alkenyl group, an alkynyl group, a silyl group, an aryl group, a heteroaryl group, and a heterocyclic group, said alkyl, alkenyl, alkynyl, aryl, heteroaryl, silyl, or heterocyclic groups optionally being substituted.

6. The method according to claim 1, wherein, when n=m=1, the organic compound is of formula (V); and in the compound of formula (I), Z is X and X represents an oxygen atom, where R.sub.5 is chosen from the group formed by a hydrogen atom; and independently from each other, R.sub.3 and R.sub.4 are chosen from the group formed by a hydrogen atom, an alkyl group, a halogenoalkyl group, an alkenyl group, a cyclic alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, and a heterocyclic group, said alkyl, alkenyl, alkynyl, aryl, heteroaryl, or heterocyclic groups optionally being substituted.

7. The method according to claim 1, wherein, when n=m=1, the organic compound is of formula (V); and in the compound of formula (I), Z is X and X represents an oxygen atom, where R.sub.5 is chosen from the group formed by a hydrogen atom; and together with the carbon atom to which they are bonded, R.sub.3 and R.sub.4 form a cyclic alkyl containing 3 to 20 carbon atoms, said cyclic alkyl optionally being substituted.

8. The method according to claim 1, wherein, when n=m=1, the organic compound is of formula (V); and in the compound of formula (I), Z is X and X represents a CR.sub.aR.sub.b group, where: independently from each other, R.sub.a and R.sub.b represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, a silyl group, or a heterocyclic group, said alkyl, aryl, heteroaryl, silyl, or heterocyclic groups optionally being substituted; and R.sub.5 is chosen from the group formed by a hydrogen atom; and independently from each other, R.sub.3 and R.sub.4, are chosen from the group formed by a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, a silyl group, and a heterocyclic group, said alkyl, aryl, heteroaryl, silyl, or heterocyclic groups optionally being substituted.

9. The method according to claim 1, wherein, when n=m=1, the organic compound is of formula (V); and in the compound of formula (I), Z is X and X represents a CR.sub.aR.sub.b group, where: independently from each other, R.sub.a and R.sub.b represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, a silyl group, or a heterocyclic group, said alkyl, aryl, heteroaryl, silyl, or heterocyclic groups optionally being substituted; and R.sub.5 is chosen from the group formed by a hydrogen atom; and together with the carbon atom to which they are bonded, R.sub.3 and R.sub.4 form an optionally substituted cyclic alkyl; or together with the carbon atom to which they are bonded, R.sub.3 and R.sub.4 form an optionally substituted cyclic alkenyl; said cyclic alkyl and cyclic alkenyl groups optionally being substituted.

10. The method according to claim 1, wherein, when n=m=1, the organic compound is of formula (V); and in the compound of formula (I), Z is X and X represents an NR.sub.6 group, where: R.sub.6 represents a hydrogen atom, an alkyl group, a silyl group, or an aryl group, said alkyl, silyl and aryl groups optionally being substituted; and R.sub.5 is chosen from the group formed by a hydrogen atom; and independently from each other, R.sub.3 and R.sub.4 are chosen from the group formed by a hydrogen atom, an alkyl group, an aryl group, and a silyl group, said alkyl, aryl, or silyl groups optionally being substituted.

11. The method according to claim 1, wherein, when n=m=1, the organic compound is of formula (VI); and in the compound of formula (I), Z is X and X represents an oxygen atom, where: R.sub.8 is chosen from the group formed by a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a silyl group, a heteroaryl group, and a heterocyclic group, said alkyl, alkenyl, alkynyl, aryl, heteroaryl, or heterocyclic groups optionally being substituted; and R.sub.3 is chosen from the group formed by a hydrogen atom, a hydroxyl group, an alkyl group, a halogenoalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, and a heterocyclic group, said alkyl, alkenyl, alkynyl, aryl, heteroaryl, or heterocyclic groups optionally being substituted; and independently from each other, R.sub.4 and R.sub.5 represent a hydrogen atom.

12. The method according to claim 1, wherein, when n=1 and m=0, the organic compound is of formula (VII), where X represents an oxygen atom; and in the compound of formula (I), Z is chosen from the group formed by —NR.sub.9R.sub.10, where: independently from each other, R.sub.9 and R.sub.10 are chosen from the group formed by a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, a heterocyclic group, and a silyl group, with the alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclic, or silyl groups optionally being substituted; and R.sub.3 is chosen from the group formed by a hydrogen atom, an alkyl group, a halogenoalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, and a heterocyclic group, said alkyl, alkenyl, alkynyl, aryl, heteroaryl, or heterocyclic groups optionally being substituted; and independently from each other, R.sub.4 and R.sub.5 represent a hydrogen atom.

13. The method according to claim 1, wherein, when n=1 and m=0, the organic compound is of formula (VII), where X represents an oxygen atom; and in the compound of formula (I), Z is chosen from the group formed by —NR.sub.9R.sub.10, where: taken together with the nitrogen atom to which they are bonded, R.sub.9 and R.sub.10 form an optionally substituted heterocycle; and R.sub.3 is chosen from the group formed by a hydrogen atom, an alkyl group, a halogenoalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, and a heterocyclic group, said alkyl, alkenyl, alkynyl, aryl, heteroaryl, or heterocyclic groups optionally being substituted; and independently from each other, R.sub.4 and R.sub.5 represent a hydrogen atom.

14. The method according to claim 1, wherein, when n=m=1, the organic compound is of formula (VIII); and in the compound of formula (I), Z is Y, and Y represents an oxygen atom, and, independently from each other, R.sub.3, R.sub.4, and R.sub.5 are chosen from the group formed by: a hydrogen atom; an alkyl group containing 1 to 12 carbon atoms and chosen from the group formed by methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and their branched isomers, said alkyl group optionally being substituted with: one or more hydroxy groups; one or more alkoxy groups in which the alkyl radical contains 1 to 12 carbon atoms and is chosen from the group formed by methoxy, ethoxy, propyloxy, butyloxy, pentyloxy, hexyloxy, heptyloxy, and the branched isomers thereof; one or more alkenyl groups that contain 2 to 16 carbon atoms, and that are chosen from the group formed by ethylenyl propylenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl and their branched isomers, said alkenyl groups optionally being substituted with an alkyl group chosen from the group formed by ethyl, propyl, butyl, pentyl, and the branched isomers thereof; one or more halogenoalkyl groups chosen from the group formed by —CF.sub.3, —CCl.sub.3, —CHCl.sub.2, —CClBrCF.sub.3; one or more siloxy groups chosen from the group formed by trimethylsiloxy, triethylsiloxy, and butyldiphenylsiloxy; or one or more aryl groups that contain 6 to 10 carbon atoms and that are chosen from the group formed by phenyl, and benzyl, optionally substituted with: one or more halogen atoms chosen from among fluorine, chlorine, bromine, and iodine atoms; one or more alkoxy groups chosen from the group formed by methoxy, ethoxy, propyloxy, butyloxy, pentyloxy, and the branched isomers thereof; one or more alkyl groups chosen from the group formed by methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and the branched isomers thereof; one or more —C(O)R.sub.13 acyl groups, where R.sub.13 represents an alkyl group that contains 1 to 12 carbon atoms and that is chosen from the group formed by methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and the branched isomers thereof, an aryl group chosen from the group formed by phenyl, and benzyl, an amino group chosen from the group formed by dimethylamino, and diethylamino, an alkoxy group chosen from the group formed by methoxy, and ethoxy, or an aryloxy group chosen from the group formed by benzyloxy, and phenoxy; one or more —OC(O)R.sub.14 carboxyl groups, where R.sub.14 represents a hydrogen atom, an alkyl group chosen from the group formed by methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and their branched isomers, or an aryl group chosen from the group formed by phenyl and benzyl; one or more nitrile groups (—CN); one or more nitro groups (—NO.sub.2); or one or more amino groups chosen from the group formed by —NH.sub.2, —NHCH.sub.3, —N(CH.sub.3).sub.2, —N(CH.sub.2CH.sub.3).sub.2, and —NH(CH.sub.2CH.sub.3); an alkenyl group that contains 2 to 16 carbon atoms, and that is chosen from the group formed by ethylenyl propylenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl and the branched isomers thereof, said alkenyl groups optionally being substituted with: one or more alkyl groups chosen from the group formed by methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and the branched isomers thereof; one or more aryl groups chosen from the group formed by phenyl, and benzyl, optionally substituted with: one or more halogen atoms chosen from among fluorine, chlorine, bromine, and iodine atoms; one or more alkoxy groups chosen from the group formed by methoxy, ethoxy, propyloxy, butyloxy, pentyloxy, and the branched isomers thereof; one or more alkyl groups chosen from the group formed by methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and the branched isomers thereof; one or more thioalkoxy groups (—S-alkyl) with the alkyl radical being chosen from the group formed by methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and the branched isomers thereof; one or more —C(O)R.sub.13 acyl groups, where R.sub.13 represents an alkyl group that contains 1 to 12 carbon atoms and that is chosen from the group formed by methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and the branched isomers thereof, an aryl group chosen from the group formed by phenyl, and benzyl, an amino group chosen from the group formed by dimethylamino, and diethylamino, an alkoxy group chosen from the group formed by methoxy, and ethoxy, or an aryloxy group chosen from the group formed by benzyloxy, and phenoxy; one or more —OC(O)R.sub.14 carboxyl groups, where R.sub.14 represents a hydrogen atom, an alkyl group chosen from the group formed by methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and the branched isomers thereof, or an aryl group chosen from the group formed by phenyl and benzyl; one or more nitrile groups (—CN); one or more nitro groups (—NO.sub.2); or one or more amino groups chosen from the group formed by —NH.sub.2, —NHCH.sub.3, —N(CH.sub.3).sub.2, —N(CH.sub.2CH.sub.3).sub.2, and —NH(CH.sub.2CH.sub.3); a —C(O)R.sub.13 acyl group, where R.sub.13 is an alkyl group that contains 1 to 12 carbon atoms and that is chosen from the group formed by methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and the branched isomers thereof; an aryloxy group in which the aryl radical contains 6 to 10 carbon atoms and is chosen from the group formed by phenoxy and benzyloxy; a halogenoalkyl group chosen from the group formed by —CF.sub.3, —CCl.sub.3, —CHCl.sub.2, and —CClBrCF.sub.3; an aryl group that contains 6 to 10 carbon atoms and that is chosen from the group formed by phenyl, and benzyl, optionally substituted with: one or more halogen atoms chosen from among fluorine, chlorine, bromine, and iodine atoms; one or more alkoxy groups chosen from the group formed by methoxy, ethoxy, propyloxy, butyloxy, pentyloxy, and the branched isomers thereof; one or more alkyl groups chosen from the group formed by methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and the branched isomers thereof; one or more thioalkoxy groups (—S-alkyl) with the alkyl radical being chosen from the group formed by methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and the branched isomers thereof; one or more —C(O)R.sub.13 acyl groups, where R.sub.13 represents an alkyl group that contains 1 to 12 carbon atoms and that is chosen from the group formed by methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and the branched isomers thereof; one or more —OC(O)R.sub.14 carboxyl groups, where R.sub.14 represents a hydrogen atom, or an alkyl group chosen from the group formed by methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and the branched isomers thereof; one or more nitrile groups (—CN); one or more nitro groups (—NO.sub.2); or one or more amino groups chosen from the group formed by —NH.sub.2, —NHCH.sub.3, —N(CH.sub.3).sub.2, —N(CH.sub.2CH.sub.3).sub.2, and —NH(CH.sub.2CH.sub.3); and a heteroaryl group that contains 5 to 12 members including at least 2 carbon atoms and at least one heteroatom chosen from nitrogen, oxygen, and sulphur, said heteroaryl group being chosen from the group formed by furyl, thienyl, pyrrolyl, pyridyl, imidazolyl, and thiazolyl.

15. The method according to claim 1, wherein, when n=m=1, the organic compound is of formula (VIII); and in the compound of formula (I), Z is Y, and Y represents an oxygen atom, and, together with the carbon atom to which they are bonded, R.sub.3, R.sub.4 and R.sub.5 form an aryl that contains 6 to 10 carbon atoms, and that is chosen from the group formed by phenyl and benzyl, optionally substituted with: one or more halogen atoms chosen from among fluorine, chlorine, bromine, and iodine atoms; one or more alkoxy groups chosen from the group formed by methoxy, ethoxy, propyloxy, butyloxy, pentyloxy, and the branched isomers thereof; one or more aryloxy groups chosen from phenoxy and benzyloxy; one or more alkyl groups chosen from the group formed by methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and the branched isomers thereof; one or more thioalkoxy groups (—S-alkyl) with the alkyl radical being chosen from the group formed by methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and the branched isomers thereof; one or more —C(O)R.sub.13 acyl groups, where R.sub.13 represents an alkyl group that contains 1 to 12 carbon atoms and that is chosen from the group formed by methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and the branched isomers thereof, an aryl group chosen from the group formed by phenyl, and benzyl, an amino group chosen from the group formed by dimethylamino, and diethylamino, an alkoxy group chosen from the group formed by methoxy, and ethoxy, or an aryloxy group chosen from the group formed by benzyloxy, and phenoxy; one or more —OC(O)R.sub.14 carboxyl groups, where R.sub.14 represents a hydrogen atom, or an alkyl group chosen from the group formed by methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and the branched isomers thereof; one or more nitrile groups (—CN); one or more nitro groups (—NO.sub.2); or one or more amino groups chosen from the group formed by —NH.sub.2, —NHCH.sub.3, —N(CH.sub.3).sub.2, —N(CH.sub.2CH.sub.3).sub.2, and —NH(CH.sub.2CH.sub.3).

16. The method according to claim 1, wherein, when n=m=1, the organic compound is of formula (VIII); and in the compound of formula (I), Z is Y and Y represents an oxygen atom, where: R.sub.5 represents a hydrogen atom; and together with the carbon atom to which they are bonded, R.sub.3 and R.sub.4 form a monocyclic or polycyclic alkyl that contains 3 to 20 carbon atoms and that is chosen from the group formed by cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicyclo[2,1,1]hexyl, bicyclo[2,2,1] heptyl, and 2-adamantyl, said monocyclic or polycyclic alkyl group optionally being substituted with: one or more hydroxy groups; one or more alkoxy groups in which the alkyl radical contains 1 to 12 carbon atoms and is chosen from the group formed by methoxy, ethoxy, propyloxy, butyloxy, pentyloxy, hexyloxy, heptyloxy, and the branched isomers thereof; one or more alkenyl groups that contain 2 to 16 carbon atoms, and that are chosen from the group formed by ethylenyl propylenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl and the branched isomers thereof, said alkenyl groups optionally being substituted with an alkyl group chosen from the group formed by ethyl, propyl, butyl, pentyl, and the branched isomers thereof; one or more halogenoalkyl groups chosen from the group formed by —CF.sub.3, —CCl.sub.3, —CHCl.sub.2, and —CClBrCF.sub.3; one or more siloxy groups chosen from the group formed by trimethylsiloxy, triethylsiloxy, and butyldiphenylsiloxy; or one or more aryl groups that contain 6 to 10 carbon atoms and that are chosen from the group formed by phenyl, and benzyl.

17. The method according to claim 1, wherein, when n=m=1, the organic compound is of formula (VIII); and in the compound of formula (I), Z is Y and Y represents an oxygen atom, where: R.sub.5 represents a hydrogen atom; and together with the carbon atom to which they are bonded, R.sub.3 and R.sub.4 form a cyclic alkenyl that contains 3 to 20 carbon atoms and at least one double bond chosen from the group formed by cyclopentenyl, cyclohexenyl, and 2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthrenyl; or together with the carbon atom to which they are bonded, R.sub.3 R.sub.4, and R.sub.5 form a cyclic alkenyl that contains 3 to 20 carbon atoms and at least one double bond chosen from the group formed by cyclopentenyl, and cyclohexenyl; said cyclic alkenyl group optionally being substituted with: one or more halogen atoms chosen from among fluorine, chlorine, bromine, and iodine atoms; one or more alkoxy groups chosen from the group formed by methoxy, ethoxy, propyloxy, butyloxy, pentyloxy, and the branched isomers thereof; one or more aryloxy groups chosen from between phenoxy and benzyloxy; one or more alkyl groups chosen from the group formed by methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and the branched isomers thereof; one or more thioalkoxy groups (—S-alkyl) with the alkyl radical being chosen from the group formed by methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and the branched isomers thereof; one or more —C(O)R.sub.13 acyl groups, where R.sub.13 represents an alkyl group that contains 1 to 12 carbon atoms and that is chosen from the group formed by methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and the branched isomers thereof; one or more —OC(O)R.sub.14 carboxyl groups, where R.sub.14 represents a hydrogen atom, or an alkyl group chosen from the group formed by methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and the branched isomers thereof; one or more nitrile groups (—CN); one or more nitro groups (—NO.sub.2); or one or more amino groups chosen from the group formed by —NH.sub.2, —NHCH.sub.3, —N(CH.sub.3).sub.2, —N(CH.sub.2CH.sub.3).sub.2, and —NH(CH.sub.2CH.sub.3).

18. The method according to claim 1, wherein, when n=m=1, the organic compound is of formula (VIII); and in the compound of formula (I), Z is Y, and Y represents a sulphur atom, and, together with the carbon atom to which they are bonded, R.sub.3, R.sub.4 and R.sub.5 form an aryl that contains 6 to 10 carbon atoms, and that is chosen from the group formed by phenyl and benzyl, optionally substituted with: one or more halogen atoms chosen from among fluorine, chlorine, bromine, and iodine atoms; one or more alkoxy groups chosen from the group formed by methoxy, ethoxy, propyloxy, butyloxy, pentyloxy, and the branched isomers thereof; one or more aryloxy groups chosen from between phenoxy and benzyloxy; one or more alkyl groups chosen from the group formed by methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and the branched isomers thereof; one or more thioalkoxy groups (—S-alkyl) with the alkyl radical being chosen from the group formed by methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and the branched isomers thereof; one or more —C(O)R.sub.13 acyl groups, where R.sub.13 represents an alkyl group that contains 1 to 12 carbon atoms and that is chosen from the group formed by methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and the branched isomers thereof; one or more —OC(O)R.sub.14 carboxyl groups, where R.sub.14 represents a hydrogen atom, or an alkyl group chosen from the group formed by methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and the branched isomers thereof; one or more nitrile groups (—CN); one or more nitro groups (—NO.sub.2); or one or more amino groups chosen from the group formed by —NH.sub.2, —NHCH.sub.3, —N(CH.sub.3).sub.2, —N(CH.sub.2CH.sub.3).sub.2, and —NH(CH.sub.2CH.sub.3).

19. The method according to claim 1, wherein, in the compound of formula (I) and the silylated formiate of formula (II), independently of one another, R.sub.0, R.sub.1 and R.sub.2 are chosen from the group formed by an alkoxy group in which the alkyl group contains 1 to 12 carbon atoms, an alkyl group containing 1 to 20 carbon atoms, an aryl group containing 6 to 20 carbon atoms, or an aryloxy group in which the aryl group contains 6 to 20 carbon atoms, said alkyl, aryl, alkoxy, and aryloxy groups optionally being substituted.

20. The method according to claim 1, wherein it takes place in the presence of a catalyst chosen from the group formed by metallic salts or metallic complexes of: alkaline earth metals chosen from magnesium, and calcium; and transition metals chosen from molybdenum, nickel, iron, cobalt, zinc, copper, rhodium, ruthenium, platinum, palladium, and iridium.

21. The method according to claim 1, wherein it takes place in the presence of an additive chosen from: triadamantylephosphine (PAdm.sub.3), tris[2-diphenylephosphino)ethyl]phosphine (PP.sub.3), 1,1,1-tris(diphenylphosphinomethyl)ethane (triphos), 1,3-Bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr), tricyclohexylphosphine, acetate (AcO), acetylacetonate (acac), 1,2-bis-diphenylphosphinoethane (dppe), N,N,N′,N′-tetra-methyl-ethylenediamine (TMEDA), N,N′-bis(2,6-diisopropylphenyl) β-dicetiminate (BDI), 1,2-bis(diphenylphosphino)ethane (dppb), or pyridine; trifluoromethanesulfonic acid (TfOH), trifluoroacetic acid (TFA), or bis(trifluoromethane)sulfonamide (HNTf.sub.2); boron trifluoride (BF.sub.3), tris(pentafluorophenyl)borane (B(C.sub.6F.sub.5).sub.3), or aluminium trichloride (AlCl.sub.3); triethylamine, potassium tert-butoxide (tBuOK); lithium chloride (LiCl), sodium chloride (NaCl), or potassium chloride (KCl); and carbenes chosen from the group formed by salts of 1,3-bis(2,6-diisopropylphenyl)-1H-imidazol-3-ium (also known as “IPr”), 1,3-bis(2,6-diisopropylphenyl)-4,5-dihydro-1H-imidazol-3-ium (also known as “s-IPr”), 1,3-bis(2,4,6-trimethylphenyl)-1H-imidazol-3-ium (also known as “IMes”), 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydro-1H-imidazol-3-ium (also known as “s-IMes”), 4,5-dichloro-1,3-bis(2,6-diisopropylphenyl)-1H-imidazol-3-ium (also known as “Cl.sub.2—IPr”), 1,3-di-tert-butyl-1H-imidazol-3-ium (also known as “ItBu”), and 1,3-di-tert-butyl-4,5-dihydro-1H-imidazol-3-ium (also known as “s-ItBu”), said salts being in the form of chloride salts or tetraphenylborate salts.

22. The method according to claim 1, wherein the quantity of the organic compound of formula (III), (IV), (V), (VI), (VII), (VIII) or (IX) is 0.1 to 1 molar equivalent, and preferably 0.5 to 1 molar equivalent, limits included, relative to the silylated formiate of formula (II).

23. The method according to claim 1, wherein the quantity of catalyst is 0.0001 to 0.2 molar equivalent, and preferably 0.005 to 0.1 molar equivalent, limits included, relative to the organic compound of formula (III), (IV), (V), (VI), (VII), (VIII) or (IX).

24. The method according to claim 1, wherein the quantity of the additive is 0.001 to 2 molar equivalents, and preferably 0.01 to 1 molar equivalent, limits included, relative to the organic compound of formula (III), (IV), (V), (VI), (VII), (VIII) or (IX).

25. (canceled)

Description

[0475] Other advantages and characteristics of the present invention appear upon reading the following examples that are given by way of illustrative and non-limiting examples, and upon examining the appended figures.

[0476] FIG. 1 thus shows the main paths of access to hydrosilanes and chlorosilanes of the “core type”: carbothermal reduction of silica SiO.sub.2 or of silicates SiO.sub.4.sup.4− (step 1); oxidation of metallurgical-grade silicon (step 2); functionalisation of trichlorosilane (step 3);

[0477] FIG. 2 shows a summary of the problems related to preparation of hydrosilanes (sections 1 and 2): synthesis of hydrosilanes by reduction and oxidation of silicon (section 1); and redox-neutral synthesis of hydrosilanes by LiAlH.sub.4 (section 2);

[0478] FIG. 3 shows radical transfer hydrosilylation with the cyclohexa-1,4-diene (1,4-CHDN)s substituted in position 2 with silylated groups (silylated 1,4-CHDNs 1 and 9);

[0479] FIG. 4 shows ionic transfer hydrosilylation of 1-methylcyclohexene catalysed by B(C.sub.6F.sub.5).sub.3 as described by M. Oestreich et coll. (Angewandte Chemie Int. Ed. 2013, 52, 11905-11907);

[0480] FIG. 5 shows ionic hydrosilylation of alkynes, of ketones, and of imines catalysed by B(C.sub.6F.sub.5).sub.3;

[0481] FIG. 6 shows transfer dehydrogenative coupling of octanol (24) catalysed by B(C.sub.6F.sub.5).sub.3 as described by M. Oestreich et coll. (European Journal of Organic Chemistry 2014, 2014, 2077-2083);

[0482] FIG. 7 shows redox-neutral synthesis of silylated formiate as renewable hydrosilane equivalents;

[0483] FIG. 8 summarises the transfer hydrosilylation and dehydrogenative coupling reactions with different types of organic substrate;

[0484] FIG. 9 summarises the transfer hydrosilylation and transfer dehydrogenative coupling reactions with amides;

[0485] FIG. 10 shows examples of N-heterocyclic carbenes that can be used as additives and as ligands; and

[0486] FIG. 11 shows a selection of ligands that are mentioned above and that can be used as additives.

EXAMPLES

[0487] A set of results is presented below, giving examples of transfer hydrosilylation of carbonyls (aldehydes and ketones) (example 1) and of transfer dehydrogenative coupling (example 2) with various silylated formiates. These reactions are catalysed by transition metals, optionally in the presence of additives. The abbreviations used to describe the catalysts used are defined at the end of the table. The yields are obtained by integrating the signals of the silylated product relative to the signals of the mesitylene used as internal standard. In some cases, a yield of isolated product (after purification as described above) is also given.

[0488] The yields are always calculated by using the following formula:

[00001]$\rho \left(\mathrm{transfer}\right)=\frac{n\left(\mathrm{product}\right)}{n_0\left(\mathrm{substrate}\right)}$

[0489] where:

[0490] ρ(transfer): yield in terms of optionally silylated product after transfer of the hydrosilane (%)

[0491] n.sub.0(substrate): quantity of matter in terms of organic substrate added initially (mmol); and

[0492] n(silylated product): quantity of matter in terms of product after transfer of the hydrosilane (mmol).

[0493] Protocol for Preparing the Silylated Formiates of Formula (II)

[0494] The silylated formiates of formula (II) may be prepared using any method known to a person skilled in the art. For example, Et3SiOCHO may be prepared from Et.sub.3SiCl and from sodium formiate (HCO.sub.2Na) according to the protocol described by F. A. Leblanc, W. E. Piers, M. Parvez, Angew. Chem. Int. Ed., 2014, 53, 789-792. In addition, Me.sub.3SiOCHO may be obtained from Me.sub.3SiCl and from formic aid in the presence of an organic base such as pyridine in diethyl ether according to the protocol described by Etienne (Y. Etienne, C. R. Hebd. Seances Acad. Sci., 1952, 235, 966-968).

[0495] In the present invention, the silylated formiates are synthesised from formic acid, from a chlorosilane having the general formula R.sub.0(x)R.sub.1(y)R.sub.2(z)Si(Cl).sub.4−(x+y+z) (x=0 or 1; y=0 or 1; z=0 or 1) optionally in the presence of a base and of a solvent:

[0496] For example, these syntheses may be performed according to the following experimental protocol:

[0497] 1. In an inert atmosphere, in a glovebox, chlorosilane, formic acid (in the range 1 molar equivalent to 4.4 molar equivalents relative to chlorosilane) and, optionally, the solvent are added to a round-bottom flask. The order in which the reagents are added is unimportant. The flask is then removed from the glovebox while maintaining the reaction medium in an inert atmosphere, and the base is added drop-by-drop (in the same proportions as the formic acid) at 0° C. Once the addition of the base is finished, the reaction mixture is heated to ambient temperature and is agitated vigorously for 15 hours in an inert atmosphere. The crude reaction mixture is then filtered through a Buchner funnel, and then the filtrate is transferred to a round-bottom flask and the solvent is evaporated in a vacuum. The resulting residue is purified by fractional distillation. This general protocol is exemplified with the synthesis of Et.sub.3SiOCHO from Et.sub.3SiCl:

[0498] 1. In an inert atmosphere, in a glovebox, Et.sub.3SiCl (10.4 mL, 62 mmol, 1 equiv.), anhydrous ether (100 mL) and formic acid (2.4 mL, 62 mmol, 1 equiv.) are added to a 500-mL round-bottom two-neck flask.

[0499] 2. The flask is then removed from the glovebox while maintaining the reaction medium in an inert atmosphere, and the triethylamine is added drop-by-drop (8.4 mL; 62 mmol; 1 equiv.) at 0° C. Once the addition of the triethylamine is finished, the reaction mixture is heated to ambient temperature and is agitated vigorously for 15 hours in an inert atmosphere. The crude reaction mixture is then filtered through a Buchner funnel, the solid is washed with diethyl ether (3×20 mL) and then with pentane (20 mL). The filtrate is transferred to a round-bottom flask and the volatile compounds are evaporated in a vacuum at 0° C. The resulting residue is purified by fractional distillation to obtain 6.1 g (61%) of the colourless liquid Et.sub.3SiOCHO (62° C.-64° C. at 27 mmHg). The following table gives some results obtained for synthesis of various silylated formiates:

TABLE-US-00001 Quantity of Chlorosilane formic Base Solvent Silylated (mmol) acid (mmol) (mmol) (mL) formiate Yield (%) Me.sub.3SiCl 85 Pyridine Et.sub.2O Me.sub.3SiOCHO 67% (85) (85) (20) Et.sub.3SiCl 62 NEt.sub.3 Et.sub.2O Et.sub.3SiOCHO 61% (62) (62) (100) (iPr).sub.3SiCl 24, 7 NEt.sub.3 Et.sub.2O (iPr).sub.3SiOCHO 58% (24.7) (25) (50) Ph.sub.2MeSiCl 19, 2 NEt.sub.3 Et.sub.2O Ph.sub.2MeSiOCHO 65% (19) (19.2) (50) (EtO).sub.3SiCl 24 NEt.sub.3 Et.sub.2O (EtO).sub.3SiOCHO 57% (24) (24.1) (50)

[0500] Once the silylated formiates have been obtained, the method of the invention can be implemented according to the following experimental protocol:

[0501] 1. In an inert atmosphere, in a glovebox, the silylated formiate having the general formula R.sub.0(x)R.sub.1(y)R.sub.2(z)Si(OCHO).sub.4−(x+y+z) (x=0 or 1; y=0 or 1; z=0 or 1) (0.1 molar equivalents to 500 molar equivalents relative to the organic compound), the organic compound, the catalyst (from 0.001 molar equivalents to 0.5 molar equivalents relative to the organic compound) and/or the solvent and/or the additive are added to a Schlenk tube that may optionally be sealed with a J. Young stopcock. The order in which the reagents are added is unimportant. 2. The reaction mixture is then agitated in an inert atmosphere at a temperature lying in the range 0° C. to 150° C. (preferably >40° C.) until the organic substrate is totally converted (reaction time in the range 1 minute to 72 hours). The reaction is monitored by .sup.1H (proton) NMR and/or by .sup.13C (carbon-13) NMR and/or by gas chromatography-mass spectrometry (GC-MS) and/or by thin-layer chromatography (TLC). Once the reaction is finished, and if the reaction has been conducted in a sealed tube, the pressure in the tube is released. In all cases, the solvent is evaporated in a vacuum. The resulting residue after evaporation of the solvent is then purified by distillation or by column chromatography on silica gel or on alumina.

[0502] This general protocol is exemplified below with transfer hydrosilylation of benzaldehyde in the presence of Et.sub.3SiOCHO and of the catalyst [Ru(κ.sup.1-OAc)(κ.sup.2-OAc)(κ.sup.3-triphos)]:

[0503] 1. In an inert atmosphere, in a glovebox, the catalyst Ru(κ.sup.1-OAc)(κ.sup.2-OAc)(κ.sup.3-triphos)] (8.5 mg; 0.01 mmol) and acetonitrile (2 mL) are added to a 10-mL Schlenk tube. The resulting reaction mixture is agitated for 5 minutes until a homogenous yellow solution is obtained, and then the benzaldehyde (51 μL; 0.5 mmol; 1 equiv.) and Et.sub.3SiOCHO (96 mg; 0.6 mmol; 1.2 equiv.) are added to the reaction medium. The Schlenk tube is then sealed and the reaction medium is agitated in an inert atmosphere at a temperature lying in the range 70° C. to conversion for 1 hour.

[0504] 3. The volatile compounds are evaporated in a vacuum and the resulting residue is purified by column chromatography on silica gel (99:1 petroleum ether/ethyl acetate). PhCH.sub.2OSiEt.sub.3 (colourless oil) is obtained with a yield of 91%.

Example 1: Transfer Hydrosilylation

[0505]

TABLE-US-00002 (1) [00011] Silylated Catalyst t (h)/ Yield formiate Substrate (% mol) Additive Solvent T (° C.) Product (%) Et.sub.3SiOCHO PhCHO [Ru(p- — MeCN 26/100 PhCH.sub.2OSiEt.sub.3 73 cymene)Cl.sub.2].sub.2 (2) Et.sub.3SiOCHO PhCHO [RuCl.sub.2(dmso).sub.4] triphos MeCN 1.5/95 PhCH.sub.2OSiEt.sub.3 >99 (4) Et.sub.3SiOCHO PhCHO [Ru(p- triphos MeCN 22/70 PhCH.sub.2OSiEt.sub.3 >99 cymene)Cl.sub.2].sub.2 (2) Et.sub.3SiOCHO PhCHO [Ru(p- PAdm.sub.3 MeCN 26/100 PhCH.sub.2OSiEt.sub.3 cymene)Cl.sub.2].sub.2 (2) Et.sub.3SiOCHO PhCHO Ru(Me- — MeCN 7/70 PhCH.sub.2OSiEt.sub.3 >99 allyl).sub.2(COD) (4) Et.sub.3SiOCHO PhCHO Ru(Me- dppp MeCN 3.5/70 PhCH.sub.2OSiEt.sub.3 >99 allyl).sub.2(COD) (4) Et.sub.3SiOCHO PhCHO Ru(Me- triphos MeCN 50 min/70 PhCH.sub.2OSiEt.sub.3 >99 allyl).sub.2(COD) (4) Et.sub.3SiOCHO PhCHO [Ru(k.sup.1-OAc)(k.sup.2- — MeCN >5 min/70 PhCH.sub.2OSiEt.sub.3 >99 OAc)(k.sup.3- triphos)] (4) Et.sub.3SiOCHO PhCHO [Ru(k.sup.1-OAc)(k.sup.2- — MeCN 14/TA PhCH.sub.2OSiEt.sub.3 >99 OAc)(k.sup.3- triphos)] (4) Et.sub.3SiOCHO PhCHO [Ru(k.sup.1-OAc)(k.sup.2- — MeCN 0.5/70 PhCH.sub.2OSiEt.sub.3 >99 OAc)(k.sup.3- triphos)] (2) Et.sub.3SiOCHO PhCHO [Ru(k.sup.1-OAc)(k.sup.2- — THF 0.5/70 PhCH.sub.2OSiEt.sub.3 >99 OAc)(k.sup.3- triphos)] (2) Me.sub.3SiOCHO PhCHO [Ru(k.sup.1-OAc)(k.sup.2- — MeCN 0.5/70 PhCH.sub.2OSiMe.sub.3 >99 OAc)(k.sup.3- triphos)] (2) Ph.sub.2MeSiOCHO PhCHO [Ru(k.sup.1-OAc)(k.sup.2- — MeCN 0.5/70 PhCH.sub.2OSiMePh.sub.2 >99 OAc)(k.sup.3- triphos)] (2) (EtO).sub.3SiOCHO PhCHO [Ru(k.sup.1-OAc)(k.sup.2- — MeCN 2/70 PhCH.sub.2OSi(OEt).sub.3 50 OAc)(k.sup.3- triphos)] (2) Et.sub.3SiOCHO [00012] [Ru(k.sup.1-OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (2) — MeCN 0.5/70 [00013] >99 Et.sub.3SiOCHO [00014] [Ru(k.sup.1-OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (2) — MeCN 0.5/70 [00015] >99 Et.sub.3SiOCHO [00016] [Ru(k.sup.1-OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (2) — MeCN 0.5/70 [00017] >99 Et.sub.3SiOCHO [00018] [Ru(k.sup.1-OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (2) — MeCN 0.5/70 [00019] >99 (95) Et.sub.3SiOCHO [00020] [Ru(k.sup.1-OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (2) — MeCN 0.5/70 [00021] >99 (92) Et.sub.3SiOCHO [00022] [Ru(k.sup.1-OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (2) — MeCN 0.5/70 [00023] >99 Et.sub.3SiOCHO [00024] [Ru(k.sup.1-OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (2) — MeCN 0.5/70 [00025] >99 Et.sub.3SiOCHO [00026] [Ru(k.sup.1-OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (2) — MeCN 0.5/70 [00027] >99 Et.sub.3SiOCHO [00028] [Ru(k.sup.1-OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (2) — MeCN 0.5/70 [00029] >99 Et.sub.3SiOCHO [00030] [Ru(k.sup.1-OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (2) — MeCN 0.5/70 [00031] 91 Et.sub.3SiOCHO [00032] [Ru(k.sup.1-OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (2) — MeCN 0.5/70 [00033] >99 Et.sub.3SiOCHO [00034] [Ru(k.sup.1-OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (2) — MeCN 1.5/70 [00035] >99 Et.sub.3SiOCHO [00036] [Ru(k.sup.1-OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (2) — MeCN 0.5/70 [00037] >99 Et.sub.3SiOCHO [00038] [Ru(k.sup.1-OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (2) — MeCN 0.5/70 [00039] >99 Et.sub.3SiOCHO [00040] [Ru(k.sup.1-OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (2) — MeCN 0.5/70 [00041] >99 Et.sub.3SiOCHO [00042] [Ru(k.sup.1-OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (2) — MeCN 0.5/70 [00043] >99 Et.sub.3SiOCHO [00044] [Ru(k.sup.1-OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (2) — MeCN 0.5/70 [00045] >99 (95) Et.sub.3SiOCHO [00046] [Ru(k.sup.1-OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (2) — MeCN 0.5/70 [00047] >99 (90) Et.sub.3SiOCHO [00048] [Ru(k.sup.1-OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (2) — MeCN 0.5/70 [00049] >99 Et.sub.3SiOCHO [00050] [Ru(k.sup.1-OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (2) — MeCN 0.5/70 [00051] >99 (85) Et.sub.3SiOCHO [00052] [Ru(k.sup.1-OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (2) — MeCN 0.5/70 [00053] >99 (98) Et.sub.3SiOCHO [00054] [Ru(k.sup.1-OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (2) — MeCN 0.5/70 [00055] >99 [00056]

[0506] Reaction conditions: silylated formiate (0.12-0.15 mmol); carbonyl (0.1 mmol); solvent (0.4 mL). The yields in parentheses are isolated yields after purification and are determined by adapting the preceding reaction conditions so that the quantity of substrate is 0.5 mmol.

[0507] The abbreviations used to describe the catalysts and the additives used are: dppp (1,3-bis(diphenylphosphino)propane); triphos (1,1,1-tris(diphenylphosphinomethyl)ethane); COD (cyclooctadiene); Me-allyl (methylallyl); dmso=dimethylsulfoxide; Adm=adamantyl, PAdm.sub.3=triadamantylephosphine.

[0508] All of the catalysts, ligands and aldehydes present in the table above are commercially available except for the complex [Ru(κ.sup.1-OAC)(κ.sup.2-OAc)(κ.sup.3-triphos)] that can easily be synthesised by a person skilled in the art from commercially available reagents according to the protocol described below.

##STR00057##

[0509] In a glovebox, in an inert atmosphere, the commercially available complex Ru(COD)(methylallyl).sub.2 (160 mg, 0.5 mmol, 1 equivalent), triphos (0.5 mmol, 312 mg, 1 equivalent) and 20 mL of anhydrous THF are added to a 100-mL round-bottom flask equipped with a J-Young valve. A yellow and homogeneous solution is obtained, to which the acetic acid (70 μL, 1.2 mmol, 2.4 equivalents) is added in one go using a syringe. The flask is then sealed, removed from the glovebox and heated at 90° C. in an oil bath for 15 hours. The reaction mixture is then cooled to ambient temperature (20° C.±5° C.) and the solvent and the volatile compounds are evaporated in a vacuum. A yellow solid is obtained and is taken up in about 5 mL of diethyl ether previously cooled to −20° C. The solid in suspension is then recovered by filtering through a Buchner funnel, washed with 5 mL of Et.sub.2O that is also cooled and dried in a high vacuum (10.sup.−2 mbars). The complex [Ru(κ.sup.1-OAc)(κ.sup.2-OAc)(triphos)] (323 mg, 78%) is obtained in the form of a yellow powder and is characterised.

[0510] .sup.1H NMR (200 MHz, CD.sub.2Cl.sub.2) δ 7.38 (m, 12H), 7.23-7.07 (m, 6H), 6.98 (t, J=6.8 Hz, 12H), 2.20 (s, 6H), 1.87 (s, 6H), 1.51 (s, 3H).

[0511] .sup.13C NMR (50 MHz, CD.sub.2Cl.sub.2) δ 181.74 (s), 137.27 (dd, J=29.0, 15.0 Hz), 132.78 (dd, J=6.4, 3.2 Hz), 129.30 (s), 128.06 (dd, J=6.4, 3.2 Hz), 39.07-38.41 (m), 38.32-37.57 (m), 35.00-33.74 (m), 25.66 (s).

[0512] .sup.31P NMR (81 MHz, CD.sub.2Cl.sub.2) δ 40.99 (s).

[0513] Elemental analysis: calcd (%) for C.sub.45H.sub.45O.sub.4P.sub.3Ru (843.84 g.Math.mol.sup.−1): C, 64.05, H, 5.38, found: C, 63.16, H, 5.32.

Example 2: Transfer Dehydrogenative Coupling

[0514]

TABLE-US-00003 (2) [00058] Silylated formiate Substrate Catalyst Additive t (h)/ Yield (mmol) (mmol) (mmol) (mmol) Solvent T (° C.) Product (%) Et.sub.3SiOCHO PhCH.sub.2OH [Ru(k.sup.1- — MeCN 0.5/70 PhCH.sub.2OSiEt.sub.3 >99 (0.15) (0.1) OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) Et.sub.3SiOCHO PhCH.sub.2OH [Ru(k.sup.1- — THF 4.5/70 PhCH.sub.2OSiEt.sub.3 >99 (0.15) (0.1) OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) Et.sub.3SiOCHO PhCH.sub.2OH [Ru(k.sup.1- — DCM 8.5/70 PhCH.sub.2OSiEt.sub.3 >99 (0.15) (0.1) OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) Et.sub.3SiOCHO PhCH.sub.2OH [Ru(k.sup.1- — CH.sub.3NO.sub.2 1.5/70 PhCH.sub.2OSiEt.sub.3 >99 (0.15) (0.1) OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) iPr.sub.3SiOCHO PhCH.sub.2OH [Ru(k.sup.1- — MeCN 2.5/70 PhCH.sub.2OSi(iPr).sub.3  31 (0.15) (0.1) OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) (OEt).sub.3SiOCHO. PhCH.sub.2OH [Ru(k.sup.1- — MeCN 18/70 PhCH.sub.2OSi(OEt).sub.3  93 (0.15) (0.1) OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) MePh.sub.2SiOCHO PhCH.sub.2OH [Ru(k.sup.1- — MeCN 1/70 PhCH.sub.2OSiMePh.sub.2 >99 (0.15) (0.1) OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) Me.sub.3SiOCHO PhCH.sub.2OH [Ru(k.sup.1- — MeCN 1/70 PhCH.sub.2OSiMe.sub.3 >99 (0.15) (0.1) OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) Et.sub.3SiOCHO (0.15) [00059] [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — MeCN 1/70 [00060]  93 iPr.sub.3SiOCHO (0.15) [00061] [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — MeCN 2.5/70 [00062] >99 (OEt).sub.3SiOCHO (0.15) [00063] [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — MeCN 18/70 [00064]  62 MePh.sub.2SiOCHO (0.15) [00065] [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — MeCN 1/70 [00066] >99 Me.sub.3SiOCHO (0.15) [00067] [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — MeCN 1/70 [00068] >99 Et.sub.3SiOCHO (0.15) [00069] [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — Dichloromethane (DCM) 1/70 [00070] >99 Et.sub.3SiOCHO (0.15) [00071] [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — Benzene 1/70 [00072] >99 Et.sub.3SiOCHO (0.15) [00073] [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — THF 1/70 [00074]  95 Et.sub.3SiOCHO (0.15) Acetoin (0.1) [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — MeCN 4/70 [00075]  27 Et.sub.3SiOCHO (0.15) [00076] [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — MeCN 1/70 [00077] >99 Et.sub.3SiOCHO (0.15) [00078] [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — MeCN 1/70 [00079] >99 Et.sub.3SiOCHO (0.15) [00080] [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — MeCN 1/70 [00081]  98 Et.sub.3SiOCHO (0.15) [00082] [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — MeCN 1/70 [00083] >99 Et.sub.3SiOCHO (0.15) [00084] [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — MeCN 1/70 [00085] >99 Et.sub.3SiOCHO (0.15) [00086] [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — MeCN 1/70 [00087] >99 Et.sub.3SiOCHO (0.15) [00088] [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — MeCN 1/70 [00089]  54 Et.sub.3SiOCHO (0.15) [00090] [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — MeCN 1/70 [00091]  95 Et.sub.3SiOCHO (0.15) [00092] [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — MeCN 5/70 [00093]  65 Et.sub.3SiOCHO (0.15) [00094] [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — MeCN 1/70 [00095]  90 Et.sub.3SiOCHO (0.15) [00096] [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — MeCN 1/70 [00097]  80 Et.sub.3SiOCHO (0.15) [00098] [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — MeCN 1/70 [00099] >99 Et.sub.3SiOCHO (0.15) [00100] [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — MeCN 1/70 [00101]  98 Et.sub.3SiOCHO (0.15) [00102] [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — MeCN 1/70 [00103] >99 Me.sub.3SiOCHO (0.15) [00104] [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — MeCN 1.5/70 [00105] >99 Me.sub.3SiOCHO (0.15) [00106] [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — MeCN 1/70 [00107]  98 Me.sub.3SiOCHO (0.15) [00108] [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — MeCN 1/70 [00109] >99 Et.sub.3SiOCHO (0.15) [00110] [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — MeCN 1/70 [00111] >99 Et.sub.3SiOCHO (0.15) [00112] [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — MeCN 1/70 [00113] >99 Et.sub.3SiOCHO (0.15) 4-methoxy- thiophenol (0.1) [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — MeCN 18/70 [00114]  31 Et.sub.3SiOCHO (0.15) Amino-heptane (0.1) [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — MeCN 0.5/70 [00115]  80 Et.sub.3SiOCHO (0.15) Amino-heptane (0.1) [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — MeCN 96/25 [00116]  80 Et.sub.3SiOCHO (0.15) Morpholine (0.1) [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — MeCN 1/70 [00117] >99 Et.sub.3SiOCHO (0.15) Morpholine (0.1) [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — MeCN 96/25 [00118] >99 Et.sub.3SiOCHO (0.15) 2-aminophenol (0.1) [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — MeCN 1/70 [00119] >99 Et.sub.3SiOCHO PhCH.sub.2OH Fe(OAc).sub.2 PP.sub.3 THF 20/70 PhCH.sub.2OSiEt.sub.3 >99 (0.15) (0.1) (5%) (5%) Et.sub.3SiOCHO PhCH.sub.2OH Fe(OAc).sub.2 PP.sub.3 benzene 4/70 PhCH.sub.2OSiEt.sub.3  84 (0.15) (0.1) (5%) (5%) Et.sub.3SiOCHO PhCH.sub.2OH Fe(OAc).sub.2 PP.sub.3 DCM 0.75/70 PhCH.sub.2OSiEt.sub.3 >99 (0.15) (0.1) (5%) (5%) Et.sub.3SiOCHO PhCH.sub.2OH FeCl.sub.2 PP.sub.3 DCM 0.75/70 PhCH.sub.2OSiEt.sub.3  53 (0.15) (0.1) (5%) (5%) Et.sub.3SiOCHO PhCH.sub.2OH Fe(acac).sub.2 PP.sub.3 DCM 0.75/70 PhCH.sub.2OSiEt.sub.3 >99 (0.15) (0.1) (5%) (5%) tBuMe.sub.2SiOCHO (0.15) [00120] [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — MeCN 1/70 [00121]  98 Et.sub.3SiOCHO (0.15) [00122] [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — MeCN 2.5/70 [00123] >99 Et.sub.3SiOCHO (0.15) [00124] [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — MeCN 2/70 [00125] >99 Et.sub.3SiOCHO (0.15) [00126] [Ru(k.sup.1- OAc)(k.sup.2- OAc)(k.sup.3- triphos)] (1%) — MeCN 3/70 [00127] >99 Et.sub.3SiOCHO PhCH.sub.2OH Fe(OAc).sub.2 PP.sub.3 DCM 5/70 PhCH.sub.2OSiEt.sub.3 >99 (0.12) (0.1) (2%) (2%) Et.sub.3SiOCHO PhCH.sub.2OH Fe(OAc).sub.2 PP.sub.3 DCM 24/70 PhCH.sub.2OSiEt.sub.3 >99 (0.12) (0.1) (1%) (1%) Et.sub.3SiOCHO PhCH.sub.2OH Fe(OAc).sub.2 PP.sub.3 DCM 21/20 PhCH.sub.2OSiEt.sub.3 >99 (0.12) (0.1) (2%) (2%) Me.sub.3SiOCHO PhCH.sub.2OH Fe(OAc).sub.2 PP.sub.3 DCM 3/70 PhCH.sub.2OSiMe.sub.3 >99 (0.12) (0.1) (2%) (2%) tBuMe.sub.2SiOCHO PhCH.sub.2OH Fe(OAc).sub.2 PP.sub.3 DCM 16/70 PhCH.sub.2OSitBuMe.sub.2  56 (0.12) (0.1) (2%) (2%) iPr.sub.3SiOCHO PhCH.sub.2OH Fe(OAc).sub.2 PP.sub.3 DCM 48/70 PhCH.sub.2OSiiPr.sub.3  34 (0.12) (0.1) (2%) (2%) Ph.sub.2MeSiOCHO PhCH.sub.2OH Fe(OAc).sub.2 PP.sub.3 DCM 1/70 PhCH.sub.2OSiPh.sub.2Me >99 (0.12) (0.1) (2%) (2%) PhMe.sub.2SiOCHO PhCH.sub.2OH Fe(OAc).sub.2 PP.sub.3 DCM 1/70 PhCH.sub.2OSiPhMe.sub.2 >99 (0.12) (0.1) (2%) (2%) Et.sub.2Si(OCHO).sub.2 PhCH.sub.2OH Fe(OAc).sub.2 PP.sub.3 DCM 1.5/70 (PhCH.sub.2O).sub.2SiEt.sub.2  85 (0.6) (0.1) (2%) (2%) Et.sub.3SiOCHO (0.12) [00128] Fe(OAc).sub.2 (2%) PP.sub.3 (2%) DCM 1.5/90 [00129]  96 Et.sub.3SiOCHO (0.12) [00130] Fe(OAc).sub.2 (2%) PP.sub.3 (2%) DCM 1.5/90 [00131] >99 Et.sub.3SiOCHO (0.12) [00132] Fe(OAc).sub.2 (2%) PP.sub.3 (2%) DCM 1.5/90 [00133]  97 Me.sub.3SiOCHO (0.12) [00134] Fe(OAc).sub.2 (2%) PP.sub.3 (2%) DCM 1.25/90 [00135]  84 Et.sub.3SiOCHO (0.12) [00136] Fe(OAc).sub.2 (2%) PP.sub.3 (2%) DCM 3/90 [00137]  91 Et.sub.3SiOCHO (0.12) [00138] Fe(OAc).sub.2 (2%) PP.sub.3 (2%) DCM 1.75/90 [00139]  90 Et.sub.3SiOCHO (0.12) [00140] Fe(OAc).sub.2 (2%) PP.sub.3 (2%) DCM 1.5/90 [00141]  87 Me.sub.3SiOCHO (0.12) [00142] Fe(OAc).sub.2 (2%) PP.sub.3 (2%) DCM 2/90 [00143]  92 Et.sub.3SiOCHO (0.12) [00144] Fe(OAc).sub.2 (2%) PP.sub.3 (2%) DCM 1/90 [00145]  96 Et.sub.3SiOCHO (0.12) [00146] Fe(OAc).sub.2 (2%) PP.sub.3 (2%) DCM 1/90 [00147]  97 Et.sub.3SiOCHO (0.12) [00148] Fe(OAc).sub.2 (2%) PP.sub.3 (2%) DCM 3.75/90 [00149]  94 Et.sub.3SiOCHO (0.12) [00150] Fe(OAc).sub.2 (2%) PP.sub.3 (2%) DCM 2.25/90 [00151] >99 Et.sub.3SiOCHO (0.24) [00152] Fe(OAc).sub.2 (2%) PP.sub.3 (2%) DCM 1.75/90 [00153]  96 Et.sub.3SiOCHO (0.12) [00154] Fe(OAc).sub.2 (2%) PP.sub.3 (2%) DCM 0.75/90 [00155]  97 [00156]DCM = dichloromethane.