Hydrosilane/Lewis acid adduct, particularly aluminum, iron, and zinc, method for preparing same, and use of said same in reactions for reducing carbonyl derivatives

Patent metadata

Field	Value
Publication number	US-10099986-B2
Application number	US-201615547425-A
Country	US
Kind code	B2
Filing date	Jan 29, 2016
Priority date	Jan 30, 2015
Publication date	Oct 16, 2018
Grant date	Oct 16, 2018

Abstract

Disclosed is an adduct between a Lewis acid, preferably aluminum trichloride, iron trichloride, or zinc dichloride, and a hydrosilane;—a method for preparing same; and a method for for reducing, particularly, an aldehyde, a ketone, an α,β-unsaturated ketone, an imine, or an α,β-unsaturated imine.

First claim

The invention claimed is:

1. A pre-formed adduct between a Lewis acid selected from the salts of zinc (II), tin (II) or (IV), iron (II) or iron (III), copper (I), palladium (II), titanium (III) or (IV), bismuth (III) or aluminium (III) and a hydrosilane.

2. The adduct according to claim 1 , wherein the Lewis acid is a salt of zinc (II), a salt of iron (III), or a salt of aluminium (III).

3. The adduct according to claim 1 , wherein the hydrosilane is selected from the group selected from consisting of trialkylsilanes, tris(trimethylsilyl)silane, triphenylsilane, polymethylhydrosiloxanes (PMHS), polydimethylsiloxanes having a terminal Si—H group, a methylhydro-dimethylsiloxane copolymer, a methylhydrophenyl-methylsiloxane copolymer, a methylhydrocyanopropylsiloxane copolymer, a methylhydromethyloctylsiloxane copolymer, poly(1,2-dimethylhydrosilazane), a 1-methyl-hydrosilazane (1,2-dimethylhydrosilazane) copolymer, and methylhydrocyclosiloxane.

4. The adduct according to claim 3 , wherein the hydrosilane is selected from the group consisting of polymethylhydrosiloxane, tetramethyldisiloxane and triethylsilane.

5. The adduct according to claim 1 , further comprising another Lewis acid, a metal salt, an alcohol, or a dihalogen.

6. The adduct according to claim 5 , comprising an alcohol.

7. An adduct AlCl 3 /triethylsilane/isopropanol in a molar ratio of 0.3:1:0.6.

8. An adduct FeCl 3 /triethylsilane/iso-propanol or FeCl 3 /triethylsilane /tert-butanol in a molar ratio of x:1:2x, where X varies from 0.01 to 1.

9. A method for performing a reaction of reduction of an aldehyde, an α,β-unsaturated aldehyde, a ketone, an α,β-unsaturated ketone, an imine, or an α,β-unsaturated imine, comprising providing the adduct of claim 1 , and combining the adduct with the aldehyde, α,β-unsaturated aldehyde, ketone, α,β-unsaturated ketone, imine, or α,β-unsaturated imine.

10. The method according to claim 9 , wherein the reduction is of a ketone or an α,β-unsaturated ketone.

11. The method according to claim 9 , wherein the reduction is of a ketone, an α,β-unsaturated ketone, an imine, or an α,β-unsaturated imine of formula (Ia):

in which:
X is O or N R a , R a being selected from the group consisting of a linear or branched alkyl having at most 12 carbon atoms, a linear or branched alkylene having at most 6 carbon atoms, a carbocyclic or heterocyclic aryl, and an aralkyl radical, each of said alkyl, alkylene, aralkyl or aryl radicals being optionally substituted,
is a single bond or a double bond,

R 1 is a linear or branched alkyl radical having at most 12 carbon atoms, a linear or branched alkylene having at most 12carbon atoms, or a saturated or unsaturated cycloalkyl radical having 3 to 7 carbon atoms and optionally comprising one or more heteroatoms selected from nitrogen, sulfur or oxygen atoms, a carbocyclic or heterocyclic aryl radical, an aralkyl radical, each of said alkyl, alkylene, aralkyl or aryl radicals being optionally substituted,
R 2 is hydrogen, linear or branched alkyl having at most 12 carbon atoms, a linear or branched alkylene having at most 6carbon atoms, a carbocyclic or heterocyclic aryl, or an aralkyl radical, each of said alkyl, alkylene, aralkyl or aryl radicals being optionally substituted,
R 3 and R 4 , which are identical or different, are hydrogen, a linear or branched alkyl having at most 12 carbon atoms, a linear or branched alkylene having at most 6 carbon atoms, a carbocyclic or heterocyclic aryl, or an aralkyl radical, each of said alkyl, alkylene, aralkyl or aryl radicals being optionally substituted, and
when is a single bond,
R 5 is hydrogen, a linear or branched alkyl having at most 12 carbon atoms, a linear or branched alkylene having at most 12 carbon atoms, a carbocyclic or heterocyclic aryl, or an aralkyl radical, each of said alkyl, alkylene, aralkyl or aryl radicals being optionally substituted, and
R 6 is hydrogen, a linear or branched alkyl having at most 12 carbon atoms, a linear or branched alkylene having at most 12 carbon atoms, a carbocyclic or heterocyclic aryl, or an aralkyl radical, each of said alkyl, alkylene, aralkyl or aryl radicals being optionally substituted,
or a cyclic ketone, α, β-unsaturated ketone, imine or α, β-unsaturated imine of formula (Ib):

in which:
n =0 or 1,
X and are as defined above,
R 7 is a linear or branched alkyl radical having at most 12 carbon atoms, a linear or branched alkylene having at most 12carbon atoms, or a saturated or unsaturated cycloalkyl radical having 3 to 7 carbon atoms and optionally comprising one or more heteroatoms selected from nitrogen, sulfur or oxygen atoms, a carbocyclic or heterocyclic aryl radical, an aralkyl radical, each of said alkyl, alkylene, aralkyl, aryl or cycloalkyl radicals being optionally substituted,
R 9 is a hydrogen, a linear or branched alkyl radical having at most 12 carbon atoms, a linear or branched alkylene having at most 12 carbon atoms, or a saturated or unsaturated cycloalkyl radical having from 3 to 7 carbon atoms and optionally comprising one or more heteroatoms selected from nitrogen, sulfur or oxygen atoms, a carbocyclic or heterocyclic aryl radical, an aralkyl radical, each of said alkyl, alkylene, aralkyl or aryl radicals being optionally substituted, or a CHR 12 —COOR 13 group, in which R 12 is hydrogen or a linear or branched alkyl radical having at most 12 carbon atoms, and R 13 is a linear or branched alkyl radical having at most 12 carbon atoms or a saturated or unsaturated cycloalkyl radical having from 3 to 7 carbon atoms, and optionally comprising one or more heteroatoms selected from nitrogen, sulfur or oxygen atoms, a carbocyclic aryl radical, an aralkyl radical, each of said alkyl, alkylene, aralkyl or aryl radicals being optionally substituted, and
when is a single bond,
R 8 , and R 10 , which are identical or different, are a hydrogen, a linear or branched alkyl radical having at most 12carbon atoms, a linear or branched alkylene having at most 12carbon atoms, or a saturated or unsaturated cycloalkyl radical having from 3 to 7 carbon atoms and optionally comprising one or more heteroatoms selected from nitrogen, sulfur or oxygen atoms, a carbocyclic or heterocyclic aryl radical, an aralkyl radical, each of said alkyl, alkylene, aralkyl or aryl radicals being optionally substituted, or a CHR 12 —COOR 13 group, in which R 12 is hydrogen or a linear or branched alkyl radical having at most 12 carbon atoms, and R 13 is a linear or branched alkyl radical having at most 12 carbon atoms or a saturated or unsaturated cycloalkyl radical having from 3 to 7 carbon atoms, and optionally comprising one or more heteroatoms selected from nitrogen, sulfur or oxygen atoms, a carbocyclic aryl radical,
R 11 is hydrogen, a linear or branched alkyl radical having at most 12 carbon atoms, a linear or branched alkylene having at most 12 carbon atoms, or a saturated or unsaturated cycloalkyl radical having from 3 to 7 carbon atoms and optionally comprising one or more heteroatoms selected from nitrogen, sulfur or oxygen atoms, a carbocyclic or heterocyclic aryl radical, an aralkyl radical, each of said alkyl, alkylene, aralkyl or aryl radicals being optionally substituted, advantageously an alkyl radical having at most 12 carbon atoms,
or, when is a single bond, R 7 and R 8 are together a ═CH—R 7a group where R 7a i

Assignees

• Centre Nat Rech Scient
• Univ Montpellier

Inventors

• Grison Claude
• Escande Vincent

Classifications

• C01F7/56

  Chlorides (containing fluorine C01F7/52) · CPC title

• C07C29/175

  with simultaneous reduction of an oxo group · CPC title

• C07C45/62

  by hydrogenation of carbon-to-carbon double or triple bonds · CPC title

• C01G9/04

  Halides · CPC title

• C07F7/0896

  Compounds with a Si-H linkage · CPC title