Use for boron formates for reducing unsaturated organic functions

Patent metadata

Field	Value
Publication number	US-10273250-B2
Application number	US-201615774844-A
Country	US
Kind code	B2
Filing date	Nov 8, 2016
Priority date	Nov 10, 2015
Publication date	Apr 30, 2019
Grant date	Apr 30, 2019

Abstract

The invention also relates to the use of the method for reducing unsaturated organic compounds chosen from the group formed by the aldehydes, the ketones, the imines, the carboxylic acids, the amides, and the esters according to the invention in the preparation of methanol, methylated amines, formaldehyde and alcohols; for the preparation of reactants for Suzuki coupling reactions; and in the manufacturing of vitamins, pharmaceutical products, glues, acrylic fibers, synthetic leather, pesticides.

First claim

The invention claimed is:

1. A method for reducing unsaturated organic compounds chosen from the group formed by the aldehydes, the ketones, the imines, the carboxylic acids, the amides, and the esters, wherein said unsaturated organic compound is reacted with a boron formate having the formula (I)

in which
R 1 and R 2 , independently of one another, are chosen from the group formed by a hydroxyl group, an alkoxy group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, a heterocyclic group, a halogen atom, a silyl group, a siloxy group, a phosphino group, and an amino group, said alkyl, alkenyl, alkynyl, alkoxy, silyl, siloxy, aryl, phosphino and amino groups being optionally substituted; or
R 1 and R 2 taken together with the boron atom to which they are bonded, form an optionally substituted heterocycle;
X is chosen from the group formed by a halogen atom, a carboxylate group, a sulfonate group, a hydroxyl group, an alkoxy group, an alkyl group, an alkenyl group, an alkynyl group, a heteroaryl group, a heterocyclic group, a silyl group,
Z is a cation chosen from the group formed by a protonated organic base having a pKa greater than 3.7 chosen from the group formed by triethylammonium (HNEt 3 + ), di-isopropylethylammonium (i-Pr 2 EtNH + ), 2,2,6,6-tetramethylpiperidinium (TMPH + ), and tricyclohexylphosphonium (HPCy 3 + ); Na + ; Li + ; K + ; Cs + ; tetraphenylphosphonium (PPh 4 + ); tetramethylammonium (NMe 4 + ); tetraethylammonium (NEt 4 + ); tetrabutylammonium (NBu 4 + ) and tetraphenylammonium (NPh 4 + );
n is a whole number equal to 1;

in the presence of a solvent and optionally an organic or inorganic base.

2. The method according to claim 1 , wherein
the aldehydes, the ketones, the carboxylic acids and the esters, are reduced into alcohols;
the imines are reduced into amines; and
the amides are reduced into amines or into alcohols.

3. The method according to claim 1 , wherein in the boron formate having the formula (I),
R 1 and R 2 , independently of one another, are chosen from the group formed by an alkyl group comprising 1 to 12 atoms of carbon; an aryl comprising 6 to 20 atoms of carbon, said alkyl group and aryl groups being optionally substituted.

4. The method according to claim 1 , wherein in the boron formate having the formula (I),
R 1 and R 2 taken together with the atom of boron to which they are bonded, form a heterocycle comprising 5 to 10 members, said heterocycle being optionally substituted.

5. The method according to claim 1 , wherein in the boron formate having the formula (I), X is chosen from the group formed a halogen atom, —OCHO and a sulfonate group having the formula —OSO 2 R 7 , in which R 7 is chosen from a methyl group (CH 3 ), a trifluoromethyl group (CF 3 ), a toluene group (p-CH 3 C 6 H 4 ) and a benzene group (C 6 H 5 ).

6. The method according to claim 1 , wherein Z is a cation chosen from the group formed by triethylammonium (HNEt 3 + ), di-isopropylethylammonium (i-Pr 2 EtNH + ), 2,2,6,6-tetramethylpiperidinium (TMPH + ), tricyclohexylphosphonium (HPCy 3 + ), and Na + .

7. The method according to claim 1 , wherein the boron formates having the formula (I) are [Et 3 NH + , BCy 2 (OCHO) 2 − ], [i-Pr 2 EtNH + , BCy 2 (OCHO) 2 − ], [Et 3 NH + , n-Bu 2 B(OCHO) 2 − ], [Et 3 NH + , BBN(OCHO) 2 − ], [i-Pr 2 EtNH + , BBN(OCHO) 2 − ], [Na + , BBN(OCHO) 2 − ], [Cy 3 PH + , BBN(OCHO) 2 − ] and [TMPH + , BBN(OCHO) 2 − ].

8. The method according to claim 1 , wherein it takes place in one or a mixture of at least two solvents chosen from the group formed by:
the ethers chosen from diethyl ether, THF, diglyme, 1,4-dioxane;
the hydrocarbons chosen from benzene, or toluene;
the nitrogenous solvents chosen from pyridine, or acetonitrile;
the sulfoxides chosen from dimethyl sulfoxide;
the alkyl halides chosen from chloroform, or methylene chloride; and
a supercritical fluid chosen from supercritical CO 2 .

9. The method according to claim 1 , wherein the quantity of the unsaturated organic compounds to be reduced is from 0.5 to 2 molar equivalents, with respect to the boron formate having the formula (I).

10. The method according to claim 1 , wherein it takes place in the presence of an additive chosen from:
the crown ethers chosen from the group formed by 12-crown-4, 15-crown-5, 18-crown-6, dibenzo-18-crown-6, benzo-18-crown-6, benzo-15-crown-5, and dibenzo-15-crown-5;
the aza-crowns chosen from the group formed by 1,4,7,10-tetraazacyclododecane (cyclen), 1,4,7,10,13,16-hexaazacyclooctadecane (hexacyclen), and diaza-18-crown-6;
the crown thioethers chosen from the group formed by 1,5,9,13-tetrathiacyclohexadecane (16-Ane-S 4 ), and 1,4,7,10,13,16-hexathiacyclooctadecane (18-Ane-S 6 ).

11. The method according to claim 10 , wherein the quantity of additive is from 1 to 2 molar equivalents, inclusive, with respect to the boron formate having the formula (I).

12. The method according to claim 1 , wherein when n=1, the boron formate has the general formula (Ib)

and in that the reduction takes place in the absence of a base.

13. A method for preparing methanol, comprising
(i) a step of reducing formic acid or one of its esters having the formula HCO 2 R 8 in which R 8 is chosen from a hydrogen atom, an alkyl group, and an aryl group, with a boron formate having the formula (I) according to the method of claim 1 ,
and optionally
(ii) a step of hydrolysis.

14. A method for preparing methylated amines having the formula R 1 R 2 N—CH 3 with R 1 and R 2 as defined in claim 1 , comprising
(i) a step of reducing formic acid in the presence of a primary amine or a secondary amine, with a boron formate having the formula (I) according to the method of claim 1 , and
(ii) distillation or concentration under vacuum or column chromatography.

15. A method for preparing formaldehyde, comprising a step of reducing formic acid or one of its esters having the formula HCO 2 R 8 in which R 8 in which R 8 is R 8 is chosen from a hydrogen atom, an alkyl group, and an aryl group, with a boron formate having the formula (I) according to the method of claim 1 ,
and optionally
(ii) a step of hydrolysis.

16. A method for preparing an alcohol having the formula R 1 CH 2 OH with R 1 as defined in claim 1 , comprising
(i) a step of reducing an unsaturated organic compound chosen from the group formed by the aldehydes, the carboxylic acids and the esters with a boron formate having the formula (I) according to the method of claim 1 , and optionally
(ii) a step of hydrolysis.

Assignees

• Commissariat Energie Atomique

Inventors

• Chauvier Clément
• Cantat Thibault

Classifications

• C07B31/00

  Reduction in general · CPC title

• C07C209/50

  by reduction of carboxylic acid amides · CPC title

• C07C29/147

  of carboxylic acids or derivatives thereof · CPC title

• C07C29/14

  of a —CHO group · CPC title

• C07C209/52

  by reduction of imines or imino-ethers (C07C209/24 takes precedence) · CPC title