Process for creating carbon-carbon bonds using carbonyl compounds

Patent metadata

Field	Value
Publication number	US-9656947-B2
Application number	US-201314406065-A
Country	US
Kind code	B2
Filing date	Jun 6, 2013
Priority date	Jun 6, 2012
Publication date	May 23, 2017
Grant date	May 23, 2017

Abstract

The present invention concerns a process for preparing a compound of formula (I) by reaction between a compound of formula (II) and a compound of formula (III) in the presence of a copper-containing catalyst, a ligand and base. The invention also concerns the implementing of this process for the preparation of building blocks to prepare molecules of interest in particular in the pharmaceutical, agro-chemical fields, etc.

First claim

The invention claimed is:

1. A process for preparing a compound of formula (I) by reaction between a compound of formula (II) and a compound of formula (III) in the presence of a copper-containing catalyst, a ligand and a base

where:
R 1 is:
a hydrogen atom,
a straight-chain or branched alkyl group having 1 to 15 carbon atoms,
a straight-chain or branched alkenyl group having 1 to 15 carbon atoms and comprising at least one double bond,
a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, or
a substituted or unsubstituted heteroaryl group having 5 to 10 members including at least one heteroatom selected in particular from among a nitrogen atom or oxygen atom;

R 2 is:
a straight-chain or branched alkyl group having 1 to 15 carbon atoms,
a straight-chain or branched alkenyl group having 1 to 15 carbon atoms and comprising at least one double bond,
a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, or
a substituted or unsubstituted heteroaryl group having 5 to 10 members including at least one heteroatom selected in particular from among a nitrogen atom or oxygen atom;

R 3 is:
a substituted or unsubstituted vinyl group,
a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, or
a substituted or unsubstituted heteroaryl group having 5 to 10 members including at least one heteroatom selected in particular from among a nitrogen atom or oxygen atom;

X is a halogen atom selected from among fluorine, chlorine, bromine and iodine, a tosylate group, or mesylate group; and
the ligand is selected from among:
diketones,
diamines, and
aromatic polycyclic compounds having at least two heteroatoms, unsubstituted or substituted by one or more C1 to C10 alkyl groups, NO 2 group, aryl group having 6 to 10 carbon atoms.

2. The process according to claim 1 wherein R 3 represents an aryl having 6 to 10 carbon atoms, unsubstituted or substituted by one or more substituents selected from among:
a straight-chain or branched group of formula —(O) n alkyl having 1 to 15 carbon atoms, optionally substituted by one or more halogen atoms, and n is 0 or 1;
a straight-chain or branched alkenyl group having 1 to 15 carbon atoms and comprising at least one double bond;
a halogen atom selected from among chlorine, fluorine, bromine or iodine;
a group of formula CN;
a group of formula NH 2 ;
a substituted or unsubstituted aryl group having 6 to 10 carbon atoms;
a group of formula (CH 2 ) m -aryl wherein m is an integer ranging from 1 to 10, and the aryl group, substituted or unsubstituted, comprises 6 to 10 carbon atoms.

3. The process according to claim 1 wherein R 3 represents a phenyl substituted by one or more substituents selected from among:
a straight-chain or branched group of formula —(O) n alkyl having 1 to 10 carbon atoms, and n is 0 or 1;
a straight-chain or branched trifluoroalkyl group having 1 to 10 carbon atoms;
a fluorine atom; and
a chlorine atom.

4. The process according to claim 1 wherein the formula (II) compound is a compound of formula (IIa)

where:
X is such as defined for the formula (II) compound;
R 4 , R 5 and R 6 , the same or different, represent:
a hydrogen atom;
a straight-chain or branched alkyl group having 1 to 15 carbon atoms, possibly comprising one or more unsaturations;
a substituted or unsubstituted aryl group having 6 to 10 carbon atoms;
a halogen atom selected from among chlorine, bromine, fluorine and iodine.

5. The process according to claim 1 wherein R 3 represents a heteroaryl having 5 to 10 members including at least one heteroatom selected from among a nitrogen atom or oxygen atom, unsubstituted or substituted by one or more substituents selected from among:
a straight-chain or branched group of formula —(O) n alkyl having 1 to 15 carbon atoms, optionally substituted by one or more halogen atoms and n is 0 or 1;
a straight-chain or branched alkenyl group having 1 to 15 carbon atoms and comprising at least one double bond;
a halogen atom selected in particular from among chlorine, fluorine, bromine and iodine.

6. The process according to claim 1 wherein for the compounds of formula (I) and (III), R 1 is selected from among:
a hydrogen atom;
a straight-chain or branched alkyl group having 1 to 15 carbon atoms;
a straight-chain or branched alkenyl group having 1 to 15 carbon atoms and comprising at least one double bond;
an aryl group having 6 to 10 carbon atoms, unsubstituted or substituted by one or more substituents selected from among:
a halogen atom selected from among chlorine, bromine, fluorine or iodine;
a straight-chain or branched group of formula —(O) p alkyl having 1 to 15 carbon atoms and p is 0 or 1;
a hydroxy group;
a straight-chain or branched alkenyl group having 1 to 15 carbon atoms and comprising at least one double bond; and
a straight-chain or branched trifluoroalkyl having 1 to 10 carbon atoms.

7. The process according to claim 1 wherein for the compounds of formula (I) and (III), R 2 is selected from among:
a straight-chain or branched alkyl group having 1 to 15 carbon atoms;
a straight-chain or branched alkenyl group having 1 to 15 carbon atoms and comprising at least one double bond;
an aryl group having 6 to 10 carbon atoms unsubstituted or substituted by one or more substituents selected from among:
a halogen atom selected from among chlorine, bromine, fluorine or iodine;
a hydroxy group;
a straight-chain or branched group of formula —(O) q alkyl having 1 to 15 carbon atoms, and q is 0 or 1;
a straight-chain or branched alkenyl group having 1 to 15 carbon atoms and comprising at least one double bond; and
a straight-chain or branched trifluoroalkyl group having 1 to 10 carbon atoms.

8. The process according to claim 1 wherein X represents iodine.

9. The process according to claim 1 wherein the catalyst is selected from among metallic copper, copper(I) or copper(II) oxides, copper(I) or copper(II) hydroxides, inorganic or organic salts of copper(I) or copper(II) and complexes of copper(I) or copper(II) with ligands, or mixtures thereof.

10. The process according to claim 1 implemented in the presence of a solvent selected from among dioxane and tert-butanol.

11. The process according to claim 1 wherein the ligand is selected from among:
diketones of formula (i):

where:
R a and R b , the same or different, represent a straight-chain or branched C 1 to C 10 alkyl chain, or C 6 to C 10 aryl radical;
R c and R d are a hydrogen atom; or
R a or R b , together with their carrier group C(O) and with one of R c or R d , forms a 6-membered carbocycle; and
diamines of formula (ii)
NR e R f —(CH 2 ) r —NR g R h   (ii)

where:
R e , R f , R g , R h , the same or different, represent a hydrogen atom or C 1 to C 10 alkyl group;
r is an integer ranging from 1 to 10; or
aromatic polycyclic compounds having at least two heteroatoms, unsubstituted or substituted by one or more C 1 to C 10 alkyl groups, NO 2 group, aryl group having 6 to 10 carbon atoms.

12. The process according to claim 1 wherein the ligand is selected from among the compounds of formula:

13. The process according to claim 1 wherein the

Assignees

• Centre Nat De La Rech Scient (C N R S )
• Univ Montpellier 2 Sciences Et Techniques
• Enscm
• Centre Nat De La Rech Scient (C N R S)

Inventors

• Taillefer Marc
• Monnier Florian
• Tlili Anis
• Danoun Grégory

Classifications

• C07C49/813

  polycyclic · CPC title

• C07C37/20 Primary

  using aldehydes or ketones · CPC title

• C07C217/18

  the six-membered aromatic ring or condensed ring system containing that ring being further substituted · CPC title

• C07C213/06

  from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups · CPC title

• C07C49/83

  polycyclic · CPC title