P-chirogenic organophosphorus compounds

Patent metadata

Field	Value
Publication number	US-9707553-B2
Application number	US-201514876072-A
Country	US
Kind code	B2
Filing date	Oct 6, 2015
Priority date	Jul 11, 2011
Publication date	Jul 18, 2017
Grant date	Jul 18, 2017

Abstract

P-chirogenic organophosphorus compounds of general formula (I), a process for the synthesis of the compounds of formula (I), and intermediate products of general formulae (II), (III) and (IV), as shown below, are involved in the synthesis of compounds (I).

Metal complexes comprising compounds (I) as ligands are also described. The compounds and complexes are useful in asymmetric catalysis by transition metal complexes or organocatalysis, especially for asymmetric hydrogenation or allylation. Compounds of general formula (I) may be useful as agrochemical and therapeutic substances, or as reagents or intermediates for fine chemistry.

First claim

The invention claimed is:

1. A process for producing a compound of formula (I)

wherein
R1 and R2 may be the same or different and represent each a substituted or unsubstituted group selected from alkyl, cycloalkyl, aryl, alkyloxy, cycloalkyloxy, aryloxy, alkylamino, cycloalkylamino, arylamino, and metallocenyl;
R3, R4, R5, R6 may be the same or different and represent each a hydrogen atom or a substituted or unsubstituted group selected from the group consisting of alkyloxy, cycloalkyloxy, aryloxy, alkylamino, cycloalkylamino, and arylamino;
E represents a substituted or unsubstituted group —BR9R10;
wherein
R9 and R10 may be the same or different and represent each an halogen, an hydroxyl, a substituted or unsubstituted group selected from the group consisting of alkyloxy, aryloxy, cycloalkyloxy, alkyl cycloalkyl and aryl;

comprising
(i) reacting chlorophosphine borane (VII)

wherein R1 and R2 are as defined above,

with a reagent RM, in which M is Li and R is an alkyl or an aryl group; and
further reacting the product of this halogen-metal exchange with an aromatic compound of formula (VI)

wherein X and Y may be the same or different and each represent F, Cl, Br, or I, and R3, R4, R5and R6 are as defined above,

resulting in the corresponding P-chirogenic phosphine borane of formula (IV)

wherein X, R1, R2, R3, R4, R5 and R6 are as defined above;

wherein step (i) is carried out under cooling condition, at a temperature ranging from −110° C. to −10° C.; and
(ii) performing two chemical transformations on compound (IV) leading to compound (I): a step (ii-a) of removing of the borane group and a step (ii-b) of coupling of an electrophilic reagent, which is a boronate reagent, on the ortho position; steps (ii-a) and (ii-b) being carried out in any order.

2. The process according to claim 1 , wherein compound (VII) is chiral.

3. The process according to claim 1 , wherein compound (IV) first reacts under conditions of step (ii-a) leading to intermediate compound of formula (II),

wherein R1, R2, R3, R4, R5, R6 and X are as previously defined.

4. The process according to claim 1 , wherein compound (IV) first reacts under conditions of step (ii-b) leading to intermediate compound of formula (III),

wherein R1, R2, R3, R4, R5, R6 and E are as previously defined.

Assignees

• Centre Nat De La Rech Scient (Cnrs)
• Univ Bourgogne
• Univ Strasbourg
• Synthelor Sas

Inventors

• Juge Sylvain
• Bayardon Jerome
• Remond Emmanuelle
• Laureano Hugo
• Henry Jean-Christophe
• Leroux Frederic
• Colobert Francoise

Classifications

• C07B37/04

  Substitution · CPC title

• C07F15/00

  Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table · CPC title

• C07F9/50

  Organo-phosphines · CPC title

• C07F17/00

  Metallocenes · CPC title

• C07F9/6596

  having atoms other than oxygen, sulfur, selenium, tellurium, nitrogen or phosphorus as ring hetero atoms · CPC title