Processes for the preparation of pyrrolidine intermediates

Patent metadata

Field	Value
Publication number	US-9469633-B2
Application number	US-201214346773-A
Country	US
Kind code	B2
Filing date	Sep 28, 2012
Priority date	Oct 3, 2011
Publication date	Oct 18, 2016
Grant date	Oct 18, 2016

Abstract

The present invention relates to processes for the enantio-selective preparation of spyrrolidine derivatives useful in the manufacture of pesticidally active compounds, as well as to intermediates in the processes. The processes include those comprising
(a-i) reacting a compound of formula Ia

wherein

P is alkyl, aryl or heteroaryl, each optionally substituted, wherein the heteroaryl is connected at P via a ring carbon atom;

R 1 is chlorodifluoromethyl or trifluoromethyl;

R 2 is aryl or heteroaryl, each optionally substituted;

with a source of cyanide in the presence a chiral catalyst to give a compound of formula IIa

wherein P, R 1 and R 2 are as defined for the compound of formula Ia; and

(a-ii) oxidizing the compound of formula IIa with a peroxy acid, or peroxide in the presence of an acid to give a compound of formula VI

wherein R 1 and R 2 are as defined for the compound of formula Ia.

First claim

The invention claimed is:

1. A compound, wherein the compound is a compound of formula IIc,

wherein
P is alkyl, hydroxy, alkoxy, aryloxy, alkylsulfinyl, or arylsulfinyl, each optionally substituted,
R 1 is chlorodifluoromethyl or trifluoromethyl, and
R 2 is aryl or heteroaryl, each optionally substituted;
a compound of formula III,

wherein
R 1 is chlorodifluoromethyl or trifluoromethyl, and
R 2 is aryl or heteroaryl, each optionally substituted;
a compound of formula IV,

wherein
P is hydroxy, alkoxy, aryloxy, alkylsulfinyl, arylsulfinyl, aryl or heteroaryl, each optionally substituted, and wherein the heteroaryl contains at least one ring nitrogen atom, and the heteroaryl is connected at P via a ring nitrogen atom,
R 1 is chlorodifluoromethyl or trifluoromethyl, and
R 2 is aryl or heteroaryl, each optionally substituted;
a compound of formula V,

wherein
P is hydroxy, alkoxy, aryloxy, alkylsulfinyl, arylsulfinyl, aryl or heteroaryl, each optionally substituted, and wherein the heteroaryl contains at least one ring nitrogen atom, and the heteroaryl is connected at P via a ring nitrogen atom,
R 1 is chlorodifluoromethyl or trifluoromethyl, and
R 2 is aryl or heteroaryl, each optionally substituted;
a compound of formula VI,

wherein
R 1 is chlorodifluoromethyl or trifluoromethyl, and
R 2 is aryl or heteroaryl, each optionally substituted;
a compound of formula VII,

wherein
R 1 is chlorodifluoromethyl or trifluoromethyl, and
R 2 is aryl or heteroaryl, each optionally substituted;
a compound of formula VIII,

wherein
R 1 is chlorodifluoromethyl or trifluoromethyl, and
R 2 is aryl or heteroaryl, each optionally substituted;
a compound of formula X,

wherein
R 1 is chlorodifluoromethyl or trifluoromethyl, and
R 2 is aryl or heteroaryl, each optionally substituted;
a compound of formula XIV,

wherein
P is hydroxy, alkoxy, aryloxy, alkylsulfinyl, arylsulfinyl, aryl or heteroaryl, each optionally substituted, and wherein the heteroaryl contains at least one ring nitrogen atom, and the heteroaryl is connected at P via a ring nitrogen atom,
R 1 is chlorodifluoromethyl or trifluoromethyl,
R 2 is aryl or heteroaryl, each optionally substituted, and
A′ is optionally substituted aryl or optionally substituted heteroaryl;
a compound of formula XV,

wherein
R 1 is chlorodifluoromethyl or trifluoromethyl,
R 2 is aryl or heteroaryl, each optionally substituted, and
A′ is optionally substituted aryl or optionally substituted heteroaryl;
a compound of formula XVIII,

wherein
P is alkyl, aryl or heteroaryl, each optionally substituted, wherein the heteroaryl is connected at P via a ring carbon atom,
R 1 is chlorodifluoromethyl or trifluoromethyl, and
R 2 is aryl or heteroaryl, each optionally substituted; or
a compound of formula XII,

wherein
R 1 is chlorodifluoromethyl or trifluoromethyl,
R 2 is aryl or heteroaryl, each optionally substituted, and
A′ is optionally substituted aryl or optionally substituted heteroaryl.

2. A compound of claim 1 , wherein the compound is of formula XII,

wherein
R 1 is chlorodifluoromethyl or trifluoromethyl,
R 2 is aryl or heteroaryl, each optionally substituted, and
A′ is optionally substituted aryl or optionally substituted heteroaryl.

3. A mixture comprising a compound of IIc and a compound of formula IIcA,

wherein
P is alkyl, hydroxy, alkoxy, aryloxy, alkylsulfinyl, or arylsulfinyl, each optionally substituted,
R 1 is chlorodifluoromethyl or trifluoromethyl,
R 2 is aryl or heteroaryl, each optionally substituted, and
wherein the mixture is enriched for the compound of formula IIc;
a mixture comprising a compound of formula III and a compound of formula IIIA,

wherein
R 1 is chlorodifluoromethyl or trifluoromethyl,
R 2 is aryl or heteroaryl, each optionally substituted, and
wherein the mixture is enriched for the compound of formula III;
a mixture comprising a compound of formula IV and a compound of formula IVA,

P is hydroxy, alkoxy, aryloxy, alkylsulfinyl, arylsulfinyl, aryl or heteroaryl, each optionally substituted, and wherein the heteroaryl contains at least one ring nitrogen atom, and the heteroaryl is connected at P via a ring nitrogen atom,
R 1 is chlorodifluoromethyl or trifluoromethyl,
R 2 is aryl or heteroaryl, each optionally substituted, and
wherein the mixture is enriched for the compound of formula IV;
a mixture comprising a compound of formula V and a compound of formula VA,

wherein
P is hydroxy, alkoxy, aryloxy, alkylsulfinyl, arylsulfinyl, aryl or heteroaryl, each optionally substituted, and wherein the heteroaryl contains at least one ring nitrogen atom, and the heteroaryl is connected at P via a ring nitrogen atom,
R 1 is chlorodifluoromethyl or trifluoromethyl,
R 2 is aryl or heteroaryl, each optionally substituted, and wherein the mixture is enriched for the compound of formula V;
a mixture comprising a compound of formula VI and a compound of formula VIA

wherein
R 1 is chlorodifluoromethyl or trifluoromethyl,
R 2 is aryl or heteroaryl, each optionally substituted, and
wherein the mixture is enriched for the compound of formula VI;
a mixture comprising a compound of formula VII and a compound of formula VIIA

Assignees

• Syngenta Participations Ag

Inventors

• Smejkal Tomas
• Smits Helmars
• Wendeborn Sebastian Volker
• Berthon Guillaume
• Cassayre Jerome Yves
• El Qacemi Myriem

Classifications

• C07C253/30

  by reactions not involving the formation of cyano groups · CPC title

• C07D207/333

  Radicals substituted by oxygen or sulfur atoms · CPC title

• C07D207/40 Primary

  2,5-Pyrrolidine-diones · CPC title

• C07D307/46

  Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom · CPC title

• C07D409/12

  linked by a chain containing hetero atoms as chain links · CPC title