Syntheses of allyl phosphine complexes of palladium

Patent metadata

Field	Value
Publication number	US-10968244-B2
Application number	US-201916686960-A
Country	US
Kind code	B2
Filing date	Nov 18, 2019
Priority date	Jun 12, 2014
Publication date	Apr 6, 2021
Grant date	Apr 6, 2021

Abstract

The present invention provides a palladium(II) complex of formula (1) or a palladium(II) complex of formula (2).

R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 and R 24 , m, E and X are described in the specification.
The invention also provides a process for the preparation of the complexes, and their use in carbon-carbon and carbon-heteroatom coupling reactions.

First claim

What is claimed is:

1. A process for preparing a complex of formula (1), the process comprising the step of reacting a complex of formula (3) with a monodentate biaryl ligand of formula (4) to form the complex of formula (1),

wherein,
R 1 and R 2 are, independently, substituted or unsubstituted and are straight-chain alkyl, branched-chain alkyl, cycloalkyl, aryl or heteroaryl, wherein the heteroatoms of the heteroaryl are, independently, sulfur, nitrogen or oxygen, or where the substituted or unsubstituted straight-chain alkyl of R 1 and R 2 are linked to form a ring structure with E;
R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 and R 11 are, independently, H or substituted or unsubstituted groups that are straight-chain alkyl, branched-chain alkyl, cycloalkyl, alkoxy, aryl, heteroaryl, —N(alkyl) 2 wherein the alkyl groups are, independently, straight-chain or branched-chain groups, —N(cycloalkyl) 2 wherein the cycloalkyl groups are the same or different, —N(aryl) 2 wherein the aryl groups are the same or different, —N(heteroaryl) 2 wherein the heteroaryl groups are the same or different, or heterocycloalkyl; or
R 1 /R 3 or R 2 /R 3 forms a ring structure with the atoms to which they are attached and in this instance R 4 /R 5 , R 5 /R 6 , R 7 /R 8 , R 8 /R 9 , R 9 /R 10 or R 10 /R 11 may independently form a ring structure with the carbon atoms to which they are attached;
R 12 is substituted or unsubstituted and is straight-chain alkyl, branched-chain alkyl, cycloalkyl, aryl or heteroaryl wherein the heteroatoms of the heteroaryl are, independently, sulfur, nitrogen, or oxygen;
wherein:
at least one of R 7 , R 8 , R 9 , R 10 and R 11 is not H, and
when R 8 , R 9 and R 10 are H, R 7 and R 11 are not OMe;
m is 0, 1, 2, 3, 4 or 5;
E is P or As; and
X is a coordinating anionic ligand.

2. The process of claim 1 , wherein E is P.

3. The process of claim 2 , wherein R 1 and R 2 are less sterically bulky than a cyclohexyl group when R 7 , R 8 , R 9 , R 10 and/or R 11 are more sterically bulky than a cyclohexyl group.

4. The process of claim 1 , wherein R 3 , R 4 , R 5 and R 6 are —H.

5. The process of claim 1 , wherein two of R 3 , R 4 , R 5 and R 6 are —H, and the other two of R 3 , R 4 , R 5 and R 6 are, independently, unsubstituted straight-chain alkyl, unsubstituted branched-chain alkyl, unsubstituted cycloalkyl, or unsubstituted alkoxy.

6. The process of claim 1 , wherein three of R 7 , R 8 , R 9 , R 10 and R 11 are —H, and the other two of R 7 , R 8 , R 9 , R 10 and R 11 are, independently, unsubstituted straight-chain alkyl, unsubstituted branched-chain alkyl, unsubstituted cycloalkyl, unsubstituted alkoxy, unsubstituted —N(alkyl) 2 , wherein the alkyl groups are independently straight-chain or branched-chain groups, or unsubstituted —N(aryl) 2 , wherein the aryl groups are the same or different; or
wherein two of R 7 , R 8 , R 9 , R 10 and R 11 are —H, and the other three of R 7 , R 8 , R 9 , R 10 and R 11 are, independently, unsubstituted straight-chain alkyl, unsubstituted branched-chain alkyl, unsubstituted cycloalkyl, unsubstituted alkoxy, unsubstituted —N(alkyl) 2 , wherein the alkyl groups are independently straight-chain or branched-chain groups, or unsubstituted —N(aryl) 2 , wherein the aryl groups are the same or different.

7. The process of claim 1 , wherein the monodentate biaryl ligand of formula (4) is:

where

8. The process according to claim 1 , wherein X is a halo group or a trifluoroacetate group.

9. The process according to claim 1 , wherein the complex of formula (1) is:

where,

Assignees

• Johnson Matthey Plc

Inventors

• Colacot Thomas
• Chow Ruishan
• Deangelis Andrew Jon

Classifications

• C07F15/006 Primary

  Palladium compounds · CPC title

• C07D471/04

  Ortho-condensed systems · CPC title

• C07D409/04

  directly linked by a ring-member-to-ring-member bond · CPC title

• C07D405/04

  directly linked by a ring-member-to-ring-member bond · CPC title

• C07D403/04

  directly linked by a ring-member-to-ring-member bond · CPC title