Nickel pre-catalysts and related compositions and methods

Patent metadata

Field	Value
Publication number	US-2016376293-A1
Application number	US-201615191285-A
Country	US
Kind code	A1
Filing date	Jun 23, 2016
Priority date	Nov 11, 2013
Publication date	Dec 29, 2016
Grant date	—

Abstract

Described herein are nickel pre-catalysts and related compositions and methods. The nickel pre-catalysts may be activated to form catalysts which may be utilized in organic reactions.

First claim

1 . A pre-catalyst, comprising:
a nickel (II) atom, wherein the nickel (II) atom is associated with at least one phosphine ligand; at least one aryl ligand; and at least one leaving group.

2 . The pre-catalyst of claim 1 , wherein the pre-catalyst comprises two phosphine ligands.

3 . The pre-catalyst of claim 1 , wherein the pre-catalyst comprises two phosphine ligands, one aryl ligand, and one leaving group.

4 - 6 . (canceled)

7 . The pre-catalyst of claim 1 , wherein the pre-catalyst has the structure:

wherein each R 1 is independently optionally substituted alkyl, optionally substituted cycloalkyl, or optionally substituted aryl, or any two R 1 may be joined together to form a ring;
Ar is the at least one aryl ligand, and LG is the at least one leaving group.

8 . The pre-catalyst of claim 1 , wherein the pre-catalyst has the structure:

wherein each R 2 is independently optionally substituted alkyl, optionally substituted cycloalkyl, or optionally substituted aryl, or any two R 2 are joined together to form a ring;
each R 3 is —O—, optionally substituted alkylene, optionally substituted heteroalkylene, optionally substituted arylene, optionally substituted heteroarylene, or optionally substituted ferrocenylene;
n is 1, 2, 3, 4, 5, or 6; Ar is the at least one aryl ligand; and
LG is the at least one leaving group.

9 - 18 . (canceled)

19 . The pre-catalyst of claim 1 , wherein the leaving group is selected from the group consisting of halo, OTs, and OMs.

20 . A method, comprising:
activating a pre-catalyst as described in claim 1 to form a catalyst.

21 . The method of claim 20 , further comprising reacting an optionally substituted benzyl chloride with a terminal alkene in the presence of the catalyst.

22 . The method of claim 20 , further comprising reacting a terminal alkene with an aldehyde and a silyl triflate in the presence of the catalyst.

23 . The method of claim 20 , wherein the activating comprises reacting the pre-catalyst with an activating agent.

24 . The method of claim 20 , wherein the pre-catalyst does not comprise cyclooctadiene.

25 . The method of claim 20 , wherein the activating is carried out in the presence of oxygen.

26 . The method of claim 20 , wherein the reaction is stereoselective via reaction of the external position of the terminal alkene.

27 . The method of claim 20 , wherein the reaction is stereoselective via reaction of the internal position of the terminal alkene.

28 . The method of claim 20 , wherein the benzyl chloride has the structure:

wherein each R 4 is independently halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkylene, optionally substituted aryl, optionally substituted —O-alkyl, —SO 2 -alkyl, —COOH, —COO-alkyl, or any two R 4 can be joined together to form a ring; and n is 0, 1, 2, 3, 4, or 5.

29 . The method of claim 20 , wherein the terminal alkene has the structure:

wherein R 5 is optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted alkylene, optionally substituted heteroalkyl, optionally substituted alkyl-aryl, or optionally substituted aryl.

30 . The method of claim 20 , wherein the product of the reaction between the optionally substituted benzyl chloride with a terminal alkene is:

wherein each R 4 is independently halo, optionally substituted alkyl, optionally substituted heteroalkyl, optionally substituted alkylene, optionally substituted aryl, optionally substituted —O-alkyl, —SO 2 -alkyl, —COOH, —COO-alkyl, or any two R 4 can be joined together to form a ring; n is 0, 1, 2, 3, 4, or 5; and R 5 is optionally substituted alkyl, optionally substituted cycloalkyl, optionally substituted alkylene, optionally substituted heteroalkyl, optionally substituted alkyl-aryl, or optionally substituted aryl.

Assignees

• Massachusetts Inst Technology

Inventors

• Jamison Timothy F
• Standley Eric Alan

Classifications

• B01J2231/34

  Other additions, e.g. Monsanto-type carbonylations, addition to 1,2-C=X or 1,2-C-X triplebonds, additions to 1,4-C=C-C=X or 1,4-C=-C-X triple bonds with X, e.g. O, S, NH/N · CPC title

• B01J31/2414

  comprising aliphatic or saturated rings · CPC title

• B01J2531/847

  Nickel · CPC title

• B01J31/2409

  with more than one complexing phosphine-P atom · CPC title

• B01J2231/32

  Addition reactions to C=C or C-C triple bonds · CPC title