Ni(0) catalysts

Patent metadata

Field	Value
Publication number	US-10486148-B2
Application number	US-201615763468-A
Country	US
Kind code	B2
Filing date	Sep 30, 2016
Priority date	Sep 30, 2015
Publication date	Nov 26, 2019
Grant date	Nov 26, 2019

Abstract

Provided herein are nickel(O) catalysts that are stable when exposed to air and can be used to catalyze the formation of a C—C, C—O, or C—N bond.

First claim

What is claimed is:

1. A catalyst having a structure of formula (I) or (II):

wherein
the dashed line is an optional double bond;
each R 1 is independently selected from the group consisting of H, C 1-8 alkyl and C 1-2 alkylenearyl;
each R 2 is independently selected from the group consisting of H, halo, C 1-3 alkyl, and aryl, or both R 2 together with the carbons to which they are attached form a 6-membered ring;
each R 3 is the same and is H, C 1-4 alkyl, or aryl;
each R 4 is the same and is C 1-6 alkyl, C 0-2 alkylene-aryl or C 0-2 alkylene-C 2-8 alkene;
each R 5 is the same and is H, C 1-6 alkyl, aryl, CO 2 C 0-2 alkylene-aryl, CO 2 C 0-2 alkylene-C 2-8 alkene, CO 2 iPr or CO 2 tBu; and
each R 6 is the same and is H, C 1-6 alkyl, C 1-6 alkoxy, or O-aryl, with the proviso that at least one of R 1 and R 6 is not H.

2. The catalyst of claim 1 , wherein the dashed line represents a double bond.

3. The catalyst of claim 1 , wherein each R 1 is the same.

4. The catalyst of claim 1 , wherein R 1 is selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, isobutyl, t-butyl, pentyl, 3-pentyl, and diphenylmethyl.

5. The catalyst of claim 1 , wherein each R 2 is selected from H, chloro, and methyl, or wherein both R 2 together with the carbons to which they are attached form a 6-membered ring.

6. The catalyst of claim 1 , wherein R 3 is aryl.

7. The catalyst of claim 1 , wherein R 3 is C 1-4 alkyl or H.

8. The catalyst of claim 1 , wherein R 4 is C 0-2 alkylene-aryl.

9. The catalyst of claim 1 , wherein R 4 is C 0-2 alkylene-C 2-8 alkene.

10. The catalyst of claim 1 , wherein R 4 is C 2-6 alkyl.

11. The catalyst of claim 1 , wherein R 5 is H.

12. The catalyst of claim 1 , wherein R 5 is C 1-6 alkyl.

13. The catalyst of claim 1 , wherein R 5 is aryl.

14. The catalyst of claim 1 , wherein R 5 is CO 2 C 0-2 alkylene-aryl, or CO 2 C 0-2 alkylene-C 2-8 alkene.

15. The catalyst of claim 1 , wherein R 6 is H or C 1-6 alkyl.

16. The catalyst of claim 1 , wherein R 6 is C 1-6 alkoxy.

17. The catalyst of claim 1 , wherein R 6 is O-aryl.

18. A catalyst selected from the group consisting of

wherein Tol is

Ph(OMe) is

Ph(Me) 3 is

and Ph(CO 2 Me) is

19. A catalyst having a structure of formula (I) or (II):

wherein
the dashed line is an optional double bond;
each R 1 is independently selected from the group consisting of H, C 1-8 alkyl and C 1-2 alkylenearyl;
each R 2 is independently selected from the group consisting of H, halo, C 1-3 alkyl, and aryl, or both R 2 together with the carbons to which they are attached form a 6-membered ring;
each R 3 is the same and is H, C 1-4 alkyl, or aryl;
each R 4 is the same and is C 1-6 alkyl, C 0-2 alkylene-aryl or C 0-2 alkylene-C 2-8 alkene;
each R 5 is H; and
each R 6 is the same and is H, C 1-6 alkyl, C 1-6 alkoxy, or O-aryl, with the proviso that at least one of R 1 and R 6 is not H.

20. The catalyst of claim 19 , wherein R 4 is C 0-2 alkylene-aryl.

Assignees

• Univ Michigan Regents
• Fundacio Institut Catala Dinvestigacio Quim Iciq

Inventors

• Montgomery John
• Nett Alex J
• Robo Michael
• Roman Santiago Cañellas

Classifications

• C07D295/073

  with the ring nitrogen atoms and the substituents separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings · CPC title

• B01J31/2273

  with only nitrogen as heteroatomic ring members, e.g. 1,3-diarylimidazoline-2-ylidenes · CPC title

• C07B47/00

  Formation or introduction of functional groups not provided for in groups C07B39/00 - C07B45/00 · CPC title

• B01J2231/4283

  using N nucleophiles, e.g. Buchwald-Hartwig amination · CPC title

• B01J2231/4288

  using O nucleophiles, e.g. alcohols, carboxylates, esters · CPC title