Group 5 metal complexes for catalytic amine functionalization

Patent metadata

Field	Value
Publication number	US-11034707-B2
Application number	US-201816616689-A
Country	US
Kind code	B2
Filing date	May 25, 2018
Priority date	May 26, 2017
Publication date	Jun 15, 2021
Grant date	Jun 15, 2021

Abstract

This application pertains to group 5 metal complexes having the structure of Formula I:

and their potential utility in catalyzing α-alkylation of secondary amine-containing moieties.

First claim

What is claimed is:

1. A metal complex having the structure of Formula I:

wherein:
(i) R 1 and R 2 are each independently H; a C 1 -C 40 substituted or unsubstituted linear, branched or cyclic alkyl, alkenyl or alkynyl; a substituted or unsubstituted aryl; or a substituted or unsubstituted heterocyclic group; or
R 1 and R 2 are bonded together thereby forming, together with the nitrogen atom they are both bound to, a heterocycle; and
R 3 is H; a C 1 -C 40 substituted or unsubstituted linear, branched or cyclic alkyl, alkenyl or alkynyl; a substituted or unsubstituted aryl; or a substituted or unsubstituted heterocyclic group; or

(ii) R 1 is H; a C 1 -C 40 substituted or unsubstituted linear, branched or cyclic alkyl, alkenyl or alkynyl; a substituted or unsubstituted aryl; or a substituted or unsubstituted heterocyclic group; and
R 3 is bonded together with R 2 to form a heterocycle;

M is a group 5 metal;
a=1or 2 and b=2 or 3, wherein the sum of a and b is 4;
each X is a halogen substituent; and
each R 4 is independently H; or a C 1 -C 20 substituted or unsubstituted, linear, branched or cyclic alkyl, optionally comprising heteroatoms.

2. The metal complex of claim 1 , wherein each X is independently Cl or Br, a=1 and b=3.

3. The metal complex of claim 1 , wherein R 1 and R 2 are bonded together to form, together with the nitrogen atom they are both bound to, a 6-membered ring, which optionally may be substituted.

4. The metal complex of claim 1 , wherein:
R 1 and R 2 are each phenyl;
R 1 is phenyl and R 2 is isopropyl;
R 1 and R 2 are bonded together to form, together with the nitrogen atom they are both bound to, piperidinyl;
R 1 is phenyl and R 2 is methyl;
R 1 is methyl and R 2 is 1-phenylethyl;
R 1 is methyl and R 2 is isopropyl; or
R 1 is methyl and R 2 is diphenylmethyl.

5. The metal complex of claim 1 , wherein R 3 is: phenyl; 2,6-dimethyl phenyl; 2,6-di(isopropyl) phenyl; or

6. The metal complex of claim 1 , wherein R 3 is bonded together with R 2 to form, together with each of the nitrogen atoms they are bound to, a 5-membered ring, which optionally may be substituted.

7. The metal complex of claim 6 , having the structure:

wherein
R 1 is methyl, tert-butyl, phenyl, cyclohexyl or adamantyl.

8. The metal complex of claim 1 , wherein R 4 is —CH 2 Si(CH 3 ) 3 .

9. The metal complex of claim 1 , wherein M is tantalum (Ta).

10. The metal complex of claim 1 , which metal complex is:

11. A method of synthesizing a metal complex of Formula I, the method comprising reacting a group 5 metal salt of Formula VII with one equivalent of an amide of Formula VIII according to the following reaction:

wherein:
(i) R 1 and R 2 are each independently H; a C 1 -C 40 substituted or unsubstituted linear, branched or cyclic alkyl, alkenyl or alkynyl; a substituted or unsubstituted aryl; or a substituted or unsubstituted heterocyclic group; or
R 1 and R 2 are bonded together thereby forming, together with the nitrogen atom they are both bound to, a heterocycle; and
R 3 is H; a C 1 -C 40 substituted or unsubstituted linear, branched or cyclic alkyl, alkenyl or alkynyl; a substituted or unsubstituted aryl; or a substituted or unsubstituted heterocyclic group; or

(ii) R 1 is H; a C 1 -C 40 substituted or unsubstituted linear, branched or cyclic alkyl, alkenyl or alkynyl; a substituted or unsubstituted aryl; or a substituted or unsubstituted heterocyclic group; and
R 3 is bonded together with R 2 to form a heterocycle;

M is a group 5 metal;
a=1 or 2 and b=2 or 3, wherein the sum of a and b is 4;
c=2 or 3 and d=2 or 3, wherein the sum of c and d is 5;
each X is a halogen substituent; and
each R 4 is independently H; or a C 1 -C 20 substituted or unsubstituted, linear, branched or cyclic alkyl, optionally comprising heteroatoms.

12. A method for α-alkylation of a secondary amine-containing moiety, the method comprising: (i) reacting said secondary amine-containing moiety with an olefin in the presence of a metal complex as defined in claim 1 .

13. The method of claim 12 , further comprising: (ii) isolating a product formed in step (i).

14. The method of claim 12 , wherein the secondary amine-containing moiety is a C 4 -C 100 linear, branched, or cyclic alkyl, optionally substituted and/or comprising heteroatoms.

15. The method of claim 12 , wherein the secondary amine-containing moiety is substituted with a halogen, an ether, another amine, an alkyl, an alkene, an acetal, a phosphine, an amide, an alkyne, an imine, a nitrile, an isocyanide, an epoxide, a boronic acid ester, a phenyl that optionally may be substituted and/or part of a condensed ring system, or any combination thereof.

16. The method of claim 12 , wherein the olefin is:

17. The method of claim 12 , wherein the secondary amine-containing moiety is: pyrrolidine;

wherein Z is H, OCF 3 , F, Cl, Br, I, or OCH 3 .

18. The method of claim 12 , wherein the reaction conditions comprise a reaction temperature in the range from 90° C. to 150° C.

19. The method of claim 12 , wherein the reaction conditions comprise a solvent, wherein the solvent is toluene, benzene, or a mixture thereof.

20. The method of claim 12 , wherein the metal complex is generated in situ from a group 5 metal salt of Formula VII
MX c (R 4 ) d   (Formula VII)

wherein:
M is a group 5 metal;

c=2 or 3 and d=2 or 3, wherein the sum of c and d is 5; and
each R 4 is independently H; or a C 1 -C 20 substituted or unsubstituted, linear, branched or cyclic alkyl, optionally comprising heteroatoms, in combination with an amide of Formula VIII

wherein:
(i) R 1 and R 2 are each independently H; a C 1 -C 40 substituted or unsubstituted linear, branched or cyclic alkyl, alkenyl or alkynyl; a substituted or unsubstituted aryl; or a substituted or unsubstituted heterocyclic group; or
R 1 and R 2 are bonded together thereby forming, together with the nitrogen atom they are both bound to, a heterocycle; and
R 3 is H; a C 1 -C 40 substituted or unsubstituted linear, branched or cyclic alkyl, alkenyl or alkynyl; a substituted or unsubstituted aryl; or a substituted or unsubstituted heterocyclic group; or

(ii) R 1 is H; a C 1 -C 40 substituted or unsubstituted linear, branched or cyclic alkyl, alkenyl or alkynyl; a substituted or unsubstituted aryl; or a substituted or unsubstituted heterocyclic group; and
R 3 is bonded together with R 2 to form a heterocycle.

Assignees

• Univ British Columbia

Inventors

• Schafer Laurel
• Rosca Sorin-Claudiu
• Dipucchio Rebecca

Classifications

• B01J2531/50

  Complexes comprising metals of Group V (VA or VB) as the central metal · CPC title

• C07C11/02

  Alkenes · CPC title

• C07D215/06

  having only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, attached to the ring nitrogen atom · CPC title

• C07C2601/18

  with a ring being at least seven-membered · CPC title

• B01J2540/40

  Non-coordinating groups comprising nitrogen · CPC title