Chelation directed C—H activation reactions catalyzed by solid-supported palladium(II) catalysts

Patent metadata

Field	Value
Publication number	US-10000453-B2
Application number	US-201515532828-A
Country	US
Kind code	B2
Filing date	Dec 3, 2015
Priority date	Dec 5, 2014
Publication date	Jun 19, 2018
Grant date	Jun 19, 2018

Abstract

Chelation directed C—H activation reactions that are catalyzed by Pd(11) on Multi-Walled Carbon Nanotubes (MWCNT), Single-Walled Carbon Nanotubes (SWCNT), or graphene are provided. The reactions are used to directly and regioselectively or regiospecifically functionalize specific C—H bonds, e.g. to build complexity into small molecules. Features and advantages of the present invention will be set forth in the description of invention that follows, and in part will be apparent from the description or may be learned by practice of the invention. The invention will be realized and attained by the compositions and methods particularly pointed out in the written description and claims hereof.

First claim

We claim:

1. A method for regioselectively or regiospecifically producing functionalized aryl or heteroaryl compounds by oxidative N-chelation-directed C—H activation, comprising the steps of:
combining
i) an aryl or heteroaryl compound containing a) a C—H group and b) a second atom capable of forming a Pd(II) chelate with C of the C—H group after loss of H;
ii) a solid-supported Pd(II) catalyst selected from the group consisting of Pd(II)/MWCNT, Pd(II)/SWCNT and Pd(II)/graphene; and
iii) an oxidant comprising an atom or functional group that can replace H of the C—H group in the aryl or heteroaryl compound,
wherein said combining is performed under conditions wherein
a) H is lost from the C—H group and C of the C—H group and the second atom chelate Pd(II) of the solid-supported Pd(II) catalyst to form a first Pd(II) chelation adduct;
b) the atom or functional group is lost from the oxidant species and Pd(II) of the first chelation adduct is oxidized to form a second Pd(IV) chelation adduct in which Pd(IV) is chelated by the second atom, the C of the C—H group and the atom or functional group of the oxidant species; and
c) the second Pd(IV) chelation adduct undergoes reductive elimination to
1) produce a functionalized aryl or heteroaryl compound comprising the atom or functional group, and
2) regenerate Pd(II).

2. The method of claim 1 further comprising the steps of
recovering said solid-supported Pd(II) catalyst after said separating step; and
repeating said steps of combining and separating using at least some of said solid-supported Pd(II) catalyst recovered in said recovering step.

3. The method of claim 1 wherein said aryl or heteroaryl compound and said oxidant each contain at least one aryl or heteroaryl moiety.

4. The method of claim 1 wherein said aryl or heteroaryl compound and said oxidant each contain at least one pyridine.

5. The method of claim 1 wherein said aryl or heteroaryl compound and said oxidant each contain at least one phenyl.

6. The method of claim 1 wherein said aryl or heteroaryl compound and said oxidant each contain at least one cycloalkyl.

7. The method of claim 1 wherein said aryl or heteroaryl compound and said oxidant each contain at least a second phenyl.

8. The method of claim 1 wherein said aryl or heteroaryl compound and said oxidant each contain at least one pyridine.

9. The method of claim 1 wherein said functional group is a halogen.

10. The method of claim 1 wherein said functional group is a alkyl or aryl moiety.

11. The method of claim 1 wherein said functional group is an ether or ester.

12. The method of claim 11 wherein said functional group is an ether OR, where R is a alkyl or alkaryl moiety of 1 to 25 carbons.

13. The method of claim 1 , wherein the C of the C—H group is sp 2 or sp 3 hybridized.

14. The method of claim 1 , wherein the second atom is separated from the C of the C—H group by 2 to 4 atoms.

15. The method of claim 1 , wherein the first Pd(II) chelation adduct is 5-, 6- or 7-membered palladacycle.

16. The method of claim 1 , wherein the method is regiospecific.

17. The method of claim 1 , wherein the atom or functional group of the oxidant species is not fluorine.

18. The method of claim 1 , wherein the atom or functional group of the oxidant species is Cl, Br or I.

Assignees

• Univ Virginia Commonwealth

Inventors

• Ellis Keith C
• Gupton Frank B

Classifications

• C07C249/04

  of oximes · CPC title

• C07D213/30

  Oxygen atoms · CPC title

• B01J21/185

  Carbon nanotubes (carbon nanotubes per se C01B32/15) · CPC title

• C07C2602/10

  the other ring being six-membered, e.g. tetraline · CPC title

• C07D213/26

  Radicals substituted by halogen atoms or nitro radicals · CPC title