Photoredox-catalyzed direct C—H functionalization of arenes

Patent metadata

Field	Value
Publication number	US-12534437-B2
Application number	US-202318159647-A
Country	US
Kind code	B2
Filing date	Jan 25, 2023
Priority date	Jun 3, 2015
Publication date	Jan 27, 2026
Grant date	Jan 27, 2026

Abstract

The invention generally relates to methods of making substituted arenes via direct C—H amination. More specifically, methods of making para- and ortho-substituted arenes via direct C—H amination are disclosed. This abstract is intended as a scanning tool for purposes of searching in the particular art and is not intended to be limiting of the present invention.

First claim

What is claimed is:

1 . A compound having a structure represented by a formula:

wherein X is selected from BF 4 , TfO, PF 6 , and ClO 4 ;
wherein R 9 is phenyl substituted with 1, 2, or 3 groups independently selected from halogen, —CF 3 , —NH 2 , C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylamino, (C1-C4) (C1-C4) dialkylamino; and
wherein R 10 is selected from C1-C4 alkyl and phenyl substituted with 0, 1, 2, or 3 groups independently selected from halogen and C1-C4 alkyl.

2 . The compound of claim 1 , wherein X is BF 4 .

3 . The compound of claim 1 , wherein R 10 is phenyl substituted with 0, 1, 2, or 3 groups independently selected from halogen and C1-C4 alkyl.

4 . The compound of claim 1 , wherein R 10 is phenyl substituted with 0, 1, 2, or 3 groups independently selected from C1-C4 alkyl.

5 . The compound of claim 1 , wherein the compound has a structure represented by a formula:

6 . A catalyst system comprising an acridinium photocatalyst, a nucleophile, and an oxidant, wherein the acridinium photocatalyst is of the formula:

wherein X is selected from BF 4 , TfO, PF 6 , and ClO 4 ;
wherein R 9 is selected from C1-C4 alkyl and phenyl substituted with 0, 1, 2, or 3 groups independently selected from halogen, —CF 3 , —NH 2 , C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylamino, (C1-C4) (C1-C4) dialkylamino; and
wherein R 10 is selected from C1-C4 alkyl and phenyl substituted with 0, 1, 2, or 3 groups independently selected from halogen and C1-C4 alkyl.

7 . The catalyst system of claim 6 , further comprising a compound having a structure represented by a formula:

wherein E is an electron donating group;
wherein each of Q 1 and Q 3 is independently selected from N and CR 1 ; wherein each of Q 2 and Q 4 is independently selected from N and CR 2 ;
wherein each occurrence of R 1 and R 2 is independently selected from hydrogen, halogen, C1-C8 alkyl, C1-C8 alkoxy, and —C(═O) NR 3a R 3b ; or wherein R 1 and R 2 are optionally covalently bonded and, together with the intermediate atoms, form a 5- to 6-membered cycle or heterocycle having 0, 1, or 2 heteroatoms and substituted with 0, 1, 2, or 3 groups independently selected from halogen, C1-C8 alkyl, C1-C8 alkoxy, and —C(═O)NR 3a R 3b ;
wherein each of R 3a and R 3b is independently selected from hydrogen and C1-C4 alkyl; wherein Z is selected from halogen, —CN, —NH 2 , —OH, C1-C8 alkenyl, C1-C8 alkoxy, C1-C8 thioalkoxy, C1-C8 alkylamino, (C1-C8) (C1-C8) dialkylamino, arylamino, diarylamino, C1-C8 alkarylamino, —NNR 4 , —OC(═O)R 5 , and Ar 1 ;
wherein R 4 is selected from hydrogen and C1-C8 alkyl;
wherein R 5 is selected from C1-C8 alkyl; and
wherein Ar 1 is a 3- to 6-membered heterocycle substituted with 0, 1, 2, or 3 groups independently selected from halogen and C1-C8 alkyl.

8 . The catalyst system of claim 6 , wherein X is BF 4 .

9 . The catalyst system of claim 6 , wherein R 9 is C1-C4 alkyl.

10 . The catalyst system of claim 6 , wherein R 9 is methyl.

11 . The catalyst system of claim 6 , wherein R 9 is phenyl substituted with 0, 1, 2, or 3 groups independently selected from halogen, —CF 3 , —NH 2 , C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylamino, (C1-C4) (C1-C4) dialkylamino.

12 . The catalyst system of claim 6 , wherein R 9 is unsubstituted phenyl.

13 . The catalyst system of claim 6 , wherein R 10 is phenyl substituted with 0, 1, 2, or 3 groups independently selected from halogen and C1-C4 alkyl.

14 . The catalyst system of claim 6 , wherein the acridinium photocatalyst has a structure represented by the formula:

15 . The catalyst system of claim 6 , wherein the acridinium photocatalyst is selected from:

16 . The catalyst system of claim 6 , wherein the acridinium photocatalyst is:

Assignees

• Univ North Carolina Chapel Hill

Inventors

• Nicewicz David
• Romero Nathan
• Margrey Kaila
• Tay Nicholas

Classifications

• C07C69/78

  Benzoic acid esters · CPC title

• C07C67/05

  with oxidation · CPC title

• C07C43/29

  containing halogen · CPC title

• C07C41/22

  by introduction of halogens; by substitution of halogen atoms by other halogen atoms · CPC title

• C07C255/50

  to carbon atoms of non-condensed six-membered aromatic rings · CPC title