Copper(II)-Catalyzed Direct Sulfonylation of C(sp²)–H Bonds with Sodium Sulfinates

Abstract

A copper-catalyzed direct sulfonylation of C(sp(2))-H bonds with sodium sulfinates using a removable directing group is described. This reaction tolerates a wide range of functional groups, providing an efficient protocol for the synthesis of diverse aryl sulfones. Moreover, a series of 2,6-disubstituted benzamides could be synthesized via sequential C-H functionalization.

Copper‐Catalyzed or ‐Mediated CH Bond Functionalizations Assisted by Bidentate Directing Groups

“…[43] Thec ombination of Cu(OAc) 2 as catalyst andAg 2 CO 3 as oxidant provided an efficient protocolf or the synthesis of diverse aryl sulfones.…”

α,α-Dimethyl-2-pyridinemethanamine

“…5 It has been proposed that the gemdimethyl substitution may increase the rate of cyclization and the stability of the resulting metallacycles due to the Thorpe-Ingold effect. 5, 6 The PIP auxiliary has been widely used for the cleavage of C-H bonds and the formation of C-O, 7-9 C-C, 1b,2,10-15 C-N, 1b C-S, [16][17][18][19] and C-X 20,21 bonds. Various transition metals, such as palladium, copper, and nickel, have been used for these transformations.…”

“…This reaction tolerates a large number of functional groups and can be scaled up to gram scale (eq 21) 19. …”

One‐pot reactions for the synthesis of 5‐sulfonyl quinolines via domino N‐acylation and remote C‐H sulfonylation

“…[16][17][18][19] Recently, catalytic latent C-H bond sulfonylation with the assistance of chelating auxiliary using various sulfonylating reagents has emerged as another practical tool in the synthesis of structurally diverse sulfonyl compounds. [20][21][22][23] As typical substrates allowing the C-H activation-based elaboration, the N-acyl 8-aminoquinolines [24][25][26][27][28] have received extensive research interest in synthesizing sulfonylated N-acyl 8-aminoquinoline derivatives. Generally, depending on the catalytic conditions and property of sulfonylating reagents, two types of C-H sulfonylation model are known.…”