Ru(II)-Catalyzed C–H Aminocarbonylation of N-(Hetero)aryl-7-azaindoles with Isocyanates

Abstract

The ruthenium(II)-catalyzed C-H aminocarbonylation of N-(hetero)aryl-7-azaindoles with isocyanates is described. The excellent site selectivity at the ortho-position within the N-(hetero)aryl ring was observed to provide ortho-amidated N-(hetero)aryl-7-azaindoles under the mild reaction conditions. The resulting 7-azaindole derivatives can be readily transformed into 7-azaindoles containing carboxylic acid and alkyl amine functional groups.

Recent Advances in the N-Aryl C—H Functionalization Using 7-Azaindole as Intrinsic Directing Group

“…A variety of amidated N-(hetero)aryl-7-azaindoles were formed in good yields (Scheme 9). [19] This transformation features with a wide range of substrates with excellent site-and chemoselectivity under mild conditions. It is worth noting that the ortho-amidated N-(hetero)aryl-7-azaindole can be further converted into corresponding carboxylic acid and alkylamine derivatives.…”

Ru(II)‐Catalyzed ortho C—H Allylation of N‐Aryl‐7‐azaindoles with 2‐Methylidene Cyclic Carbonate

“…In the past few decades, transition‐metal‐catalyzed C—H functionalization has been proven to be an efficient strategy to construct N ‐aryl‐7‐azaindole moieties, because of its high atomic step economy and environmental sustainability. [ 3 ] To date, 7‐azaindole as a guiding group, transition‐metal‐catalyzed ortho C—H functionalization of aryl group, including amination, [ 4 ] sulfurization, [ 5 ] alkylation, [ 6 ] olefination, [ 7 ] alkynylation, [ 8 ] cyclization, [ 9 ] acylation, [ 10 ] cyanation/arylation, [ 11 ] have been extensively reported. Although significant progress has been made in the field, [ 12 ] the C—H allylation reaction of N ‐aryl‐7‐azaindole with 2‐methylidene cyclic carbonate has not been reported yet.…”

Cobalt(III)-Catalyzed C–H Amidation of 7-Azaindoles with Dioxazolones: Synthesis of 7-Azaindole Amidated Derivatives

“…Due to their appealing properties, various protocols were established to modify the structure of 7-azaindoles . Very recently, the ruthenium­(II)-catalyzed direct C–N amidation reaction of 7-azaindoles with isocyanates was described (Scheme , eq 1) . Before this, a novel selective synthesis of a diversity of C–C or C–N amidated 7-azaindole derivatives from 7-azaindoles and acyl azides has been first reported by our group (Scheme , eq 2) .…”

“…9 Very recently, the ruthenium(II)-catalyzed direct C−N amidation reaction of 7-azaindoles with isocyanates was described (Scheme 1, eq 1). 10 Before this, a novel selective synthesis of a diversity of C−C or C−N amidated 7-azaindole derivatives from 7-azaindoles and acyl azides has been first reported by our group (Scheme 1, eq 2). 11 However, the substituents of nitrogen are limited to aromatic rings with the use of noble metal catalysts.…”