CuBr/TBHP-mediated synthesis of N-acyl sulfonimidamides via the oxidative cross-coupling of sulfonimidamides and aldehydes

Abstract

N-Acyl sulfonimidamides were synthesized via a Cu-catalyzed double C-H/N-H activation protocol. The imino end of sulfonimidamides was acylated using aldehyde as the acylating agent and t-butyl hydrogen peroxide (TBHP) as the oxidant in acetonitrile (MeCN) at 82 °C. The mild reaction conditions afforded low-to-moderate yields of N-acyl sulfonimidamides with high structural diversity.

Aldehydes: magnificent acyl equivalents for direct acylation

“…In 2017, Cijil Raju and co-workers reported a Cu-catalyzed double C-H/N-H activation protocol between sulfonimidamides and aldehydes affording a diversity of Nacyl sulfonimidamides in low to moderate yields (Scheme 67). 100 In this typical procedure, a mixture of sulfonimidamides (4.0 equiv. ), aldehydes (1.0 equiv.)…”

Catalyst‐Controlled Dual Reactivity of Sulfonimidamides: Synthesis of Propargylamines and N‐Propargyl Sulfonimidamides

“…As a part of our ongoing research work on the exploration of the chemistry of sulfonimidamides (SIAs), recently we disclosed the mild synthesis of N ‐imidoyl and N ‐oxoimidoyl sulfonimidamides through the three‐component coupling of SIAs, azides, and alkynes . A dual C−H/N−H activation protocol to achieve N ‐acyl SIAs also has been developed . In a latest study, we described the design and synthesis of novel sulfonimidoyl azides, that is, the mono aza‐analogues of sulfonyl azides, and applied these azides to provide N ‐acyl SIAs and N ‐sulfonimidoyl amidines in one‐step process .…”

“…1 HNMR ( 5, 133.7, 130.1, 129.9, 129.0, 128.5, 125.5, 121.7, 84.1, 83.9, 67.2, 61.5, 49.9 3,130.7,130.1,129.4,128.9,127.0,125.4,125.3,121.8,84.3,83.6,67.2,61.4,49.8. HRMS (ESI) 140.0, 138.4, 131.7, 129.0, 126.2, 124.2, 119.6, 87.5, 83.6, 67.1, 57.9, 49.6, 21.5, 15.4 6,128.9,120.1,86.3,86.2,67.1,59.8,49.7,26.1,21.4,11.2. HRMS (ESI) 9, 138.3, 136.8, 134.7, 132.5, 131.6, 129.2, 129.1, 128.8, 128.0, 127.2, 120.3, 90.1, 83.7, 66.6, 47.6, 46.5, 21.5, 21. 9, 137.1, 135.0, 132.6, 131.8, 129.3, 128.8, 128.8, 128.3, 127.3, 120.6, 90.7, 83.4, 66.3, 48.0, 47.0, 21.5, 21.3 134.4, 132.7, 131.7, 131.4, 129.1, 129.0, 128.5, 128.5, 128.0, 123.0, 121.3, 90.2, 84.1, 66.5, 47.5, 46.3 8, 132.8, 131.9, 131.7, 129.1, 129.0, 128.3, 128.2, 128.1, 123.3, 123.2, 121.4, 90.6, 83.9, 66.2, 47.7, 47. 9, 141.0, 139.9, 138.3, 132.7, 131.6, 129.4, 129.1, 128.9, 128.3, 128.0, 120.4, 90.0, 83.8, 48.3, 46.3, 25.7, 23.8, 21.6, 21.5 9, 141.7, 137.9, 132.9, 132.9, 131.7, 129.4, 128.8, 128.7, 128.6, 128.3, 120.4, 90.4, 83.7, 47.7, 47.6, 25.4, 23.7, 21.6, 21.5 = 246.9,12.6 Hz),139.0,138.6,134.2,132.7,131.4,129.2,128.9,127.8,…”

“…[5] Ad ualC ÀH/NÀHa ctivation protocol to achieve N-acyl SIAs also has been developed. [6] In al atest study,w ed escribed the design and synthesis of novel sulfonimidoyl azides, that is, the monoa za-analogues of sulfonyl azides, and applied these azides to provide N-acyl SIAs and Nsulfonimidoyl amidines in one-step process. [7a] In view of the growingb iological and synthetic importance of SIAs, and also of our interesti ne xploring their chemistry and 'S'-related compounds, [7b-d] herein, we revealed that SIAs can act as amine surrogateu nder certain conditions to provide propargylamines.…”

Cu‐Catalysed Mild Synthesis of N‐Imidoyl and N‐Oxoimidoyl Sulfonimidamides through the Three‐Component Coupling of Sulfonimidamides, Azides, and Alkynes

“…These are restricted to alkylation, arylation, vinylation, alkynylation, and acylation . We also recently developed a new protocol for the synthesis of N ‐acylated sulfonimidamides by a C–H/N–H dual‐activation technique . Consequently, there are enormous possibilities to enrich the chemistry and biological importance of this scaffold.…”