Copper‐Catalyzed Oxidative Cross‐Coupling of Sulfoximines and Alkynes

Abstract

A 'Cu'te couple: A synthetically useful protocol for the preparation of N‐alkynylated sulfoximines (yne sulfoximines) has been developed. The method involves a mild copper‐catalyzed oxidative cross‐coupling of NH‐sulfoximines and terminal alkynes (see scheme). The corresponding N‐acyl sulfoximines were also obtained selectively after acid‐catalyzed hydrolysis of the yne sulfoximines.

Highly Efficient Curtius Rearrangement Approach for the Synthesis of Unsymmetrical Sulfonimidoyl Ureas

“…There are several methods that are focusedo nt he preparation of functionalized sulfoximine derivatives. [15] For the study of unsymmetrical N-sulfonimidoyl ureas, known reports mostly employ aromatic or alkyl isocyanates or carbamoyl chlorides to react with sulfoximines[ Scheme 1a]. [10a, 16] Bolm and co-workers disclosed the application of chiral thiourea-sulfoximined erivatives in the catalytic desymmetrization reaction of cyclic meso-anhydride and in the catalytic asymmetricB iginelli reaction.…”

Cu(OAc)2‐Catalysed Oxidative Dual C–H/N–H Activation of Terminal Alkynes and N‐Deprotected Sulfonimidamides: An Easy Access to N‐Alkynylated Sulfonimidamides

“…Stahl's group has reported a method3a for the oxidative amidation of terminal alkynes using molecular oxygen as the external oxidant. Evano3b and Bolm3e have also used Stahl's protocol for the alkynylation of diaryl imines and sulfoximines, respectively. Based on these seminal reports, we introduced molecular oxygen as an external oxidant; this modification improved the yield of the expected product (i.e., 3a ) to 76 %, and limited dimer 4 to trace amounts.…”

Novel ynamide structural analogues and their synthetic transformations

“…2.6 Yne-sulfoximines Bolm 35 described the first preparations of yne-sulfoximines 61 through a copper catalyzed oxidative cross-coupling of sulfoximines 59 with terminal alkynes 60. These yne-sulfoximines…”

“…Very recently, preparations of structural analogues of ynamides have emerged as novel N-containing alkyne building blocks. [27][28][29][30][31][32][33][34][35][36] These preparations mainly are based on modified methods for ynamide synthesis [22][23][24][25][26] as described in Scheme 1. With the belief that these novel analogues will also become versatile synthons that will be tremendously useful to organic synthesis, especially in the arena of N-heterocycle constructions, we highlight herein syntheses and reactions of de novo ynamide analogues: diaminoacetylenes 2, ynimides 3, yne-imines 4, yne-hydrazides 5, amidinylynamides 6, and yne-sulfoximines 7 (Scheme 1).…”