Direct One‐Pot Construction of Diaryl Thioethers and 1,3‐Diynes through a Copper(I)‐Catalyzed Reaction of λ³‐Iodanes with Thiophenols

Abstract

Herein, an efficient method for both aryl C(sp2)−S and C(sp)−C(sp) bond formation to construct both diaryl thioethers and 1,3‐diynes in excellent yield from spirocyclic λ3‐iodanes and benzenethiols under copper(I) catalysed conditions, has been developed. We proposed that a Ullmann reaction of benzenethiols with aryl iodonium intermediates form the diaryl thioethers, and a homocoupling of alkyne radical provided the 1,3‐diynes. This reaction takes fully advantage of the “waste” part of substrates.

Aryl-, Akynyl-, and Alkenylbenziodoxoles: Synthesis and Synthetic Applications

“…The first representatives of spirocyclic alkynylbenziodoxoles 59 were prepared by exposure to EBXs 51 of α-bromoamide 58 under basic conditions at room temperature (Scheme 14) [83,84]. Vinylbenziodoxole (VBX) 60 has been formed as a by-product during the reaction course, but at low temperatures its formation was maximal and, finally, compound 60 was isolated, with a yield of 45%.…”

“…Vinylbenziodoxole (VBX) 60 has been formed as a by-product during the reaction course, but at low temperatures its formation was maximal and, finally, compound 60 was isolated, with a yield of 45%. Spirocyclic EBXs 59 have been employed in the synthesis of 1,3-diynes 61 [83,84], diaryl thioethers 62 [84], and 4,1-benzoxazepine-2,5diones 63 [83] under copper(I) catalysis. [82].…”