The Aryl Sulfide Synthesis via Sulfide Transfer

Abstract

Aryl sulfides are in great demands in drugs and materials sciences. To avoid using nucleophilic and noxious thiols, many efforts have been focused on exploring novel sulfide resources. Herein, a reductive Pd-catalyzed, Ni-mediated method to synthesize aryl sulfides via a sulfide transfer reaction is developed. The utility and scope of this reaction is exemplified by various aryl electrophiles and aryl sulfides.Mechanistic studies reveal two competing catalytic cycles of sulfide transfer and aryl transfer in this reaction, where the former one is favored over the later one because of the large energy barrier difference during the transmetalation. Moreover, two important chemicals are late-stage functionalized by this method, exhibiting the potential applications in drugs and materials science.

A Thiol-Free Route to Alkyl Aryl Thioethers

“…A range of primary alcohols with varying carbon chain lengths (C 1 –C 8 ) bearing different functionalities are competent partners in this three-step, one-pot telescoped sequence, delivering the corresponding alkyl aryl thioethers in 43–82% yields. Importantly, the protocol is suitable for the introduction of methylthio (thioethers 2i – 2l ) and ethylthio (thioethers 2d – 2h ) groups into an aromatic ring without the use of the corresponding extremely volatile methyl and ethyl mercaptans, thus providing a practical alternative to the current Pd-catalyzed cross-coupling reactions . Employing CD 3 OD allowed us to obtain deuterated thioether 2m in 57% yield with the complete incorporation of deuterium.…”