Synthesis of Epoxides from Alkyl Bromides and Alcohols with in Situ Generation of Dimethyl Sulfonium Ylide in DMSO Oxidations

Abstract

Direct conversion of the readily available alkyl bromides and alcohols to value-added epoxides using dimethyl sulfoxide (DMSO) under mild reaction conditions has been developed. Benzyl and allyl bromides, and activated and unactivated alcohols all proceeded smoothly to give epoxides in high to excellent yield. Dimethyl sulfide, generated by DMSO oxidations, was in situ elaborated to form the substituted dimethyl sulfonium ylide species that participates in the Corey–Chaykovsky epoxidation in a domino and one-pot fashion, respectively.

Electro-oxidative quinylation of sulfides to sulfur ylides in batch and continuous flow

“… 24 , 25 , 26 , 27 , 28 , 29 In general, deprotonation of sulfonium salts in the presence of base gave the corresponding sulfur ylides. 30 , 31 Most recently, Martin’s sulfurane (bis[α,α-bis(trifluoromethyl)benzyloxy] diphenylsulfur) was proved to be the efficient reagent to give the sulfur ylides. 32 , 33 Moreover, sulfur ylides could also be prepared from metal carbenes which could be generated from diazo compounds 34 , 35 , 36 , 37 or iodonium ylides 38 in the presence of metal catalyst.…”

Catalyst- and additive-free [3 + 3] cyclization–aromatization of β,γ-dioxobutanoate with amines for synthesis ofp-aminophenols

“…We report herein an unprecedented [3 + 3] aldol cyclization–aromatization reactions of β,γ-dioxobutanoate and various amines for the synthesis of p -aminophenols. β,γ-Dioxobutanoate is easily prepared on a 20-gram scale by Kornblum oxidation 18 of the commercially available 4-chloroacetoacetate. This cyclization–aromatization proceeds smoothly under mild, green and sustainable reaction conditions without any catalysts and additives.…”

Visible-Light Photoredox-Catalyzed Synthesis of trans-Oxiranes via Decarboxylative Stereospecific Epoxidation of trans-Cinnamic Acids by Aryldiazonium Salts

“…The use of an in situ -generated sulfur ylide by the reaction of sulfoxide and benzyne has also been employed to synthesize epoxides from carbonyl compounds . A direct conversion of alkyl bromides and alcohols to epoxides is also described using in situ -generated dimethyl sulfonium ylide . Dioxiranes, peracids, oxaziridines, and oxaziridinium salts are some other useful oxidation reagents for the transformation of olefins to epoxides .…”