Iodine-Promoted Reductive Sulfenylation Using Ketones as Hydride Donors

Abstract

Herein, an iodine-promoted reductive sulfenylation reaction of ketones with disulfides has been developed. This method provides an approach for synthesizing unsymmetrical alkyl−alkyl and alkyl−aryl sulfides in a single step. Investigation of the reaction mechanism revealed that ketones play a dual role in this process. They react with disulfides to produce vinyl thioethers and act as effective organic hydride donors, reducing the number of vinyl thioethers that are formed in situ. This study expands the range of applications of ketones in chemical synthesis.

Expedient Syntheses of Alkyl and Aryl Thioethers using Xanthates as Thiol-Free Reagents

“…Most thiols are air-sensitive and readily oxidized to produce disulfides under aerobic atmospheric conditions. To overcome these limitations, the attractive alternative methods for the sulfuration of alkyl halides and aryl halides involve the use of other sulfurizing agents, e.g., S powder [7][8][9][10], bunte salts [11][12][13], dimethyl sulfoxide (DMSO) [14,15], carenesulfonyl Cyanides [16], S-methylisothiourea [17], N-substituted sulfanylsuccinimides [18,19], disulfides [20][21][22], sulfonyl chlorides [23,24], sodium sulfinates [25][26][27], and sulfonyl hydrazides [28,29], because these off-the-shelf thiol-free sulfurizing agents generally release little to no odors.…”

Expedient Synthesis of Alkyl and Aryl Thioethers Using Xanthates as Thiol-Free Reagents

“…Most thiols are air-sensitive and readily oxidized to produce disulfides under aerobic atmospheric conditions. To overcome these limitations, the attractive alternative methods for the sulfuration of alkyl halides and aryl halides involve the use of other sulfurizing agents, e.g., S powder [ 7 , 8 , 9 , 10 ], bunte salts [ 11 , 12 , 13 ], dimethyl sulfoxide (DMSO) [ 14 , 15 ], carenesulfonyl cyanides [ 16 ], S-methylisothiourea [ 17 ], N-substituted sulfanylsuccinimides [ 18 , 19 ], disulfides [ 20 , 21 , 22 ], sulfonyl chlorides [ 23 , 24 ], sodium sulfinates [ 25 , 26 , 27 ], and sulfonyl hydrazides [ 28 , 29 ], because these off-the-shelf thiol-free sulfurizing agents generally release little to no odors.…”