Bis(arylsulfonyl) Peroxide-Mediated Difunctionalization of Cyclic Enol Ethers

Abstract

A bis(arylsulfonyl) peroxide-mediated 1,2-difunctionalization of cyclic enol ethers is reported. Bis(nosyl) peroxide selectively sulfonylates the 3position of enol ethers, generating an oxocarbenium ion that is trapped by a carboxylic acid nucleophile at the 2-position. The reaction proceeds in a good yield and tolerates a variety of cyclic enol ethers, including glycals as well as various carboxylic acids, which act as the oxocarbeium ion trapping reagents.

A Study of Alkene Disulfonoxylation

“…Relative to alkene dihydroxylation, [1][2][3] alkene disulfonoxylation remains less explored (Scheme 1). [4][5][6][7][8][9][10] As diols are often subsequently converted into the corresponding tosylates or mesylates, one step syntheses of such compounds from alkene starting materials would be desirable from the perspective of step economy and reagent waste. Existing protocols for disulfonoxylation [4][5][6][7][8][9][10] have greatly inspired this study and most employ the use of hypervalent iodine reagents, [11][12][13][14][15][16][17] which are convenient alternatives to toxic metals such as osmium.…”