Direct Sulfination of Nonactivated Alcohols with Arylsulfonylmethyl Isocyanides

Abstract

A direct sulfination of nonactivated alcohols with arylsulfonylmethyl isocyanides under mild conditions [10 mol‐% of Bi(OTf)3, 25 °C] was developed to afford sulfinates instead of the usually favored sulfones. The in situ multiple alcohol activation strategies, along with the properties of sulfones and sulfinate anions, were proposed to explain the reversed sulfinate/sulfone selectivity.

Isocyanide‐Induced Esterification of Sulfinic Acids to Access Sulfinates

“…On the above finding and previous reports, [4b,d,5a,d,e] a possible reaction pathway was outlined and described in Scheme 3. The 4‐methylbenzenesulfinic acid ( 1 b ) was first nucleophilic attacked by ethyl 2‐isocyanoacetate to obtain intermediate A , which underwent rearrangement and isomerization to obtain intermediate compound B .…”

Modern Stereoselective Synthesis of Chiral Sulfinyl Compounds

“…Esters were formed in 57–82% yield. Sulfination of nonactivated alcohols with the use of sulfonyl isocyanides was achieved by Ji et al 171 A double activation was provided by Lewis acid (bismuth(III) triflate) and Brønsted acid (CCl 3 COOH). Asymmetric variant of these two protocols was not proposed.…”