Regio- and stereoselective ring contraction of 1,2-dithianes to 1,2-dithiolanes

Monobenzoylated 1,2-dithiane-4,5 diols undergo a novel ring contraction reaction under Mitsunobu con-ditions to produce 3,4-disubstituted 1,2-dithiolanes. This transformation is stereoselective and proceeds with retention of configuration. The yields for the trans isomers are higher than those of the cis series for a variety of O, N and S nucleophiles. A plausible pathway for forming the 1,2-dithiolanes involves the for-mation of a S-episulfonium intermediates.(c) 2023 Elsevier Ltd. All rights reserved.

Automated summary

Monobenzoylated 1,2-dithiane-4,5 diols undergo a novel ring contraction reaction under Mitsunobu conditions to produce 3,4-disubstituted 1,2-dithiolanes. This transformation is stereoselective and proceeds with retention of configuration. The yields for the trans isomers are higher than those of the cis series for a variety of O, N and S nucleophiles. A plausible pathway for forming the 1,2-dithiolanes involves the formation of a S-episulfonium intermediates.(c) 2023 Elsevier Ltd. All rights reserved.