Indirect cation pool method. Rapid generation of alkoxycarbenium ion pools from thioacetals

Seiji Suga; Kouichi Matsumoto; Koji Ueoka; Jun-ichi Yoshida

doi:10.1021/ja0625778

Indirect cation pool method. Rapid generation of alkoxycarbenium ion pools from thioacetals

J Am Chem Soc. 2006 Jun 21;128(24):7710-1. doi: 10.1021/ja0625778.

Authors

Seiji Suga¹, Kouichi Matsumoto, Koji Ueoka, Jun-ichi Yoshida

Affiliation

¹ Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510, Japan.

PMID: 16771464
DOI: 10.1021/ja0625778

Abstract

A sequential one-pot indirect cation pool method has been developed. The method involves the electrochemical generation and accumulation of ArS(ArSSAr)+ at low temperature (step 1) and the follow-up reaction with a thioacetal to generate an alkoxycarbenium ion pool (step 2), which reacts with various carbon nucleophiles (step 3). Steps 2 and 3 are extremely fast. The electrogenerated ArS(ArSSAr)+ was well-characterized by 1H NMR and CSI-MS. The alkoxycarbenium ion pool generated by the present indirect method exhibited 1H and 13C NMR spectra and thermal stability similar to those of the alkoxycarbenium ion pool generated by the direct electrochemical method.