Catalytic regioselective sulfonylation of alpha-chelatable alcohols: scope and mechanistic insight

Michael J Martinelli; Rajappa Vaidyanathan; Joseph M Pawlak; Naresh K Nayyar; Ulhas P Dhokte; Christopher W Doecke; Lisa M H Zollars; Eric D Moher; Vien Van Khau; Berta Kosmrlj

doi:10.1021/ja016031r

Catalytic regioselective sulfonylation of alpha-chelatable alcohols: scope and mechanistic insight

J Am Chem Soc. 2002 Apr 10;124(14):3578-85. doi: 10.1021/ja016031r.

Authors

Michael J Martinelli¹, Rajappa Vaidyanathan, Joseph M Pawlak, Naresh K Nayyar, Ulhas P Dhokte, Christopher W Doecke, Lisa M H Zollars, Eric D Moher, Vien Van Khau, Berta Kosmrlj

Affiliation

¹ Chemical Process R&D, Lilly Research Laboratories, Lilly Corporate Center, Eli Lilly and Company, Indianapolis, Indiana 46285-4813, USA. mjm@lilly.com

PMID: 11929246
DOI: 10.1021/ja016031r

Abstract

This paper describes a convenient protocol for the regioselective sulfonylation of alpha-chelatable alcohols. Typically, the reaction of alpha-heterosubstituted alcohols with 1 equiv of p-TsCl and 1 equiv of Et(3)N in the presence of 2 mol % of Bu(2)SnO leads to rapid, regioselective, and exclusive monotosylation. The pK(a) of the amine was correlated to the reaction rate. A plausible mechanism for this reaction has been proposed on the basis of (119)Sn NMR studies.