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Communication

Efficient Synthesis of 1,2,4-Dithiazolidine-3,5-diones [Dithiasuccinoyl-Amines] from Bis(chlorocarbonyl)disulfane Plus Bis(trimethylsilyl)amines

Supporting Info

Michael J. Barany,^†^§ Robert P. Hammer,^† R. B. Merrifield,^‡ and George Barany*^†^‡

University of Minnesota, Department of Chemistry, 207 Pleasant Street S.E., Minneapolis, Minnesota 55455, and The Rockefeller University, 1230 York Avenue, New York, New York 10021

J. Am. Chem. Soc., 2005, 127 (2), pp 508–509

DOI: 10.1021/ja0455446

Publication Date (Web): December 23, 2004

†

University of Minnesota.

Current Address: Roseville Area High School, 1240 W County Rd B2, Roseville, MN 55113.

‖

Permanent Address: Department of Chemistry, 232 Choppin Hall, Louisiana State University, Baton Rouge, LA 70803.

‡

The Rockefeller University.

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

barany@umn.edu

Abstract

The 1,2,4-dithiazolidine-3,5-dione heterocycle, also referred to as a dithiasuccinoyl (Dts)-amine, serves as a readily removable amino protecting group for building blocks used in syntheses of peptides, glycopeptides, and PNA; it is also useful as a masked isocyanate and (inversely) as a sulfurization reagent for trivalent phosphorus. Bis(chlorocarbonyl)disulfane, the two-sulfur analogue of succinyl chloride, has been envisioned as a reagent for facile single-step elaboration of the heterocycle. However, reactions of bis(chlorocarbonyl)disulfane directly with primary amines fail to yield Dts-amines for reasons that are discussed. Inspired by several precedents from the organosilicon chemistry literature that a trimethylsilyl group may serve as a “large proton,” a successful, high-yield preparation of Dts-amines through reactions of bis(chlorocarbonyl)disulfane with bis(trimethylsilyl)amines has been developed. Studies aimed at elucidating mechanistic reasons for these observations are also presented.

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