Improved Synthesis of 1‐Benzenesulfinyl Piperidine and Analogs for the Activation of Thioglycosides in Conjunction with Trifluoromethanesulfonic Anhydride*

* Dedicated with respect to the memory of Professor Jacques H. Van Boom.

Abstract

An improved protocol for the large‐scale production of 1‐benzenesulfinyl piperidine and other sulfinamides is described. It is demonstrated that 1‐benzenesulfinyl pyrrolidine and N,N‐diethyl benzenesulfinamide function analogously to 1‐benzenesulfinyl piperidine in the trifluoromethanesulfonic anhydride‐mediated activation of thioglycosides, and that their less crystalline nature enables them to be used at −78°C as opposed to the −60°C required to keep 1‐benzenesulfinyl piperidine in solution. N,N-Dicyclohexyl benzenesulfinamide does not activate thioglycosides in combination with trifluoromethanesulfonic anhydride, which is attributed to its greater steric bulk.

* Dedicated with respect to the memory of Professor Jacques H. Van Boom.

Keywords:

• Glycosylation
• Sulfinamide
• Thioglycoside
• Trifluoromethanesulfonate

Acknowledgments

We thank the NIH (GM 62160) for support of this work.

Notes

* Dedicated with respect to the memory of Professor Jacques H. Van Boom.