Hexamethyldisilazane (HMDS) Promotes Highly Efficient Oxidative Coupling of Thiols by DMSO Under Nearly Neutral Reaction Conditions

Abstract

A variety of thiols were efficiently converted to their disulfides using DMSO in the presence of hexamethyldisilazane (HMDS) under almost neutral reaction conditions. Due to the neutrality of the reaction medium in this protocol, acid sensitive functional groups survived intact.

oxidation - oxidative coupling - thiols - disulfides - hexamethyldisilizane - DMSO

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<A NAME="RG31301ST-8">8</A>

General Procedure for Oxidative Coupling of Thiols to Disulfides: To a solution of thiol (3 mmol) and DMSO (9 mmol) in anhyd acetonitrile (5 mL), HMDS (3.6 mmol) was added and the resulting solution was magnetically stirred at r.t. The progress of the reaction was monitored by TLC. After completion of the reaction, the mixture was poured into 10% aq NaOH solution. The organic layer was separated and the aq phase was extracted with ether (3 × 50 mL). The organic extracts were combined together and was washed successively with 10% NaOH (25 mL) and water (2 × 50 mL) and dried over anhyd Na₂SO₄. Evaporation of the solvent under reduced pressure gave the almost pure disulfide. Further purification of the product was achieved by re-crystallization or column chromatography through a short silica-gel column.