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Recycling the tert-Butanesulfinyl Group in the Synthesis of Amines Using tert-Butanesulfinamide

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journal contribution
posted on 03.04.2009, 00:00 by Masakazu Wakayama, Jonathan A. Ellman
A practical process for recycling the tert-butanesulfinyl group upon deprotection of N-tert-butanesulfinyl amines has been achieved. Treatment of N-tert-butanesulfinyl amines with HCl in cyclopentyl methyl ether results in complete conversion to tert-butanesulfinyl chloride and the corresponding amine hydrochloride salt, which is isolated by filtration in analytically pure form and in quantitative yield. Treatment of the resulting sulfinyl chloride solution with aqueous ammonia then provides analytically pure tert-butanesulfinamide in 97% yield. Alternatively, the tert-butanesulfinyl chloride solution can be treated with ethanol and catalytic quinidine as a sulfinyl transfer catalyst to provide a cyclopentyl methyl ether solution of ethyl tert-butanesulfinate with 88% ee. Addition of NaNH2 in ammonia followed by simple trituration of the product with octane provides tert-butanesulfinamide with 99% ee and in 67% overall isolated yield based upon the starting N-tert-butanesulfinyl amine.