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Please login or sign up for a free trial to access the full content. Via Mixed Sulfonic Anhydrides

DOI: 10.1055/sos-SD-120-00045

Mourad, A. K.; Czekelius, C.Science of Synthesis Knowledge Updates, (2011378.

Sulfonyl halides are frequently used for the preparation of esters. In particular, 4-toluenesulfonyl chloride (TsCl),[‌2‌,‌3‌] methanesulfonyl chloride (MsCl),[‌4‌,‌5‌] sulfuryl chloride fluoride (SO2ClF),[‌6‌] and N,N-dimethylchlorosulfonamide (Me2NSO2Cl)[‌7‌,‌8‌] have been reported in this context. For example, 3,5-dinitrobenzoic acid (1) and 3-phenylpropanoic acid (3) are transformed into tert-butyl 3,5-dinitrobenzoate (2) and phenyl 3-phenylpropanoate (4), respectively (Table 1). The use of methanesulfonyl chloride can lead to diminished yields due to sulfene formation by deprotonation of the methyl group. A variant of the procedure is the application of polymer-supported sulfonyl halides such as poly(styrylsulfonyl chloride).[‌9‌] In addition to sulfonyl halides, related reagents, such as 1-tosylimidazole,[‌10‌] trifluoromethanesulfonic anhydride (Tf2O),[‌11‌,‌12‌] 1-(chlorosulfonyloxy)-N,N-dimethyl­meth­animinium chloride [ClS(O)OCH═NMe2+ Cl-],[‌13‌] or 4,5-dichloro-2-[(4-nitrophenyl)sulfonyl]pyridazin-3(2H)-one (6)[‌14‌] are successfully employed in this context. Use of the last of these reagents is exemplified by the synthesis of methyl diphenylacetate (7) from di­phen­ylacetic acid (5).

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