Manganese(III)-Mediated Radical Additions of Dimethyl Malonate to Olefins. The Chemoselective Synthesis of Diesters and Lactones

Abstract
The radical addition of dimethyl malonate (1) to alkyl-substituted olefins 2a-d can be mediated by potassium permanganate and allows the chemoselective synthesis of saturated esters 4a-d. A high degree of stereoselectivity is observed with 1,5-cyclooctadiene (2d) and trans-stilbene (2f). In the presence of Mn(OAc)3 the lactone 6f is obtained in diastereomerically pure form in 86% yield.

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