Substrate-Directable Electron Transfer Reactions. Dramatic Rate Enhancement in the Chemoselective Reduction of Cyclic Esters Using SmI2–H2O: Mechanism, …

…, KA Choquette, RA Flowers, DJ Procter

Index: Szostak, Michal; Spain, Malcolm; Choquette, Kimberly A.; Flowers, Robert A.; Procter, David J. Journal of the American Chemical Society, 2013 , vol. 135, # 42 p. 15702 - 15705

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Citation Number: 27

Abstract

Substrate-directable reactions play a pivotal role in organic synthesis, but are uncommon in reactions proceeding via radical mechanisms. Herein, we provide experimental evidence showing dramatic rate acceleration in the Sm (II)-mediated reduction of cyclic esters that is enabled by transient chelation between a directing group and the lanthanide center. This process allows unprecedented chemoselectivity in the reduction of cyclic esters using ...