Substrate-Directable Electron Transfer Reactions. Dramatic Rate Enhancement in the Chemoselective Reduction of Cyclic Esters Using SmI2–H2O: Mechanism, Scope, and Synthetic Utility | Zendy

Michal Szostak | Zendy; Malcolm Spain | Zendy; Kimberly A. Choquette | Zendy; Robert A. Flowers | Zendy; David J. Procter | Zendy

Open Access

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

Author(s) -

Michal Szostak,

Malcolm Spain,

Kimberly A. Choquette,

Robert A. Flowers,

David J. Procter

Publication year - 2013

Publication title -

journal of the american chemical society

Language(s) - English

Resource type - Journals

SCImago Journal Rank - 7.115

H-Index - 612

eISSN - 1520-5126

pISSN - 0002-7863

DOI - 10.1021/ja4078864

Subject(s) - chemistry , chemoselectivity , substrate (aquarium) , lanthanide , electron transfer , redox , scope (computer science) , combinatorial chemistry , reaction mechanism , photochemistry , chelation , organic chemistry , catalysis , ion , oceanography , computer science , programming language , geology

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 SmI2-H2O and for the first time proceeds with a broad substrate scope. Initial studies on the origin of selectivity and synthetic application to form carbon-carbon bonds are also disclosed.

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