5 years ago

Reversibility of Ketone Reduction by SmI2–Water and Formation of Organosamarium Intermediates

Reversibility of Ketone Reduction by SmI2–Water and Formation of Organosamarium Intermediates
William R. Anderson, Robert A. Flowers, Tesia V. Chciuk
The reduction of ketones by SmI2–water has long been thought to proceed through a reversible initial electron transfer with the formation of organosamarium intermediates in a follow-up step. Kinetic experiments on the reduction of two model ketones and structurally similar ketones with a pendant alkene are shown to be consistent with a rate-limiting reduction by SmI2–water through a proton-coupled electron-transfer (PCET). Literature values for the rates of radical cyclizations and reduction of radicals by SmI2 and thermochemical data for radical reduction by SmI2–water further support a rate-limiting initial step for ketone reductions. These data suggest that discrete organosamarium species may not be intermediates in ketone reductions by SmI2–water.

Publisher URL: http://dx.doi.org/10.1021/acs.organomet.7b00392

DOI: 10.1021/acs.organomet.7b00392

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