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

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posted on 25.07.2017 by Tesia V. Chciuk, William R. Anderson, Robert A. Flowers
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.