50986-80-6Relevant academic research and scientific papers
Reversibility of Ketone Reduction by SmI2-Water and Formation of Organosamarium Intermediates
Chciuk, Tesia V.,Anderson, William R.,Flowers, Robert A.
, p. 4579 - 4583 (2017)
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.
