10.1021/acs.organomet.7b00392.s002
Tesia
V. Chciuk
Tesia
V.
Chciuk
William R. Anderson
William R.
Anderson
Robert A. Flowers
Robert A.
Flowers
Reversibility of Ketone Reduction by SmI<sub>2</sub>–Water and Formation of Organosamarium Intermediates
American Chemical Society
2017
PCET
SmI
ketone reductions
2017-07-25 18:47:30
Dataset
https://acs.figshare.com/articles/dataset/Reversibility_of_Ketone_Reduction_by_SmI_sub_2_sub_Water_and_Formation_of_Organosamarium_Intermediates/5244538
The reduction of ketones by SmI<sub>2</sub>–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 SmI<sub>2</sub>–water
through a proton-coupled electron-transfer (PCET). Literature values
for the rates of radical cyclizations and reduction of radicals by
SmI<sub>2</sub> and thermochemical data for radical reduction by SmI<sub>2</sub>–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 SmI<sub>2</sub>–water.