Open AccessConversion of Primary Alcohols and Butadiene to Branched Ketones via Merged Transfer Hydrogenative Carbonyl Addition–Redox Isomerization Catalyzed by Rhodium
Author(s) -
Brian J. Spinello,
Jing Wu,
Yoon Cho,
Michael J. Krische
Publication year - 2021
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/jacs.1c07230
Subject(s) - chemistry , rhodium , isomerization , aldehyde , photochemistry , redox , catalysis , dissociation (chemistry) , alcohol oxidation , sodium formate , ketone , organic chemistry
The first examples of rhodium-catalyzed carbonyl addition via hydrogen autotransfer are described, as illustrated in tandem butadiene-mediated carbonyl addition-redox isomerizations that directly convert primary alcohols to isobutyl ketones. Related reductive coupling-redox isomerizations of aldehyde reactants mediated by sodium formate also are reported. A double-labeling crossover experiment reveals that the rhodium alkoxide obtained upon carbonyl addition enacts redox isomerization without dissociation of rhodium at any intervening stage.