Understanding
Halide Counterion Effects in Enantioselective
Ruthenium-Catalyzed Carbonyl (α-Aryl)allylation: Alkynes as
Latent Allenes and Trifluoroethanol-Enhanced Turnover in The Conversion
of Ethanol to Higher Alcohols via Hydrogen Auto-transfer
posted on 2021-10-04, 17:34authored byEliezer Ortiz, Jonathan Z. Shezaf, Yu-Hsiang Chang, Théo P. Gonçalves, Kuo-Wei Huang, Michael J. Krische
Crystallographic characterization
of RuX(CO)(η3-C3H5)(JOSIPHOS),
where X = Cl, Br, or I, reveals
a halide-dependent diastereomeric preference that defines metal-centered
stereogenicity and, therefrom, the enantioselectivity of C−C
coupling in ruthenium-catalyzed anti-diastereo- and
enantioselective C−C couplings of primary alcohols with 1-aryl-1-propynes
to form products of carbonyl anti-(α-aryl)allylation.
Computational studies reveal that a non-classical hydrogen bond between
iodide and the aldehyde formyl CH bond stabilizes the favored transition
state for carbonyl addition. An improved catalytic system enabling
previously unattainable transformations was developed that employs
an iodide-containing precatalyst, RuI(CO)3(η3-C3H5), in combination with trifluoroethanol,
as illustrated by the first enantioselective ruthenium-catalyzed C−C
couplings of ethanol to form higher alcohols.