Lewis Base-Catalyzed
Enantioselective Conjugate Reduction
of β,β-Disubstituted α,β-Unsaturated
Ketones with Trichlorosilane: E/Z‑Isomerization, Regioselectivity,
and Synthetic Applications
Posted on 2019-09-06 - 20:29
The
chiral bisphosphine dioxide-catalyzed asymmetric conjugate
reduction of acyclic β,β-disubstituted α,β-unsaturated
ketones with trichlorosilane affords saturated ketones having a stereogenic
carbon center at the carbonyl β-position with high enantioselectivities.
Because the E/Z-isomerizations of enone substrates
occur concomitantly, reduction products with the same absolute configurations
are obtained from either (E)- or (Z)-enones. Conjugate reduction is accelerated in the presence of an
electron-rich aryl group at the β-position of the enone owing
to its carbocation-stabilizing ability. Computational studies were
also conducted in order to elucidate the origin of the observed enantioselectivity.
The regio- and enantioselective reductions of dienones were realized
and applied to the syntheses of ar-turmerone, turmeronol
A, mutisianthol, and jungianol, which are optically active sesquiterpenes.
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Sugiura, Masaharu; Ashikari, Yasuhiko; Takahashi, Yuka; Yamaguchi, Koki; Kotani, Shunsuke; Nakajima, Makoto (2019). Lewis Base-Catalyzed
Enantioselective Conjugate Reduction
of β,β-Disubstituted α,β-Unsaturated
Ketones with Trichlorosilane: E/Z‑Isomerization, Regioselectivity,
and Synthetic Applications. ACS Publications. Collection. https://doi.org/10.1021/acs.joc.9b01298
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AUTHORS (6)
MS
Masaharu Sugiura
YA
Yasuhiko Ashikari
YT
Yuka Takahashi
KY
Koki Yamaguchi
SK
Shunsuke Kotani
MN
Makoto Nakajima
KEYWORDS
carbonyl β- positionconjugate reductionchiral bisphosphine dioxide-catalyzedSynthetic Applicationsenantioselective reductionsenone substratesLewis Base-Catalyzed Enantioselective Conjugate Reductionβ- positionstereogenic carbon centerelectron-rich aryl groupComputational studiesConjugate reductionreduction productscarbocation-stabilizing abilityketone