TY - JOUR
T1 - Enantioselective Synthesis of (E)-δ-Boryl-Substituted anti-Homoallylic Alcohols Using Palladium and a Chiral Phosphoric Acid
AU - Miura, Tomoya
AU - Nakahashi, Junki
AU - Murakami, Masahiro
N1 - Funding Information:
This work was supported by Grants-in-Aid for Scientific Research (S) (15H05756) and (C) (16K05694) from MEXT.
Publisher Copyright:
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2017/6/6
Y1 - 2017/6/6
N2 - (E)-δ-Boryl-substituted anti-homoallylic alcohols are synthesized in a highly diastereo- and enantioselective manner from 1,1-di(boryl)alk-3-enes and aldehydes. Mechanistically, the reaction consists of 1) palladium-catalyzed double-bond transposition of the 1,1-di(boryl)alk-3-enes to 1,1-di(boryl)alk-2-enes, 2) chiral phosphoric acid catalyzed allylation of aldehydes, and 3) palladium-catalyzed geometrical isomerization from the Z to E isomer. As a result, the configurations of two chiral centers and one double bond are all controlled with high selectivity in a single reaction vessel.
AB - (E)-δ-Boryl-substituted anti-homoallylic alcohols are synthesized in a highly diastereo- and enantioselective manner from 1,1-di(boryl)alk-3-enes and aldehydes. Mechanistically, the reaction consists of 1) palladium-catalyzed double-bond transposition of the 1,1-di(boryl)alk-3-enes to 1,1-di(boryl)alk-2-enes, 2) chiral phosphoric acid catalyzed allylation of aldehydes, and 3) palladium-catalyzed geometrical isomerization from the Z to E isomer. As a result, the configurations of two chiral centers and one double bond are all controlled with high selectivity in a single reaction vessel.
KW - allylation
KW - asymmetric synthesis
KW - homoallylic compounds
KW - organocatalysis
KW - palladium
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U2 - 10.1002/anie.201702611
DO - 10.1002/anie.201702611
M3 - Article
C2 - 28488388
AN - SCOPUS:85019109359
VL - 56
SP - 6989
EP - 6993
JO - Angewandte Chemie - International Edition
JF - Angewandte Chemie - International Edition
SN - 1433-7851
IS - 24
ER -