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Chiral Phosphoric Acid Dual‐Function Catalysis: Asymmetric Allylation with α‐Vinyl Allylboron Reagents
Author(s) -
Gao Shang,
Duan Meng,
Houk Kendall N.,
Chen Ming
Publication year - 2020
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.202000039
Subject(s) - phosphoric acid , catalysis , chemistry , enantioselective synthesis , steric effects , reagent , substituent , alkyl , organic chemistry , diol , combinatorial chemistry
We report a dual function asymmetric catalysis by a chiral phosphoric acid catalyst that controls both enantioselective addition of an achiral α‐vinyl allylboronate to aldehydes and pseudo‐axial orientation of the α‐vinyl group in the transition state. The reaction produces dienyl homoallylic alcohols with high Z ‐selectivities and enantioselectivities. Computational studies revealed that minimization of steric interactions between the alkyl groups of the diol on boron and the chiral phosphoric acid catalyst influence the orientation of α‐vinyl substituent of the allylboronate reagent to occupy a pseudo‐axial position in the transition state.