Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 61, Issue 46, Pages -Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202212948
Keywords
Allylic Alcohol; Asymmetric Catalysis; Stereodiyergent; Synergistic Catalysis; alpha-Amino Acid
Categories
Funding
- NSFC [220711186, 22101216, 22073067]
- Hubei Province Natural Science Foundation [2020CFA036]
- China Postdoctoral Science Foundation [2021M702514]
- Fundamental Research Funds for the Central Universities [2042022kf1180]
Ask authors/readers for more resources
Cooperative bimetallic catalysis enables regio-/stereodivergent asymmetric alpha-allylations of aldimine esters. By employing Et3B as the key activator, racemic allylic alcohols can be directly ionized to form Pd or Ir-pi-allyl species in the presence of achiral Pd or chiral Ir complexes, respectively. The reaction exhibits high regioselectivity and excellent stereoselectivity.
We describe cooperative bimetallic catalysis that enables regio-/stereodivergent asymmetric alpha-allylations of aldimine esters. By employing Et3B as the key activator, racemic allylic alcohols can be directly ionized to form Pd or Ir-pi-allyl species in the presence of achiral Pd or chiral Ir complexes, respectively. The less or more substituted allylic termini of the metal-pi-allyl species are amenable to nucleophilic attack by the chiral Cu-azomethine ylide, the formation of which is simultaneously facilitated by Et3B, affording alpha-quaternary alpha-amino acids with high regioselectivity and excellent stereoselectivity. The use of readily available allylic alcohols as electrophilic precursors represents an improvement from an environmental and atom/step economy perspective. Computational mechanistic studies reveal the crucial role of the Et3B additive and the origins of stereo- and regioselectivities by analyzing steric effects, dispersion interactions, and frontier orbital population.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available