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Asymmetric Hydride Shift Reactions Catalyzed by Chiral Aluminium Complexes

Year: 2025

Type: article

Abstract: An asymmetric intramolecular hydride shift reaction has been developed that is catalyzed by Al Lewis acids in conjunction with a chiral BINOL‐derived ligand. Racemic THP substrates are transformed into cyclohexene products via a prochiral intermediate ring opened enone; which then undergoes a key 1,5‐hydride shift reaction. This reaction is operationally simple, works well on a gram scale, and the desired products are formed with very high enantioselectivity (up to >98:2 e.r.). Importantly, the cyclohexene products contain functionality that can be easily derivatized and this is exemplified in the paper. Finally, a model is presented for the enantioselective hydride shift that is based on previous DFT studies.

Source: Angewandte Chemie

DOI: 10.1002/ange.202521374

Authors: Mostafa M. Amer, Jingyan Hou, Jinfang Wang, Akvile Mazeikaite, Timothy J. Donohoe

Institution: University of Oxford

Language: English

Topic: Asymmetric Synthesis and Catalysis

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $5,790

Funder: Engineering and Physical Sciences Research Council