Asymmetric Hydride Shift Reactions Catalyzed by Chiral Aluminium Complexes
Abstract
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.
Article Details
Authors (5)
Mostafa M. Amer
Department of Chemistry University of Oxford, Chemistry Research Laboratory Mansfield Road Oxford OX1 3TA UK
Jingyan Hou
Department of Chemistry University of Oxford, Chemistry Research Laboratory Mansfield Road Oxford OX1 3TA UK
Jinfang Wang
Department of Chemistry University of Oxford, Chemistry Research Laboratory Mansfield Road Oxford OX1 3TA UK
Akvile Mazeikaite
Department of Chemistry University of Oxford, Chemistry Research Laboratory Mansfield Road Oxford OX1 3TA UK
Timothy J. Donohoe
Department of Chemistry, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA, U.K.