biostudies-literatureAmer MMLithuanian State Studies FoundationEPSRCEngineering and Physical Sciences Research Councile21374https://www.ebi.ac.uk/biostudies/studies/S-EPMC12850996biostudies-literatureUnknown65(5)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.Angewandte Chemie (International ed. in English)Asymmetric Hydride Shift Reactions Catalyzed by Chiral Aluminium Complexes.PMC12850996EP/W02246X/1EP/V028995/1Donohoe TJHou JMazeikaite AWang JAmer MMfalseAsymmetric Hydride Shift Reactions Catalyzed by Chiral Aluminium Complexes.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.2026-01-01T00:00:00Z2026 Jan2026-06-10T09:01:32.924Z2026-06-10T03:11:53.194ZS-EPMC128509964141030510.1002/anie.202521374