Dynamic Kinetic Resolution Allows Control of Remote Stereochemistry in Asymmetric Hydrogen Borrowing Alkylation
Year: 2025
Type: article
Abstract: A catalytic asymmetric method for the synthesis of γ-substituted ketones via hydrogen borrowing alkylation of both racemic linear precursors and 1,5-diols is described. The base mediated racemization of an intermediate cyclohexenone to facilitates a dynamic kinetic resolution, affording highly enantioenriched cyclohexanes in excellent yields, which could be further functionalized by removal of the Ph* group. DFT modelling revealed the mode of enantioinduction to be a stepwise process comprising of a hydride transfer and a coordination change to a π-allylic enolate complex with the iridium catalyst.
Institutions: University of Oxford, AstraZeneca (United Kingdom)
Language: English
Subfield: Inorganic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $5,510
Funders: Pfizer, AstraZeneca, Diamond Light Source, UK Research and Innovation, Royal Commission for the Exhibition of 1851, National Institutes of Health, Defence Science and Technology Laboratory, Engineering and Physical Sciences Research Council, Defence Science and Technology Group, H2020 Marie Skłodowska-Curie Actions
OpenAlex ID: W4407153340