Barbeira-Arán, SergioSánchez-Sordo, IreneFañanás-Mastral, MartínBarbeira Arán, SergioSánchez Sordo, IreneFañanás-Mastral, Martín2024-10-012024-10-012024-04-30Org. Lett. 2024, 26, 18, 3784–37891523-7060http://hdl.handle.net/10347/34985Bicyclo[1.1.1]pentanes (BCPs) have emerged as important structural motifs in drug design. However, asymmetric transformations that provide chiral BCPs bearing an adjacent stereocenter are still scarce. Here, we report a catalytic methodology for the enantioselective synthesis of α-chiral 1,3-difunctionalized BCPs from a three-component coupling of [1.1.1]propellane, a Grignard reagent, and an allylic phosphate. The reaction proceeds via the addition of the Grignard reagent to [1.1.1]propellane followed by an asymmetric N-heterocyclic carbene (NHC)-catalyzed allylic substitution of the resulting BCP–Grignard, providing a broad range of α-chiral BCPs with excellent levels of regioselectivity and enantioselectivityengAtribución 4.0 Internacional© 2024 The Authors. Published by American Chemical Society. This publication is licensed under CC-BY 4.0http://creativecommons.org/licenses/by/4.0/AlkylsCatalystsPhosphatesReagentsStereoselectivityjournal article10.1021/acs.orglett.4c009021523-7052open access