biostudies-literatureYao WShimadzuDivision of Advanced CyberinfrastructureOffice of the Vice President for Research, Stony Brook UniversityNational Institute of General Medical SciencesNIGMS NIH HHS3353-3359https://www.ebi.ac.uk/biostudies/studies/S-EPMC8970705biostudies-literatureUnknown144(8)Excited-state palladium catalysis has emerged as a promising strategy for developing novel and valuable reactions. Herein, we report the first excited-state Pd-catalyzed 1,2-radical migratory Mizoroki-Heck reaction that enables C2-alkenylation of carbohydrates using readily available 1-bromosugars and alkenes. The reaction tolerates a wide variety of functional groups and complex molecular architectures, including derivatives of natural products and marketed drugs. Preliminary mechanistic studies and DFT calculations suggest the involvement of visible-light-induced photoexcitation of Pd species, 1,2-spin-centered-shift (SCS) process, and Heck-type cross-coupling reaction. The reaction expands the reactivity profile of excited-state Pd catalysis and provides a streamlined protocol for the pJournal of the American Chemical SocietyExcited-State Palladium-Catalyzed Radical Migratory Mizoroki-Heck Reaction Enables C2-Alkenylation of Carbohydrates.PMC8970705R35 GM128779R35-GM119652-04S1R35-GM119652R35 GM119652ACI1548562R35-GM128779Zhou LZhao GLiu PNgai MYYao WWu YMukherjee UfalseExcited-State Palladium-Catalyzed Radical Migratory Mizoroki-Heck Reaction Enables C2-Alkenylation of Carbohydrates.Excited-state palladium catalysis has emerged as a promising strategy for developing novel and valuable reactions. Herein, we report the first excited-state Pd-catalyzed 1,2-radical migratory Mizoroki-Heck reaction that enables C2-alkenylation of carbohydrates using readily available 1-bromosugars and alkenes. The reaction tolerates a wide variety of functional groups and complex molecular architectures, including derivatives of natural products and marketed drugs. Preliminary mechanistic studies and DFT calculations suggest the involvement of visible-light-induced photoexcitation of Pd species, 1,2-spin-centered-shift (SCS) process, and Heck-type cross-coupling reaction. The reaction expands the reactivity profile of excited-state Pd catalysis and provides a streamlined protocol for the p2022-01-01T00:00:00Z2022 Mar2025-04-26T10:21:11.937Z2025-04-06T13:17:57.072ZS-EPMC89707053518876810.1021/jacs.1c13299