Rh-catalyzed desymmetrization of α-quaternary centers by isomerization-hydroacylation† †Electronic supplementary information (ESI) available: Materials and methods, reaction procedures, characterization data. CCDC 1056687, 1062118. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc01553g Click here for additional data file. Click here for additional data file.
نویسندگان
چکیده
We describe a Rh-catalyzed desymmetrization of all-carbon quaternary centers from α,α-bis(allyl)aldehydes by a cascade featuring isomerization and hydroacylation. This desymmetrization competes with two other novel olefin functionalizations that are triggered by C-H bond activation, including carboacylation and bisacylation. A BIPHEP ligand promotes enantioselective formation of α-vinylcyclopentanones. Mechanistic studies support irreversible and enantioselective olefin-isomerization followed by olefin-hydroacylation.
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Shanghai Engineering Research Center of Development, East China Normal Univers [email protected]; [email protected] School of Chemistry and Chemical Eng 530004, China NYU-ECNU Center for Computational C 200062, China † Electronic supplementary information ( optimized structures, experimental data 984118. For ESI and crystallographic data DOI: 10.1039/c7sc00257b ‡ These authors contributed equ...
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