Rh-catalyzed desymmetrization of α-quaternary centers by isomerization-hydroacylation
نویسندگان
چکیده
We describe a Rh-catalyzed desymmetrization of all-carbon quaternary centers from a,a-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 avinylcyclopentanones. Mechanistic studies support irreversible and enantioselective olefin-isomerization followed by olefin-hydroacylation.
منابع مشابه
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.
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-vinylcyclopen...
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