Opportune gem-Silylborylation of Carbonyl Compounds: A Modular and Stereocontrolled Entry to Tetrasubstituted Olefins
Enrico La Cascia
Department Química Física i Inorgànica, University Rovira i Virgili, C/Marcel⋅lí Domingo s/n, Tarragona, Spain
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Dr. Ana B. Cuenca
Department Química Física i Inorgànica, University Rovira i Virgili, C/Marcel⋅lí Domingo s/n, Tarragona, Spain
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Dr. Elena Fernández
Department Química Física i Inorgànica, University Rovira i Virgili, C/Marcel⋅lí Domingo s/n, Tarragona, Spain
Search for more papers by this authorEnrico La Cascia
Department Química Física i Inorgànica, University Rovira i Virgili, C/Marcel⋅lí Domingo s/n, Tarragona, Spain
Search for more papers by this authorCorresponding Author
Dr. Ana B. Cuenca
Department Química Física i Inorgànica, University Rovira i Virgili, C/Marcel⋅lí Domingo s/n, Tarragona, Spain
Search for more papers by this authorCorresponding Author
Dr. Elena Fernández
Department Química Física i Inorgànica, University Rovira i Virgili, C/Marcel⋅lí Domingo s/n, Tarragona, Spain
Search for more papers by this authorGraphical Abstract
Stereo-power with silylborylation: The stereocontrolled synthesis of all-carbon tetrasubstituted alkenes was achieved with gem-silylborylated structures that perform selective silicon- or boron-based cross coupling. The access to gem-silylborylated olefins from ketones and HC(Bpin)2(SiMe3) is based on B−O olefination. Selective iododesilylation accomplishes target C−Si mediated cross coupling, and hence the stereoselective preparation of tetra-substituted olefins (see example for Tamoxifen).
Abstract
An easy access to highly versatile gem-silylboronate synthons is achieved by means of a new olefination reagent, HC(Bpin)2(SiMe3). Subsequent silicon or boron-based selective functionalization allows for the modular and stereocontrolled synthesis of all-carbon tetrasubstituted alkenes. A particular attraction of this approach is the iododesilylation reaction, which becomes a pivotal tool for C−Si functionalization.
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