RESUMEN
An enantioselective synthesis of the C(1)-C(15) segment of the marine natural product amphidinolide C has been accomplished by a route that includes a stereoselective boron-Wittig reaction to furnish a trisubstituted alkenylboronate. In addition, the route employs enantioselective alkene diboration to install the C(6) hydroxyl group which undergoes intramolecular conjugate addition to establish a tetrahydrofuran ring. Lastly, a catalytic Suzuki-Miyaura cross-coupling is accomplished to construct the C(9)-C(10) bond.
Asunto(s)
Productos Biológicos/síntesis química , Furanos/química , Macrólidos/síntesis química , Alquenos/química , Productos Biológicos/química , Boro/química , Catálisis , Macrólidos/química , Estructura Molecular , EstereoisomerismoRESUMEN
Application of the boron-Wittig reaction to ketone electrophiles provides a straightforward route to trisubstituted alkenylboronic esters. With either a pentamethyldiethylenetriamine or trimethyl-1,4,7-triazacyclononane additive, the olefination can occur with very high levels of stereocontrol and in good chemical yield.
Asunto(s)
Alquenos/síntesis química , Compuestos de Boro/síntesis química , Boro/química , Indicadores y Reactivos/síntesis química , Cetonas/química , Alquenos/química , Compuestos de Boro/química , Indicadores y Reactivos/química , Estructura Molecular , EstereoisomerismoRESUMEN
This tutorial review describes recent developments in catalytic reaction design that involve catalyst-promoted 1,2-metalate shifts as a critical part of the reaction mechanism. Issues pertaining to catalysis, stereoselectivity, and reaction mechanism are discussed.
RESUMEN
Palladium-catalyzed conjunctive cross-coupling is used for the synthesis of enantioenriched allylboron reagents. This reaction employs nonsymmetric bis(alkenyl)borates as substrates and appears to occur by a mechanism that involves selective activation of the less substituted alkene followed by migration of the more substituted alkene during the course of a Pd-induced metalate rearrangement.