Tandem reactions in organic synthesis possess the power to transform simple, readily available starting materials into complex, valuable products in a direct fashion.  In addition, the number of highly enantioselective, catalytic reactions engaging simple terminal olefins as starting materials is under-developed and limited to a relatively small class of fundamental transformations.  The present methodology represents a significant contribution to this area, by using platinum catalyzed enantioselective diboration to access 1,2-diboron reagents, which subsequently participate as nucleophilic partners in regiospecific palladium catalyzed cross-coupling reactions.  After the tandem, one-pot process, the remaining carbon-boron bond is oxidized, delivering the secondary alcohols in high yield and with high enantiomeric excess.  A wide variety of both aryl and vinyl electrophiles successfully couple with the bis-boronate esters, providing a relatively rare example of alkylboronate ester participation in Suzuki-Miyaura cross-coupling.  In addition to oxidation, the remaining boronate ester provides a convenient functional handle for additional synthetic transformations.

Development of a one-pot enantioselective diboration-cross-coupling protocol for terminal olefins

245th National Meeting (2013)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.