Selective catalytic C-H alkylation of alkenes with alcohols. Science 2011 Sep 16;333(6049):1613-6
Date
09/17/2011Pubmed ID
21921195DOI
10.1126/science.1208839Scopus ID
2-s2.0-80052945833 (requires institutional sign-in at Scopus site) 153 CitationsAbstract
Alkenes and alcohols are among the most abundant and commonly used organic feedstock in industrial processes. We report a selective catalytic alkylation reaction of alkenes with alcohols that forms a carbon-carbon bond between vinyl carbon-hydrogen (C-H) and carbon-hydroxy centers with the concomitant loss of water. The cationic ruthenium complex [(C(6)H(6))(PCy(3))(CO)RuH](+)BF(4)(-) (Cy, cyclohexyl) catalyzes the alkylation in solution within 2 to 8 hours at temperatures ranging from 75° to 110°C and tolerates a broad range of substrate functionality, including amines and carbonyls. Preliminary mechanistic studies are inconsistent with Friedel-Crafts-type electrophilic activation of the alcohols, suggesting instead a vinyl C-H activation pathway with opposite electronic polarization.