2-Benzylindane radical cations in the gas phase (Part I): Substituent effects on a stereoselective McLafferty reaction and related hydrogen transfer processes
In the present and the accompanying article, the unimolecular fragmentation of the radical cations of 2-benzylindane and eleven derivatives bearing meta- or para-substituents at the benzylic moiety has been studied with a special focus on the hydrogen exc
Grützmacher, Hans-Friedrich,Kuck, Dietmar
p. 106 - 116
(2017/04/11)
Selective catalytic C-H alkylation of alkenes with alcohols
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 [(C6H6)(PCy 3)(CO)RuH]+BF4- (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.
Lee, Dong-Hwan,Kwon, Ki-Hyeok,Yi, Chae S.
scheme or table
p. 1613 - 1616
(2012/02/01)
Cinchona alkaloid catalyzed enantioselective fluorination of allyl silanes, silyl enol ethers, and oxindoles
(Chemical Equation Presented) Catalytic variant: Allyl silanes and silyl enol ethers 1 are good substrates for the catalytic highly enantioselective fluorodesilylation using a combination of a biscinchona alkaloid, N-fluorobenzenesulfonimide (NFSI), and base (see scheme). Pharmaceutically attractive 3-aryl-3-fluorooxindoles such as 3 can also be synthesized with high enantioselectivity.