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Pure Appl. Chem., 2010, Vol. 82, No. 3, pp. 635-647

http://dx.doi.org/10.1351/PAC-CON-09-10-31

Published online 2010-02-14

Heteroatoms moving protons: Synthetic and mechanistic studies of bifunctional organometallic catalysis

Douglas B. Grotjahn

Department of Chemistry and Biochemistry, San Diego State University, 5500 Campanile Drive, San Diego, CA 92182-1030, USA

Abstract: Improved organometallic catalysts resulting from including ligands capable of proton transfer or hydrogen bonding are described. Pyridyl- and imidazolylphosphines accelerate anti-Markovnikov alkyne hydration and alkene isomerization and deuteration by factors of 1000 to more than 10 000. Evidence for proton transfer and hydrogen bonding in catalytic intermediates comes from computational, mechanistic, and structural studies, where 15N NMR data are particularly revealing.