Mechanism-guided development of VO(salen)X complexes as catalysts for the asymmetric synthesis of cyanohydrin trimethylsilyl ethers

Chemistry : a European Journal
Yuri N BelokonCarl Young

Abstract

Catalyze this! Detailed study of the mechanism of asymmetric cyanohydrin synthesis catalyzed by VO(salen)X complexes (see figure) led to the development of VO(salen)NCS, as the most active vanadium-based catalyst yet developed for this reaction.The mechanism by which oxovanadium(V)(salen) complexes(1) VO(salen)X catalyze the asymmetric addition of trimethylsilyl cyanide to benzaldehyde has been studied. The reaction kinetics indicated that the structure of the counterion (X) had a significant influence on the rate, but not on the enantioselectivity of the reaction. The less coordinating the counterion, the lower the catalytic activity; a trend that was confirmed by a Hammett analysis. Variable temperature kinetics allowed the enthalpies and entropies of activation to be determined for some catalysts, and showed that, for others, the overall reaction order changes from second order to zero order as the temperature is reduced. The order with respect to the catalyst was determined for nine of the VO(salen)X complexes and showed that the less active catalysts were active predominantly as mononuclear species whilst the more active catalysts were active predominantly as dinuclear species. Mass spectrometry confirmed the formation of ...Continue Reading

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Citations

May 6, 2010·Chemical Communications : Chem Comm·Victor ChechikMarta Omedes-Pujol
Jun 5, 2010·Dalton Transactions : an International Journal of Inorganic Chemistry·Anaïs ZulaufEmmanuelle Schulz
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Sep 24, 2014·The Journal of Organic Chemistry·Indrek KalvetFranziska Schoenebeck
May 2, 2020·Chemical Reviews·Yong-Sheng WeiQiang Xu

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