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Stability and reactivity of carbenium ions are described by careful analysis of Mayr, see:, and ref. therein.
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Similarly, the enantioselective propargylic alkylation of propargylic esters in the presence of the Hayashi-Jørgensen catalyst occurred through a copper-allenylidene complex, see:,. The copper-catalyzed enantioselective alkylation of propargyl acetate working with a similar mechanism was reported, see
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Similarly, the enantioselective propargylic alkylation of propargylic esters in the presence of the Hayashi-Jørgensen catalyst occurred through a copper-allenylidene complex, see:, A. Yoshida, M. Ikeda, G. Hattori, Y. Miyake, Y. Nishibayashi, Org. Lett. 2011, 13, 592-595. The copper-catalyzed enantioselective alkylation of propargyl acetate working with a similar mechanism was reported, see
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Also in this case no reaction was reported with internal alkynyl acetates.
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At the present time we have no conclusive explanation for this remarkable behavior. As the d.r. of the reaction is determined by the approach of the carbenium ion to the chiral enamine (Scheme 2), subtle sterical and solvent effects could be involved. High level DFT calculations are in progress.
-
At the present time we have no conclusive explanation for this remarkable behavior. As the d.r. of the reaction is determined by the approach of the carbenium ion to the chiral enamine (Scheme 2), subtle sterical and solvent effects could be involved. High level DFT calculations are in progress.
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43
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79959480097
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When water is the reaction solvent, the most reactive carbocation formed by 4 a-c is rapidly intercepted by water, and thus, the reaction does not occur.
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When water is the reaction solvent, the most reactive carbocation formed by 4 a-c is rapidly intercepted by water, and thus, the reaction does not occur.
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4, then desilylated and hydrogenated with Pd/C. The same product was obtained by the Michael addition of N-methylindole to (E)-pent-2-enal, promoted in a stereoselective manner by a catalytic amount of 9-amino(9-deoxy)epi-hydroquinine, see
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4, then desilylated and hydrogenated with Pd/C. The same product was obtained by the Michael addition of N-methylindole to (E)-pent-2-enal, promoted in a stereoselective manner by a catalytic amount of 9-amino(9-deoxy)epi-hydroquinine, see:, P. Galzerano, F. Pesciaioli, A. Mazzanti, G. Bartoli, P. Melchiorre, Angew. Chem. 2009, 121, 8032-8034
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