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“…N-Bound cyanocarbanions reportedly have high specific catalytic activity for aldol and Michael reactions, and the related carbon-carbon bond-forming reactions of nitriles. [6,[8][9][10][11][12][13][14] These results provide interesting information regarding the controlled generation of these catalysts and a mechanistic rationale for these important catalytic processes. …”
Section: Resultsmentioning
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“…N-Bound cyanocarbanions reportedly have high specific catalytic activity for aldol and Michael reactions, and the related carbon-carbon bond-forming reactions of nitriles. [6,[8][9][10][11][12][13][14] These results provide interesting information regarding the controlled generation of these catalysts and a mechanistic rationale for these important catalytic processes. …”
Section: Resultsmentioning
“…A metal-sliding process, which occurs over the ÀCÀCN p-conjugated surface of the cyanocarbanion moiety, was suggested by results from kinetic studies and density functional theory (DFT) calculations. C-to-N isomerizations proceed by the above-mentioned intramolecular process, with a temperature-dependent contribution from the formation and cleavage of m bond-forming reactions between nitriles and electrophiles, which include carbonyl compounds, [6a-d, g, 11] imines, [6b, 12] nitriles, [13] electron-deficient olefins, [6b-g, 11a,b, 14] methylenecyclopropanes, [8] enynes, [9] allenes, [10] and bromobenzenes. [1d] Reductive elimination of 1 followed by a redox catalytic cycle has been postulated for palladium-catalyzed reactions, [1d, 8-10] whereas direct nucleophilic attack on electrophiles by 2 and a nonredox mechanism occur for aldol and Michael-type reactions.…”
Section: ] (4) Were Prepared By Treating [Rucl(cp)a C H T U N G T R mentioning
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