Metal-organic frameworks invert molecular reactivity: Lewis acidic phosphonium zwitterions catalyze the Aldol-Tishchenko reaction.

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Bauer, Gerald
Ongari, Daniele
Xu, Xiaoying
Tiana, Davide
Smit, Berend
Ranocchiari, Marco
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American Chemical Society
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The influence of metal–organic frameworks (MOFs) as additives is herein described for the reaction of n-alkyl aldehydes in the presence of methylvinylketone and triphenylphosphine. In the absence of a MOF, the expected Morita–Baylis–Hillman product, a β-hydroxy enone, is observed. In the presence of MOFs with UMCM-1 and MOF-5 topologies, the reaction is selective to Aldol-Tishchenko products, the 1 and 3 n-alkylesters of 2-alkyl-1,3-diols, which is unprecedented in organocatalysis. The (3-oxo-2-butenyl)triphenylphosphonium zwitterion, a commonly known nucleophile, is identified as the catalytic active species. This zwitterion favors nucleophilic character in solution, whereas once confined within the framework, it becomes an electrophile yielding Aldol-Tishchenko selectivity. Computational investigations reveal a structural change in the phosphonium moiety induced by the steric confinement of the framework that makes it accessible and an electrophile.
Metal–organic frameworks , Aldol-Tishchenko , MOFs , Phosphonium , Morita−Baylis−Hillman (MBH) reaction
Bauer, G., Ongari, D., Xu, X., Tiana, D., Smit, B. and Ranocchiari, M. (2017) 'Metal–Organic Frameworks Invert Molecular Reactivity: Lewis Acidic Phosphonium Zwitterions Catalyze the Aldol-Tishchenko Reaction', Journal of the American Chemical Society, 139(50), pp. 18166-18169. doi:10.1021/jacs.7b10928