Acid-base bifunctional and dielectric outer-sphere effects in heterogeneous catalysis: a comparative investigation of model primary amine catalysts

Journal of the American Chemical Society
John D BassAlexander Katz

Abstract

Dielectric and acid-base bifunctional effects are elucidated in heterogeneous aminocatalysis using a synthetic strategy based on bulk silica imprinting. Acid-base cooperativity between silanols and amines yields a bifunctional catalyst for the Henry reaction that forms alpha,beta-unsaturated product via quasi-equilibrated iminium intermediate. Solid-state UV/vis spectroscopy of catalyst materials treated with salicylaldehyde demonstrates zwitterionic iminium ion to be the thermodynamically preferred product in the bifunctional catalyst. This product is observed to a much lesser extent relative to its neutral imine tautomer in primary amine catalysts having outer-sphere silanols partially replaced by aprotic functional groups. One of these primary amine catalysts, consisting of a polar outer-sphere environment derived from cyano-terminated capping groups, has activity comparable to that of the bifunctional catalyst in the Henry reaction, but instead forms the beta-nitro alcohol product in high selectivity (approximately 99%). This appears to be the first observation of selective alcohol formation in primary amine catalysis of the Henry reaction. A primary amine catalyst with a methyl-terminated outer-sphere also produces alcohol...Continue Reading

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Citations

Oct 4, 2012·Accounts of Chemical Research·Satoshi Muratsugu, Mizuki Tada
Nov 23, 2011·Journal of the American Chemical Society·Kotaro SuginoMasaru Ogura
Aug 16, 2012·Journal of the American Chemical Society·Nicholas A BrunelliChristopher W Jones
May 22, 2009·Journal of the American Chemical Society·Ken MotokuraYasuhiro Iwasawa
May 23, 2009·Journal of the American Chemical Society·Francisco Rodríguez-LlansolaJuan F Miravet
Nov 7, 2006·Chemical Communications : Chem Comm· SujandiTetsu Ohsuna
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Apr 14, 2010·Chemical Communications : Chem Comm·Jonathan D Lunn, Daniel F Shantz
Jul 17, 2014·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Manuela OliverioAntonio Procopio
Feb 15, 2012·The Sociological Quarterly·Peter Kivisto
Dec 15, 2011·Development and Change·Fernando FilgueiraJorge Papadópulos
Apr 5, 2014·Journal of Molecular Recognition : JMR·Michael J WhitcombeIan A Nicholls
Jun 6, 2009·The British Journal of Sociology·Lydia Morris
May 22, 2016·The British Journal of Sociology·Thomas Olesen
May 31, 2016·Journal of the American Chemical Society·Ki Chul KimSeung Soon Jang
Sep 2, 2016·Journal of the American Chemical Society·Hai-Sen XuWei Wang
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Sep 4, 2009·ChemSusChem·Keith L Hohn, Yu-Chuan Lin
Jul 30, 2008·Chemistry, an Asian Journal·Ken MotokuraYasuhiro Iwasawa

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