What is the role of acid-acid interactions in asymmetric phosphoric acid organocatalysis? A detailed mechanistic study using interlocked and non-interlocked catalysts.

Chemical Science
Dennis JansenJochen Niemeyer

Abstract

Organocatalysis has revolutionized asymmetric synthesis. However, the supramolecular interactions of organocatalysts in solution are often neglected, although the formation of catalyst aggregates can have a strong impact on the catalytic reaction. For phosphoric acid based organocatalysts, we have now established that catalyst-catalyst interactions can be suppressed by using macrocyclic catalysts, which react predominantly in a monomeric fashion, while they can be favored by integration into a bifunctional catenane, which reacts mainly as phosphoric acid dimers. For acyclic phosphoric acids, we found a strongly concentration dependent behavior, involving both monomeric and dimeric catalytic pathways. Based on a detailed experimental analysis, DFT-calculations and direct NMR-based observation of the catalyst aggregates, we could demonstrate that intermolecular acid-acid interactions have a drastic influence on the reaction rate and stereoselectivity of asymmetric transfer-hydrogenation catalyzed by chiral phosphoric acids.

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Citations

May 12, 2020·ChemPlusChem·Dana Kauerhof, Jochen Niemeyer
Jul 25, 2020·Chemistry : a European Journal·Carel Kwamen, Jochen Niemeyer
Nov 15, 2020·The Journal of Chemical Physics·Ilya G Shenderovich

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Methods Mentioned

BETA
NMR
diffusion

Software Mentioned

RS
VTNA
COSMO

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