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The Activation of Carboxylic Acids via Self-Assembly Asymmetric Organocatalysis: A Combined Experimental and Computational Investigation

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Monaco,  Mattia Ricardo
Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Fazzi,  Daniele
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Tsuji,  Nobuya
Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Leutzsch,  Markus
Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Liao,  Saihu
Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Thiel,  Walter
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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List,  Benjamin
Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

Monaco, M. R., Fazzi, D., Tsuji, N., Leutzsch, M., Liao, S., Thiel, W., et al. (2016). The Activation of Carboxylic Acids via Self-Assembly Asymmetric Organocatalysis: A Combined Experimental and Computational Investigation. Journal of the American Chemical Society, 138(44), 14740-14749. doi:10.1021/jacs.6b09179.


Cite as: https://hdl.handle.net/11858/00-001M-0000-002C-1F48-9
Abstract
The heterodimerizing self-assembly between a phosphoric acid catalyst and a carboxylic acid has recently been established as a new activation mode in Brønsted acid catalysis. In this article, we present a comprehensive mechanistic investigation on this activation principle, which eventually led to its elucidation. Detailed studies are reported, including computational investigations on the supramolecular heterodimer, kinetic studies on the catalytic cycle, and a thorough analysis of transition states by DFT calculations for the rationalization of the catalyst structure–selectivity relationship. On the basis of these investigations, we developed a kinetic resolution of racemic epoxides, which proceeds with high selectivity (up to s = 93), giving the unreacted epoxides and the corresponding protected 1,2-diols in high enantiopurity. Moreover, this approach could be advanced to an unprecedented stereodivergent resolution of racemic α-chiral carboxylic acids, thus providing access to a variety of enantiopure nonsteroidal anti-inflammatory drugs and to α-amino acid derivatives.