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

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.

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 Creators:
Monaco, Mattia Ricardo1, Author           
Fazzi, Daniele2, Author           
Tsuji, Nobuya1, Author           
Leutzsch, Markus1, Author           
Liao, Saihu1, Author           
Thiel, Walter2, Author           
List, Benjamin1, Author           
Affiliations:
1Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445585              
2Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445590              

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 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.

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Language(s): eng - English
 Dates: 2016-09-012016-10-252016-11-09
 Publication Status: Published in print
 Pages: 10
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/jacs.6b09179
 Degree: -

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Title: Journal of the American Chemical Society
  Other : JACS
  Abbreviation : J. Am. Chem. Soc.
Source Genre: Journal
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Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 138 (44) Sequence Number: - Start / End Page: 14740 - 14749 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870