Synfacts 2017; 13(10): 1085
DOI: 10.1055/s-0036-1591223
Organo- and Biocatalysis
© Georg Thieme Verlag Stuttgart · New York

Highly Enantioselective Organocatalysis with a Mechanically Interlocked Molecule

Contributor(s): Benjamin List, Jennifer L. Kennemur
Mitra R. Zhu H. Grimme S. Niemeyer J. * University of Duisburg-Essen and Rheinische Friedrich-Wilhelms-Universität Bonn, Germany
Functional Mechanically Interlocked Molecules: Asymmetric Organocatalysis with a Catenated Bifunctional Brønsted Acid.

Angew. Chem. Int. Ed. 2017;
56: 11456-11459
Further Information

Publication History

Publication Date:
18 September 2017 (online)

 
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Significance

Niemeyer and co-workers report that the [2]-catenane (S,S)-3, containing two chiral 1,1′-binaphthylphosphoric acids (initial report: Chem. Commun. 2016, 52, 5977), imposes dramatically superior enantioinduction on the transfer hydrogenation of 2-aryl-substituted quinolines, compared with both the corresponding non-interlocked macrocycle (S)-4 and acyclic catalyst (S)-5.


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Comment

Computational studies, in which the mechanically interlocked nature of (S,S)-3 was mimicked by assuming a simplified non-dissociative dimeric structure, suggest that the interlocked catalyst proceeds through a sandwich-like transition state in the enantiodetermining step. The authors propose that this motif, involving two phosphoric acid moieties bound together in proximity to the reaction site, is responsible for the increase in enantioselectivity.


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