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Functional Mechanically Interlocked Molecules: Asymmetric Organocatalysis with a Catenated Bifunctional Brønsted Acid
Author(s) -
Mitra Raja,
Zhu Hui,
Grimme Stefan,
Niemeyer Jochen
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201704647
Subject(s) - catenane , bifunctional , organocatalysis , chemistry , catalysis , molecule , combinatorial chemistry , enantioselective synthesis , selectivity , stereochemistry , organic chemistry
Interlocked molecules, such as catenanes, rotaxanes, and molecular knots, have become interesting candidates for the development of sophisticated chemical catalysts. Herein, we report the first application of a catenane‐based catalyst in asymmetric organocatalysis, revealing that the catenated catalyst shows dramatically increased stereoselectivities (up to 98 % ee ) in comparison to its non‐interlocked analogues. A mechanistic rationale for the observed differences was developed by DFT studies, suggesting that the involvement of two catalytically active groups in the stereodetermining reaction step is responsible for the superior selectivity of the interlocked catalyst.