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Real‐Time Control of the Enantioselectivity of a Supramolecular Catalyst Allows Selecting the Configuration of Consecutively Formed Stereogenic Centers
Author(s) -
Zimbron Jeremy M.,
Caumes Xavier,
Li Yan,
Thomas Christophe M.,
Raynal Matthieu,
Bouteiller Laurent
Publication year - 2017
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201706757
Subject(s) - stereocenter , enantiomer , phosphine , supramolecular chemistry , copper , hydrosilylation , catalysis , chemistry , enantioselective synthesis , ligand (biochemistry) , monomer , chirality (physics) , stereochemistry , combinatorial chemistry , crystallography , polymer chemistry , materials science , organic chemistry , crystal structure , polymer , quark , biochemistry , receptor , nambu–jona lasinio model , chiral symmetry breaking , physics , quantum mechanics
The enantiomeric state of a supramolecular copper catalyst can be switched in situ in ca. five seconds. The dynamic property of the catalyst is provided by the non‐covalent nature of the helical assemblies supporting the copper centers. These assemblies are formed by mixing an achiral benzene‐1,3,5‐tricarboxamide (BTA) phosphine ligand (for copper coordination) and both enantiomers of a chiral phosphine‐free BTA co‐monomer (for chirality amplification). The enantioselectivity of the hydrosilylation reaction is fixed by the BTA enantiomer in excess, which can be altered by simple BTA addition. As a result of the complete and fast stereochemical switch, any combination of the enantiomers was obtained during the conversion of a mixture of two substrates.