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Reactivity and selectivity of iminium organocatalysis improved by a protein host

Nodling, Alexander R., Swiderek, Katarzyna, Castillo, Raquel, Hall, Jonathan W., Angelastro, Antonio, Morrill, Louis C., Jin, Yi, Tsai, Yu-Hsuan, Moliner, Vicent and Luk, Louis Y. P. 2018. Reactivity and selectivity of iminium organocatalysis improved by a protein host. Angewandte Chemie International Edition 57 (38) , pp. 12478-12482. 10.1002/anie.201806850

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Abstract

There has been growing interest in operating organocatalysis within a supramolecular system as means of controlling reaction reactivity and stereoselectivity. Here, a protein is used as host for iminium catalysis; a pyrrolidine moiety is covalently linked to biotin, introduced to the protein host streptavidin and tested for organocatalytic activity. Whereas in traditional systems stereoselectivity is largely controlled by the substituents added to the organocatalyst, enantiomeric enrichment by the reported supramolecular system is completely controlled by the host. Also, the yield of the model reaction increases over 10‐fold when streptavidin is included. A 1.1‐Å crystal structure of the protein‐catalyst complex and molecular simulations of a key intermediate reveal the chiral scaffold surrounding the organocatalytic reaction site. This work illustrates that proteins can be an excellent supramolecular host for driving stereoselective secondary amine organocatalysis.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Publisher: Wiley
ISSN: 1433-7851
Funders: Leverhulme Trust, Royal Society, Wellcome Trust
Date of First Compliant Deposit: 31 July 2018
Date of Acceptance: 19 July 2018
Last Modified: 31 Dec 2018 21:37
URI: http://orca.cf.ac.uk/id/eprint/113805

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