Issue 14, 2020

Enhancing the selectivity of prolinamide organocatalysts using the mechanical bond in [2]rotaxanes

Abstract

The synthesis of a pair of switchable interlocked prolinamides and their use as organocatalysts in three different enamine-activated processes are reported. A diacylaminopyridine moiety was incorporated into the thread for directing [2]rotaxane formation further allowing the association of complementary small molecules. The rotaxane-based systems were tested as organocatalysts in asymmetric enamine-mediated processes, revealing a significantly improved catalytic ability if compared with the non-interlocked thread. The presence of an electron-withdrawing nitro group at the macrocycle helps to achieve high conversions and enantioselectivities. These systems are able to interact with N-hexylthymine as a cofactor to form supramolecular catalysts displaying a divergent catalytic behaviour. The presence or absence of the cofactor controls the chemoselectivity in competitive reactions.

Graphical abstract: Enhancing the selectivity of prolinamide organocatalysts using the mechanical bond in [2]rotaxanes

Supplementary files

Article information

Article type
Edge Article
Submitted
23 jan 2020
Accepted
10 mar 2020
First published
11 mar 2020
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2020,11, 3629-3635

Enhancing the selectivity of prolinamide organocatalysts using the mechanical bond in [2]rotaxanes

M. Calles, J. Puigcerver, D. A. Alonso, M. Alajarin, A. Martinez-Cuezva and J. Berna, Chem. Sci., 2020, 11, 3629 DOI: 10.1039/D0SC00444H

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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