Issue 7, 2020

Effect of the enamine pyramidalization direction on the reactivity of secondary amine organocatalysts

Abstract

Chiral secondary amines are valuable catalysts for reactions that proceed through an enamine intermediate. Here, we explored the importance of the pyramidalization direction of the enamine-N on the reactivity of chiral enamines with a combination of computational, NMR spectroscopic, and kinetic experiments. Studies with peptidic catalysts that bear cyclic amines with different ring sizes revealed that endo-pyramidalized enamines are significantly more reactive compared to exo-pyramidalized analogs. The results show that the pyramidalization direction can have a greater effect than n→π* orbital overlap on the reactivity of chiral enamines. The data enabled the development of a catalyst with higher reactivity compared to the parent catalyst.

Graphical abstract: Effect of the enamine pyramidalization direction on the reactivity of secondary amine organocatalysts

Supplementary files

Article information

Article type
Edge Article
Submitted
25 oct. 2019
Accepted
05 janv. 2020
First published
07 janv. 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-NC license

Chem. Sci., 2020,11, 1943-1947

Effect of the enamine pyramidalization direction on the reactivity of secondary amine organocatalysts

T. Schnitzer, J. S. Möhler and H. Wennemers, Chem. Sci., 2020, 11, 1943 DOI: 10.1039/C9SC05410C

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