Jump to main content
Jump to site search

Issue 16, 2018

Can electrostatic catalysis of Diels–Alder reactions be harnessed with pH-switchable charged functional groups?

Author affiliations

Abstract

Quantum-chemical calculations at the M06-2X/6-31+G(d,p) and G3(MP2)CC levels of theory are used to assess the feasibility of harnessing charged functional groups to electrostatically catalyse Diels–Alder reactions and alter their regio selectivity. For the reaction of the polar diene 2-pyrone with substituted cyclopentene, pH switches of nearly 60 kJ mol−1 are observed in the gas-phase. To switch regioselectivity however it is necessary to toggle between negatively and positively charged functional groups. With the 6-membered cyclohexene derivatives, similar pH-switches are observed but this time an opportunity to pH-switch diastereomeric selectivity is also observed due to the asymmetry of the transition state. When 2-pyrone was replaced with a non-polar diene, cyclopentadiene, pH switches were understandably smaller but still substantial (ca. 15 kJ mol−1). Likewise pH switches are attenuated by solvent but remain substantial (ca. 30 kJ mol−1) in toluene and synthetically useful (ca. 15 kJ mol−1) even in moderately low polar solvents such as dichloromethane.

Graphical abstract: Can electrostatic catalysis of Diels–Alder reactions be harnessed with pH-switchable charged functional groups?

Supplementary files

Article information


Submitted
09 Nov 2017
Accepted
30 Nov 2017
First published
30 Nov 2017

Phys. Chem. Chem. Phys., 2018,20, 10671-10676
Article type
Paper

Can electrostatic catalysis of Diels–Alder reactions be harnessed with pH-switchable charged functional groups?

H. M. Aitken and M. L. Coote, Phys. Chem. Chem. Phys., 2018, 20, 10671 DOI: 10.1039/C7CP07562F

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.


Social activity

Search articles by author

Spotlight

Advertisements