Issue 11, 2016

Photocatalyst size controls electron and energy transfer: selectable E/Z isomer synthesis via C–F alkenylation

Abstract

Photocatalytic alkene synthesis can involve electron and energy transfer processes. The structure of the photocatalyst can be used to control the rate of the energy transfer, providing a mechanistic handle over the two processes. Jointly considering catalyst volume and emissive energy provides a highly sensitive strategy for predicting which mechanistic pathway will dominate. This model was developed en route to a photocatalytic Caryl–F alkenylation reaction of alkynes and highly-fluorinated arenes as partners. By judicious choice of photocatalyst, access to E- or Z-olefins was accomplished, even in the case of synthetically challenging trisubstituted alkenes. The generality and transferability of this model was tested by evaluating established photocatalytic reactions, resulting in shortened reaction times and access to complimentary Z-cinnamylamines in the photocatalytic [2 + 2] and C–H vinylation of amines, respectively. These results show that taking into account the size of the photocatalyst provides predictive ability and control in photochemical quenching events.

Graphical abstract: Photocatalyst size controls electron and energy transfer: selectable E/Z isomer synthesis via C–F alkenylation

Supplementary files

Article information

Article type
Edge Article
Submitted
01 Jun 2016
Accepted
13 Jul 2016
First published
21 Jul 2016
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., 2016,7, 6796-6802

Author version available

Photocatalyst size controls electron and energy transfer: selectable E/Z isomer synthesis via C–F alkenylation

A. Singh, C. J. Fennell and J. D. Weaver, Chem. Sci., 2016, 7, 6796 DOI: 10.1039/C6SC02422J

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.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements