Photocatalytic E→Z Contra-Thermodynamic Isomerization of Vinyl Silanes with Lewis Base
Related Experiment Video
Updated: Sep 21, 2025

Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst
Published on: April 22, 2016
Thi Minh Thi Le1, Thibaud Brégent1, Philippe Jubault1
1Normandie Univ., INSA Rouen, UNIROUEN, CNRS, COBRA (UMR 6014), 76000, Rouen, France.
Abstract:
Herein, we disclosed the contra-thermodynamic E→Z isomerization of alkenyl silanes, according to the in situ formation of a chromophoric species, in the presence of rac-BINAP as the catalyst. The reaction carried out in DMSO or CH3 CN under irradiation at 405 nm allowed the interconversion of the E-isomers into the Z-congeners in good to excellent yields and outstanding Z/E selectivities, on 18 examples. Finally, the mechanism of this E→Z isomerization was studied to get insight into the reaction mechanism.
Related Concept Videos
Thermal Electrocyclic Reactions: Stereochemistry
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
[3,3] Sigmatropic Rearrangement of Allyl Vinyl Ethers: Claisen Rearrangement
Thermal and Photochemical Electrocyclic Reactions: Overview
Photochemical Electrocyclic Reactions: Stereochemistry
Selection Rules: Photochemical Activation
E1 Reaction: Stereochemistry and Regiochemistry
Cycloaddition Reactions: MO Requirements for Photochemical Activation

