E/Z Photoisomerization of Olefins as an Emergent Strategy for the Control of Stereodivergence in Catalysis

The stereoselective photoisomerization of olefins via Energy Transfer (EnT) sensitization bears significant potential in the context of rational design of catalytic stereodivergent methodologies. Whereas approaches for controlling the access to E- and Z-isomers depend highly on the nature of the catalyst - and therefore are not easily implemented as a general strategy - EnT catalysis has emerged in recent years as an increasingly powerful tool for olefin geometry control in a nearly perfect step-economic fashion. Moreover, this approach presents both high functional group tolerance and, most notably, has demonstrated ample multicatalytic compatibility. This feature has enabled the development of tandem stereodivergent catalytic strategies, which are the focus of this Review. 1. Introduction 1.1. Stereodivergence in Modern Synthesis 1.2. E/Z Photoisomerization of Olefins as an Opportunity for Stereodivergence 2. Stereodivergent Methods Enabled by E/Z Photoisomerization 2.1. Auto Tandem Catalysis 2.2. Multicatalytic Tandem Processes 3. Applications to Stereodivergent Synthesis 3.1. Methods Based on Olefin Geometry Control 3.2. Photoisomerization and Enantiodivergence 3.3. Divergence through Isomerization of C=N Bonds 4. Conclusions

Automated summary

The stereoselective photoisomerization of olefins via Energy Transfer (EnT) sensitization has significant potential in designing catalytic stereodivergent methodologies. EnT catalysis has emerged as a powerful tool for olefin geometry control, with high functional group tolerance and multicatalytic compatibility.