A Unified Approach to (E)- and (Z)-Olefins Enabled by Low-Valent Tungsten Catalysis

12 January 2023, Version 1

Abstract

A positionally selective alkene isomerization in which modulation of the ligand environment of the homogeneous tungsten catalyst grants access to either the (E)- or (Z)-stereoisomer is described. Compared to previously reported alkene isomerization methods, this reaction offers exquisite chemo- and regioselectivity and is user friendly due to the use of a simple, commercial precatalyst and ligand. Preliminary mechanistic studies suggest that tungsten’s ability to adopt 7-coordinate geometry is crucial for stereoselectivity and that substrate directivity prevents over-isomerization to the conjugated alkene, as is commonly observed with other catalysts. These features allows for exclusive formation of β,γ-unsaturated carbonyl compounds that are otherwise difficult to prepare.

Content

Supplementary materials

Supporting Info
experimental procedures, characterization data for new compounds, copies of NMR spectra
W-1 CIF
Crystallographic Information File for Complex W-1
W-3 CIF
Crystallographic Information File for Complex W-3

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