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Effect of Tethered, Axial Thioether Coordination on Rhodium(II)‐Catalyzed Silyl‐Hydrogen Insertion
Author(s) -
Sheffield William,
Abshire Anthony,
Darko Ampofo
Publication year - 2019
Publication title -
european journal of organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.825
H-Index - 155
eISSN - 1099-0690
pISSN - 1434-193X
DOI - 10.1002/ejoc.201900977
Subject(s) - rhodium , thioether , chemistry , carbenoid , catalysis , silylation , selectivity , diazo , medicinal chemistry , stereochemistry , organic chemistry
The effect of tethering a thioether to a rhodium(II) paddlewheel complex are evaluated in Si–H insertion reactions. This study provides further evidence for the benefits of incorporating thioethers into the rhodium paddlewheel motif. When using a tethered complex, the in situ carbenoid formation and subsequent Si–H insertion are not impeded, yields are improved by up to 12 % at elevated temperatures, and selectivity for diazo compounds is greater when compared to non‐tethered catalysts. Computational modelling of the complexes is also presented in order to rationalize the results.