Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 58, Issue 51, Pages 18619-18626Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201910169
Keywords
alkenes; catalysis; geometric isomerisation; Hiyama-Denmark coupling; medicinal chemistry
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Funding
- Alexander von Humboldt Foundation
- WWU Mgnster
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An efficient geometrical E -> Z isomerisation of alkenyl silanes is disclosed via selective energy transfer using an inexpensive organic sensitiser. Characterised by operational simplicity, short reaction times (2 h), and broad substrate tolerance, the reaction displays high selectivity for trisubstituted systems (Z/E up to 95:5). In contrast to thermal activation, directionality results from deconjugation of the pi-system in the Z-isomer due to A(1,3)-strain thereby inhibiting re-activation. The structural importance of the beta-substituent logically prompted an investigation of mixed bis-nucleophiles (Si, Sn, B). These versatile linchpins also undergo facile isomerisation, thereby enabling a formal anti-metallometallation. Mechanistic interrogation, supported by a theoretical investigation, is disclosed together with application of the products to the stereospecific synthesis of biologically relevant target structures.
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