Premium
A Broad‐Spectrum Synthesis of Tetravinylethylenes
Author(s) -
Horvath Kelsey L.,
Newton Christopher G.,
Roper Kimberley A.,
Ward Jas S.,
Sherburn Michael S.
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201900550
Subject(s) - negishi coupling , conjugated system , chemistry , combinatorial chemistry , domino , cycloaddition , broad spectrum , stereochemistry , organic chemistry , catalysis , polymer
The first general synthesis of compounds of the tetravinylethylene (TVE) family is reported. Ramirez‐type dibromo‐olefination of readily accessible penta‐1,4‐dien‐3‐ones generates 3,3‐dibromo[3]dendralenes, which undergo twofold Negishi, Suzuki–Miyaura or Mizoroki–Heck reactions with a wide variety of olefinic coupling partners. This route delivers a broad range of unsymmetrically substituted tetravinylethylenes with up to three different alkenyl substituents attached to the central C=C bond. The extensive scope of the approach is demonstrated by the preparation of the first higher order oligo‐alkenic through‐conjugated/cross‐conjugated hybrid compounds. An unsymmetrically substituted TVE is shown to undergo a domino electrocyclization–cycloaddition with high site‐selectivity and diastereoselectivity, thereby demonstrating the substantial synthetic potential of substituted TVEs for controlled, rapid structural complexity generation.