A Broad-Spectrum Synthesis of Tetravinylethylenes |
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Authors: | Kelsey L Horvath Dr Christopher G Newton Dr Kimberley A Roper Dr Jas S Ward Prof Michael S Sherburn |
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Institution: | Research School of Chemistry, Australian National University, Canberra, ACT, 2601 Australia |
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Abstract: | 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-dibromo3]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. |
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Keywords: | cross-coupling cycloaddition electrocyclic reactions hydrocarbons polyenes |
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