Journal
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
Volume 53, Issue 50, Pages 13902-13906Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.201408416
Keywords
benzenoids; cyclization; diradicals; enediynes; monochlorination
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Funding
- Ministry of Education, Culture, Sports, Science, and Technology (MEXT), SORST (Japan)
- Science and Technology Agency (JST)
- Multidimensional Materials Science Leaders Program
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The cyanosporasidesA-F are a collection of monochlorinated benzenoid derivatives isolated from the marine actinomycetes Salinispora and Streptomyces sp. All derivatives feature one of two types of cyanocyclopenta[a]indene frameworks, which are regioisomeric in the position of a single chlorine atom. It is proposed that these chloro-substituted benzenoids are formed biosynthetically through the cycloaromatization of a bicyclic nine-membered enediyne precursor. Herein, we report the synthesis of such a bicyclic precursor, its spontaneous transannulation into a p-benzyne, and its differential 1,4 hydrochlorination reactivity under either organochlorine or chloride-salt conditions. Our bioinspired approach culminated in the first regiodivergent total synthesis of the aglycons A/F and B/C, as well as cyanosporasidesD and E. In addition, empirical insights into the site selectivity of a natural-like p-benzyne, calculated to be a ground-state triplet diradical, to hydrogen, chlorine, and chloride sources are revealed.
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