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- Title
Biomimetic Total Synthesis of Cyanosporaside Aglycons from a Single Enediyne Precursor through Site-Selective p-Benzyne Hydrochlorination.
- Authors
Yamada, Kei; Lear, Martin J.; Yamaguchi, Takaya; Yamashita, Shuji; Gridnev, Ilya D.; Hayashi, Yujiro; Hirama, Masahiro
- Abstract
The cyanosporasides A-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 cyanosporasides D 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.
- Subjects
BIOMIMETIC chemicals; ENEDIYNES; AGLYCONE synthesis; HYDROCHLORINATION; POLYCYCLIC aromatic hydrocarbons
- Publication
Angewandte Chemie International Edition, 2014, Vol 53, Issue 50, p13902
- ISSN
1433-7851
- Publication type
Article
- DOI
10.1002/anie.201408416