11 抗腫瘍性抗生物質ケダルシジンクロモフォアの構造訂正と全合成研究(口頭発表の部)

概要

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Antitumor antibiotic kedarcidin consists of an apoprotein and chromophore 1. We describe herein a synthetic study directed towards 1 and revised structure of 1. α-Chloroazatyrosyl naphthoamide fragment 2 was synthesized from naphthalene carboxylic acid 14 and chloroazatyrosine derivative 15. NMR spectra of synthetic α-chloroazatyrosyl naphthoamide 2 was not identical with the reported data. β-Chloroazatyrosyl naphthoamide 17 was then prepared. Its spectral data were identical with those of the fragment of 1. Optically active 17 was synthesized through the optical resolution of β-chloroazatyrosine derivative 16 whose absolute configuration was determined by modified Mosher's method. The absolute configuration of the fragment degraded from 1 was elucidated to be R by comparison of the optical rotations and CD. Thus, the structure of kedarcidin chromophore has been revised as 18 based on the above syntheses and NOEs. Optically pure enediyne 22 with the revised absolute configuration was synthesized. Furthermore, an efficient method for synthesizing an aryl ether was established. CsF-mediated coupling of 26 with epoxide 27 was achieved under the mild conditions.
天然有機化合物討論会の論文
1997-07-20