Benzyne-Furan Cycloaddition Approach to the Angucyclines: First Total Synthesis of Antibiotic C104

Takashi Matsumoto; Tsukasa Sohma; Hiroki Yamaguchi; Shin Kurata; Keisuke Suzuki

doi:10.1055/s-1995-4936

Synlett 1995; 1995(3): 263-266
DOI: 10.1055/s-1995-4936

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Benzyne-Furan Cycloaddition Approach to the Angucyclines: First Total Synthesis of Antibiotic C104

Takashi Matsumoto, Tsukasa Sohma, Hiroki Yamaguchi, Shin Kurata, Keisuke Suzuki^*

^*Department of Chemistry, Keio University, Hiyoshi, Kohoku-ku, Yokohama 223, Japan

Abstract

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This paper describes the first total synthesis of an angucycline-class antibiotic, C104 (1), by exploiting regioselective benzyne-furan cycloaddition. Angularly fused α-siloxyfuran 3, generated in situ by treatment of butenolide 2 with NaH-TBDMSCl in THF, was directly subjected to the reaction with α-alkoxybenzyne 5, which was generated also in situ from α-iodo triflate 4. The high head-to-head selectivity in the mode of the cycloaddition enabled the regiocontrolled construction of the characteristic benz[a]-anthraquinone framework. The D-olivosyl C-glycoside was introduced via the O→C-glycoside rearrangement. This synthesis determined the absolute stereochemistry of this compound.

Benzyne-furan cycloaddition - Total synthesis - The angucyclines - Benz[a]anthraquinone - Aryl C-glucoside

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