157131-12-9Relevant academic research and scientific papers
The total synthesis of dynemicin A leading to development of a fully contained bioreductively activated enediyne prodrug
Shair, Matthew D.,Yoon, Tae Young,Mosny, Karoline K.,Chou,Danishefsky, Samuel J.
, p. 9509 - 9525 (2007/10/03)
The title compound has been synthesized as its racemate in 33 steps. An intramolecular Diels-Alder reaction (24 → 25) was used to provide control over the eventual cis C4-C7 relationship. The installation of another cis related ethynyl group at C2 arose from transformation 40 → 42 whose directionality is governed by a benzophenone ketal functioning as a temporary steric control unit. Closure of the enediyne unit was accomplished on a trimethylsilylethoxycarbonyl (TEOC) protected dihydroquinoline derivative. It involved use of a novel bis-iodoalkyne/distannylethylene interpolative coupling transformation (61 + 58 → 63). In the terminal phase of the synthesis, a novel iminoquinone ketal 74 was condensed with homophthalic anhydride derivative 78 as indicated. The final deprotection involved cleavage of a methoxymethyl ester and two methoxymethyl phenol ethers. From this work, there arose the concept and demonstration of p-quinone monoimines 82 and 93, as bioreductively activated enediyne prodrugs.
Experiments Directed toward a Total Synthesis of Dynemicin A: A Solution to the Stereochemical Problem
Yoon, Taeyoung,Shair, Matthew D.,Danishefsky, Samuel J.,Shulte, Gayle K.
, p. 3752 - 3754 (2007/10/02)
The stereochemical issues required for a total synthesis of dynemicin A (1) have been resolved by employing an intramolecular Diels-Alder reaction and a diastereoselective addition of a magnesioacetylide to a quinoline under the influence of methyl chloro
