Synthesis of cis-Enediynes from 1,5-Diynes by Rearrangement of an Allylic Double Bond

摘要

Until the discover, of the viass of enediyne antitumor antibiotics in1985 and shortly thereafter, the beivenoid diradical derived from the cycloaromatization of enediynes, discovered in 1971-1972, had not received much attention for potential application in biomedical science. During recent years numerous enedivnes have been synthesized, and their ability to damage DMA and kill cancer ceils has been demonstrated. Synthesis of pro-enediyne compounds is a new direction of enediyne studies. Introductionof a double bond into 1,5-divnes has been achieved by elimination of mono- or diols under reductive, basic, acidic, or neutral conditions. Oxidation and photochemical processes have been also used. In this communication, we report for the first time thesynthesis of acyclic cis-enediynes 2 from 1,5-diynes 1 by an ailvlic double bond migration (Scheme 1).