スピロトリプロスタチンAの全合成

抄録

Spirotryprostatin A was isolated in 1996 from Aspergillus fumigatus by Osada and coworkers. Structurally intriguing features of this cytostatic natural product include spiro[pyrrolidine-3,3'-indolinone] core, annulated diketopiperazine and isopropylidene side chain. The key steps of our synthesis involve the intramolecular Heck reaction of aryl bromide and ethylidene moiety to construct the quarternary C3 stereocenter, as well as the installation of the nitrogen atom of the indolinone part, which was conducted by Beckmann rearrangement. Following cleavage of lactam, ozonolysis of the vinyl group and amide formation led to the convergent formation of spiroindolinone core. Highly stereoselective synthesis of spirotryprostatin A along this route will be presented.