Synthesis of the ABCDG ring skeleton of communesin F based on carboborylation of 1,3-diene and Bi(OTf)3-catalyzed cyclizations.

Communesins, isolated from the mycelium of a strain of Penicillium sp., are cytotoxic heptacyclic indole alkaloids bearing a bis-aminal structure and two contiguous quaternary carbon centers. Toward a total synthesis of communesin F, we synthesized a pentacyclic ABCDG ring skeleton via carboborylation of 1,3-diene and a Friedel-Crafts-type cyclization, resulting in the formation of an azepine ring through a Bi(OTf)3-catalyzed SN2' reaction.

Palladium-catalyzed intramolecular carboborylation of 1,3-diene and synthesis of ABCD ring of communesins.

A palladium-catalyzed intramolecular carboborylation of 1,3-diene has been developed for the synthesis of iminoindolines with a quaternary carbon centre. This method was applied to a substrate bearing several functional groups to afford a complex iminoindoline, which was subsequently converted into an ABCD ring model compound of communesins via an intramolecular Friedel-Crafts-type reaction.

Flexible strategy for syntheses of spirooxindoles using palladium-catalyzed carbosilylation and Sakurai-type cyclization.

The intramolecular carbosilylation of N-[2-(1,3-butenyl)aryl]carbamoyl chloride has been investigated. The reaction with hexamethyldisilane proceeds smoothly in the presence of a catalytic amount of [Pd(η(3)-allyl)Cl](2) to give oxindoles with an allylsilane functional group in good yield. The subsequent subjection of the products to a Sakurai-type reaction provides more advanced tricyclic spirooxindoles by controlling the stereochemistry of three contiguous stereogenic centers.