Synthesis of a pladienolide B analogue with the fully functionalized core structure.

Starting from (R)-(-)-linalool (6), terminus differentiation and chain extension via aldol type reactions led to ketophosphonate 16 (C1-C8 building block). In a Horner-Wadsworth-Emmons reaction, 16 reacted with aldehyde 22, which contained the vicinal anti-Me-OH pattern and a vinyl iodide function, to provide the C1-C13 part of pladienolide B. After Shiina macrolactonization, reduction of the enone 26 gave the core structure 27.

Gold(I)-catalyzed enantioselective polycyclization reactions.

A series of enantioselective polycyclization reactions, catalyzed by a cationic bisphosphine gold complexes, are described. The polycyclization reactions, which employ an alkyne as an initiating group, begin with a gold-promoted 6-exo-dig cyclization and can be terminated with a variety of nucleophiles including carboxylic acids, phenols, sulfonamides, and electron-rich aryl groups. This method allows for the preparation of up to four bonds in a single operation with excellent diastereo- and enantioselectivity.