Silicon-directed rhenium-catalyzed allylic substitutions with N-hydroxycarbamates, N-hydroxysulfonamides, and hydroxamic acids.

A rhenium-catalyzed N-selective allylic amination reaction of N-hydroxycarbamates has been developed. This reaction occurs with excellent N/O selectivity and with complete carbon selectivity on the allylic system. The reaction is tolerant of many functional groups and also proceeds with N-hydroxysulfonamides and hydroxamic acids.

Silicon-directed rhenium-catalyzed allylic carbaminations and oxidative fragmentations of γ-silyl allylic alcohols.

A highly regioselective allylic substitution of β-silyl allylic alcohols has been achieved that provides the branched isomer as a single product. This high level of regiocontrol is achieved through the use of a vinyl silane group that can perform a Hiyama coupling providing 1,3-disubstituted allylic amines. An unusual oxidative fragmentation product was also observed at elevated temperature that appears to proceed by a Fleming-Tamao-type oxidation-elimination pathway.

Total synthesis of (±)-coerulescine and (±)-horsfiline.

Wittig olefination-Claisen rearrangement protocol was applied to obtain 3-allyl oxindole. This oxindole was then converted to (±)-coerulescine and (±)-horsfiline.

Zeolite catalyzed solvent-free one-pot synthesis of dihydropyrimidin-2(1H)-ones--a practical synthesis of monastrol.

A zeolite-catalyzed, simple, one-pot, solvent-free, cost effective, and environmentally benign process for the synthesis of dihydropyrimidones is described. This reaction is scaleable to multigram scale and the catalyst is recyclable. This methodology has resulted in an efficient synthesis of monastrol, a potent inhibitor of kinesin Eg5.