10.1021/ja990707p
The research focuses on the concise, enantioselective synthesis of (-)-dendrobine (1), a major alkaloid constituent of the Chinese ornamental orchid Dendrobium nobile, known for its antipyretic and hypotensive activities. The purpose of the study was to develop an efficient and stereoselective synthetic route to this molecule, which was achieved in 13 steps, starting from (+)-trans-verbenol (6). The synthesis involved a cascade reaction with a carbamyl radical to form amino alcohol 3, establishing the three principal stereogenic centers. Key chemicals used in the process included Pauson-Khand reaction components, such as N-propargyl derivative 8, and various reagents for functional group transformations, like iodotrimethylsilane, phenylselenenyl bromide, diethylaluminum cyanide, and sodium borohydride. The synthesis concluded with the formation of (-)-dendrobine (1) from cyanoketone 13 through a series of reactions, including reduction, Barton-McCombie deoxygenation, and epimerization, ultimately yielding the target compound with a 75% overall yield from 14 based on the recovered 15b. The study also highlighted the intriguing solvent effect on the Pauson-Khand reaction and the efficient formation of the azatricyclo[6.2.1.04,11]undecane ring system.
10.1080/00397919408010246
The research focuses on developing an efficient method for the cyanation of enamines and 1,3-dicarbonyl compounds. The purpose of this study is to improve upon existing cyanation procedures, which often suffer from limitations such as toxicity, accessibility issues, thermal instability, or low yields. The researchers utilized acyl-substituted cyanatobenzenes and cyanatoanthraquinones as cyanating agents to react with enamines and 1,3-dicarbonyl compounds. The results demonstrated that this method yields good to excellent yields of the desired cyanoenamines and cyanoketones. The process involves treating enamines with the cyanating agents at room temperature, followed by hydrolysis to obtain the cyanoketones.