The First Total Synthesis of (–)-Lemonomycin and Progress toward the Total Synthesis of (+)-Cyanocycline A

Antibiotic;Antitumor;Dipolar Cycloaddition;Pictet-Spengler;Tetrahydroisoquinoline;Total Synthesis

Ashley, Eric Robert ; Stoltz, Brian M.

University:California Institute of Technology

Department:Chemistry and Chemical Engineering

关键词: Antibiotic;    Antitumor;    Dipolar Cycloaddition;    Pictet-Spengler;    Tetrahydroisoquinoline;    Total Synthesis;   

Others  :  https://thesis.library.caltech.edu/4579/12/ERAThesis.pdf

美国|英语

来源: Caltech THESIS

【 摘 要 】

The first total synthesis of (–)-lemonomycin has been accomplished.The synthesis features a novel, auxiliary-controlled asymmetric dipolar cycloaddition, a highly convergent Suzuki coupling, a diastereoselective enamide hydrogenation to set the C(3) stereochemistry, and a convergent, efficient, and completely diastereoselective Pictet-Spengler cyclization with a glycosyloxy acetaldehyde.

The total synthesis of (+)-cyanocycline A has been approached along two routes.Both routes feature dipolar cycloaddition reactions with alkyne-containing substrates and completely diastereoselective hydrogenations to set the C(4) stereochemistry.Proposals for the advancement of late-stage intermediates to the natural product are included.