Synthesis of (+)-casuarine.
The first synthesis of (+)-casuarine ((+)-6), a pentahydroxy pyrrolizidine alkaloid of the alexine/australine subclass, is described. The key step is a tandem [4 + 2]/[3 + 2] nitroalkene cycloaddition involving nitrobenzoate 13, chiral vinyl ether 16c, and vinyl silane 10, which establishes five of the six stereocenters present in this potent glycosidase inhibitor. The completion of the synthesis requires only four additional steps to deliver the final product in 20% overall yield.
Denmark
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Roger Adams Laboratory, Department of Chemistry, University of Illinois, Urbana, Illinois 61801, USA.
Hurd
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D000470:Alkaloids / Q000138:chemical synthesis*; D018360:Crystallography, X-Ray; D003500:Cyclization; D004791:Enzyme Inhibitors / Q000138:chemical synthesis*; D006026:Glycoside Hydrolases / Q000037:antagonists & inhibitors*; D006900:Hydroxylation; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D019441:Plant Epidermis / Q000737:chemistry; D011758:Pyrroles / Q000138:chemical synthesis*; D011763:Pyrrolizidine Alkaloids / Q000138:chemical synthesis*; D013237:Stereoisomerism
D000470:Alkaloids; D004791:Enzyme Inhibitors; D011758:Pyrroles; D011763:Pyrrolizidine Alkaloids; C409108:casuarine; D006026:Glycoside Hydrolases