Total synthesis of (-)-himandrine.
We describe the first total synthesis of (-)-himandrine, a member of the class II galbulimima alkaloids. Noteworthy features of this chemistry include a diastereoselective Diels-Alder reaction in the rapid synthesis of the tricycle ABC-ring system in an enantiomerically enriched form, the use of a formal [3+3] annulation strategy to secure the CDE-ring system with complete diastereoselection, and successful implementation of our biogenetically inspired oxidative spirocyclization of an advanced intermediate. The successful and direct late-stage formation of the F-ring in the hexacyclic core of himandrine drew on the power of biogenetic considerations and fully utilized the inherent chemistry of a plausible biosynthetic intermediate.
Movassaghi
Mohammad
M
Massachusetts Institute of Technology, Department of Chemistry, Cambridge, Massachusetts 02139, USA. movassag@mit.edu
Tjandra
Meiliana
M
Qi
Jun
J
D000470:Alkaloids / Q000138:chemical synthesis / Q000737:chemistry; D003500:Cyclization; D006576:Heterocyclic Compounds, 4 or More Rings / Q000138:chemical synthesis* / Q000737:chemistry; D010084:Oxidation-Reduction; D013141:Spiro Compounds / Q000737:chemistry; D013237:Stereoisomerism; D013379:Substrate Specificity
D000470:Alkaloids; D006576:Heterocyclic Compounds, 4 or More Rings; D013141:Spiro Compounds; C487223:himandrine