Total synthesis of (-)-stemospironine

Organic Letters

Volumn 3, Issue 17, 2001, Pages 2721-2724

  Williams, David R ^a   Fromhold, Mark G ^a   Earley, Jill D ^a  

^a INDIANA UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKALOID; POLYCYCLIC HYDROCARBON; SPIRO COMPOUND; STEMOSPIRONINE;

ANGIOSPERM; ARTICLE; CHEMISTRY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; SYNTHESIS;

ALKALOIDS; ANGIOSPERMS; MAGNETIC RESONANCE SPECTROSCOPY; POLYCYCLIC COMPOUNDS; SPIRO COMPOUNDS;

EID: 0035940098     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol016336a     Document Type: Article

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48. Previously we had shown (ref 4) that it was advantageous to introduce limited amounts of iodine solution and quench cyclizations at approximately 50% completion, yielding the desired product (30-35%) and recovered starting material (50-55%) for resubmission. In the case of stemospironine, limited quantities of 18 precluded this approach, and the complete consumption of starting alkene led to numerous polar byproducts.
49. Although we were unable to procure a sample of stemospironine from the original laboratories (ref 12), our synthetic material provided spectra and physical data which were completely consistent with data reported for the natural product as assigned by X-ray diffraction.
50. We gratefully acknowledge the assistance of Professor Yang Ye, Shanghai Institute of Materia Medica, Chinese Academy of Sciences, for providing spectra and an authentic sample of (-)-stemonidine.
51. Professor R.-S. Xu has indicated ongoing revisions of 2. See: He, X.; Lin, W.-H.; Xu, R.-S. Acta Chim. Sin. 1990, 48, 694.
52. We can visualize slight differences in the line art of the proton NMR spectra of 1 and (-)-stemonidine (see Supporting Information). However, small differences in chemical shifts and coupling constants are within the tolerances and limits of error of our instrumentation. Small quantities of these samples have precluded additional experiments.