10444-12-9Relevant articles and documents
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Wakamatsu,S.
, p. 1285 - 1288 (1962)
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A Concise Enantioselective Total Synthesis of (?)-Deoxoapodine
Okada, Kosuke,Tokuyama, Hidetoshi,Ueda, Hirofumi,Yoshida, Kei
supporting information, p. 23089 - 23093 (2020/10/20)
We have established a highly convergent 10-step route for the total synthesis of (?)-deoxoapodine, which is a hexacyclic aspidosperma alkaloid. The quaternary C5 center of the characteristic tetrahydrofuran ring was constructed by a chiral-phosphoric-acid
Synthesis of the pentacyclic skeleton of the aspidosperma alkaloids using rhodium carbenoids as reactive intermediates
Padwa, Albert,Price, Alan T.
, p. 556 - 565 (2007/10/03)
A series of diazo amido keto esters prepared from N-alkenyl-substituted 3-carbalkoxy-2-piperidone derivatives was treated with rhodium(II) acetate. Attack of the amido carbonyl oxygen at the resultant rhodium carbenoid center produced a transient push-pull carbonyl ylide dipole which underwent an intramolecular dipolar cycloaddition reaction. A related annulation sequence was used to prepare the pentacyclic skeleton of the aspidosperma family of alkaloids. Synthesis of the required diazo imide was carried out from 3- carboxy-3-ethyl-2-piperidone and N-methyl-3-indoleacetic acid. Treatment of the diazo imide with rhodium(II) acetate afforded a transient 1,3-dipole which subsequently underwent cycloaddition across the indole π-bond. The resulting clycloadduct is the consequence of endo cycloaddition with respect to the dipole which is fully in accord with the lowest energy transition state. The clycloadduct was converted in three steps into desacetoxy-4-oxo- 6,7-dihydrovindorosine. The stereochemistry of the final product was established by a X-ray crystallographic study.
