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Direct Coupling of Catharanthine and Vindoline to Provide Vinblastine: Total Synthesis of (+)- and ent-(−)-Vinblastine
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Section:Abstract
A direct coupling of catharanthine with vindoline to provide vinblastine is detailed along with key mechanistic and labeling studies. Following an Fe(III)-promoted coupling reaction initiated by generation of a presumed catharanthine amine radical cation that undergoes a subsequent oxidative fragmentation and diastereoselective coupling with vindoline, addition of the resulting reaction mixture to an Fe(III)−NaBH4/air solution leads to oxidation of the C15‘−C21‘ double bond and reduction of the intermediate iminium ion directly providing vinblastine (43%) and leurosidine (23%), its naturally occurring C21‘ alcohol isomer. The yield of coupled products, which exclusively possess the natural C16‘ stereochemistry, approaches or exceeds 80%, and the combined yield of the isomeric C21‘ alcohols is 66%.
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This article has been cited by 11 ACS Journal articles (5 most recent appear below).
10′-Fluorovinblastine and 10′-Fluorovincristine: Synthesis of a Key Series of Modified Vinca Alkaloids
Hiroaki Gotoh, Katharine K. Duncan, William M. Robertson, and Dale L. BogerACS Medicinal Chemistry Letters2011 2 (12), 948-95210′-Fluorovinblastine and 10′-Fluorovincristine: Synthesis of a Key Series of Modified Vinca Alkaloids
Hiroaki Gotoh, Katharine K. Duncan, William M. Robertson, and Dale L. BogerACS Medicinal Chemistry Letters2011 2 (12), 948-952A study on the impact of catharanthine C10 and C12 indole substituents on the biomimetic Fe(III)-mediated coupling with vindoline led to the discovery and characterization of two new and substantially more potent derivatives, 10′-fluorovinblastine and 10′-...
On the Elucidation of the Mechanism of Vinca Alkaloid Fluorination in Superacidic Medium
Emerson Giovanelli, Sébastien Leroux, Lionel Moisan, Hélène Carreyre, Pierre Thuéry, David-Alexandre Buisson, Abdelkrim Meddour, Jean-Marie Coustard, Sébastien Thibaudeau, Bernard Rousseau, Marc Nicolas, Paul Hellier, and Eric DorisOrganic Letters2011 13 (15), 4116-4119On the Elucidation of the Mechanism of Vinca Alkaloid Fluorination in Superacidic Medium
Emerson Giovanelli, Sébastien Leroux, Lionel Moisan, Hélène Carreyre, Pierre Thuéry, David-Alexandre Buisson, Abdelkrim Meddour, Jean-Marie Coustard, Sébastien Thibaudeau, Bernard Rousseau, Marc Nicolas, Paul Hellier, and Eric DorisOrganic Letters2011 13 (15), 4116-4119Detailed investigations on one of the key steps of the superacidic fluorination of Vinca alkaloids that is the origin of C20′ activation are reported. While two different pathways can be envisioned for the emergence of the transient secondary ...
Inverse Electron Demand Diels–Alder Reactions of 1,2,3-Triazines: Pronounced Substituent Effects on Reactivity and Cycloaddition Scope
Erin D. Anderson and Dale L. BogerJournal of the American Chemical Society2011 Article ASAPInverse Electron Demand Diels–Alder Reactions of 1,2,3-Triazines: Pronounced Substituent Effects on Reactivity and Cycloaddition Scope
Erin D. Anderson and Dale L. BogerJournal of the American Chemical Society2011 Article ASAPA systematic study of the inverse electron demand Diels–Alder reactions of 1,2,3-triazines is disclosed, including an examination of the impact of a C5 substituent. Such substituents were found to exhibit a remarkable impact on the cycloaddition ...
Asymmetric Total Synthesis of Vindorosine, Vindoline, and Key Vinblastine Analogues
Yoshikazu Sasaki, Daisuke Kato, and Dale L. BogerJournal of the American Chemical Society2010 132 (38), 13533-13544Asymmetric Total Synthesis of Vindorosine, Vindoline, and Key Vinblastine Analogues
Yoshikazu Sasaki, Daisuke Kato, and Dale L. BogerJournal of the American Chemical Society2010 132 (38), 13533-13544Concise asymmetric total syntheses of vindoline (1) and vindorosine (2) are detailed based on a unique intramolecular [4 + 2]/[3 + 2] cycloaddition cascade of 1,3,4-oxadiazoles inspired by the natural product structures. A chiral substituent on the tether ...
Total Synthesis and Evaluation of a Key Series of C5-Substituted Vinblastine Derivatives
Porino Va, Erica L. Campbell, William M. Robertson and Dale L. BogerJournal of the American Chemical Society2010 132 (24), 8489-8495Total Synthesis and Evaluation of a Key Series of C5-Substituted Vinblastine Derivatives
Porino Va, Erica L. Campbell, William M. Robertson and Dale L. BogerJournal of the American Chemical Society2010 132 (24), 8489-8495A remarkably concise seven- to eight-step total synthesis of a systematic series of key vinblastine derivatives is detailed and used to characterize the importance and probe the role of the C5 ethyl substituent (R = H, Me, Pr, CH═CH2, C≡CH, CH2OH, and CHO ...
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- Published In Issue January 16, 2008
- Received October 25, 2007
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