2182-14-1Relevant articles and documents
Battersby et al.
, p. 888 (1966)
Rapid Access to the Highly Oxygenated Aspidosperma Alkaloids Vindoline, Vindorosine, and Cathovaline
Danieli, Bruno,Lesma, Giordano,Palmisano, Giovanni,Riva, Renata
, p. 909 - 911 (1984)
A highly expedient and efficient synthesis of vindoline (1a) and vindorosine (1b), via the hitherto unknown azadienes (3a,b), is reported.
Asymmetric Total Syntheses of (-)-Jerantinines A, C, and E, (-)-16-Methoxytabersonine, (-)-Vindoline, and (+)-Vinblastine
Wang, Nengzhong,Liu, Jianrong,Wang, Chen,Bai, Leiyang,Jiang, Xuefeng
, p. 292 - 295 (2018)
A concise and stereocontrolled strategy for the syntheses of oxygenated Aspidosperma and Vinca alkaloids, via a stereoselective intermolecular inverse-electron-demand [4 + 2] cycloaddition, a challenging α,β-unsaturated ketone indolization rearrangement with excellent regio- and stereoselectivity, and an efficient Pd/C-catalyzed one-pot cascade reaction. The strategy has been demonstrated by the efficient asymmetric syntheses of antitumor drug (+)-vinblastine and five other oxygenated Aspidosperma alkaloids.
Asymmetric total synthesis of vindorosine, vindoline, and key vinblastine analogues
Sasaki, Yoshikazu,Kato, Daisuke,Boger, Dale L.
supporting information; experimental part, p. 13533 - 13544 (2010/12/19)
Concise 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 linking the dienophile and oxadiazole was used to control the facial selectivity of the initiating Diels-Alder reaction and set the absolute stereochemistry of the remaining six stereocenters in the cascade cycloadduct. This key reaction introduced three rings and four C-C bonds central to the pentacyclic ring system setting all six stereocenters and introducing essentially all the functionality found in the natural products in a single step. Implementation of the approach for the synthesis of 1 and 2 required the development of a ring expansion reaction to provide a 6-membered ring suitably functionalized for introduction of the Δ6,7-double bond found in the core structure of the natural products. Two unique approaches were developed that defined our use of a protected hydroxymethyl group as the substituent that controls the stereochemical course of the cycloaddition cascade. In the course of these studies, several analogues of vindoline were prepared containing deep-seated structural changes presently accessible only by total synthesis. These analogues, bearing key modifications at C6-C8, were incorporated into vinblastine analogues and used to probe the unusual importance (100-fold) and define the potential role of the vinblastine Δ6,7-double bond.
