Total Synthesis of (+)-Minfiensine: Construction of the Tetracyclic Core Structure by an Asymmetric Cascade Cyclization

• Published in: Angewandte Chemie (International ed.) Vol. 55; no. 28; pp. 8090 - 8094
• Main Authors: Zhang, Ze-Xin, Chen, Si-Cong, Jiao, Lei
• Format: Journal Article
• Language: English
• Published: WEINHEIM Blackwell Publishing Ltd 04.07.2016; Wiley; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Alkaloids; Asymmetry; Chemical synthesis; Chemistry; Chemistry, Multidisciplinary; Construction; Construction methods; cyclizations; Indoles; natural products; Palladium; Physical Sciences; Science & Technology; Strategy; total synthesis; AKUAMMILINE ALKALOIDS; (+/-)-MINFIENSINE; CONCISE TOTAL-SYNTHESIS; CATALYZED ALLYLIC ALKYLATION; IMINIUM ION CYCLIZATION; alkaloids; 3-SUBSTITUTED INDOLES; cyclizations; natural products; DEAROMATIZATION REACTIONS; PHOSPHINE-LIGANDS; palladium; total synthesis; ENANTIOSELECTIVE TOTAL-SYNTHESIS
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201602771

A new method for one‐step construction of the tetracyclic core structure of the indole alkaloid (+)‐minfiensine was developed utilizing a palladium‐catalyzed asymmetric indole dearomatization/iminium cyclization cascade. An efficient total synthesis of (+)‐minfiensine was realized using this strategy. The present method enables access to the common core structure of a series of monoterpene indole alkaloids, such as vincorine, echitamine, and aspidosphylline A. All at once: A palladium‐catalyzed asymmetric cascade cyclization enabled one‐step construction of the tetracyclic core framework of the indole alkaloid (+)‐minfiensine. A palladium‐catalyzed Heck‐type cyclization completed its total synthesis efficiently.