Total Synthesis of (+)-MPC1001B

• Published in: Angewandte Chemie (International ed.) Vol. 55; no. 1; pp. 283 - 287
• Main Authors: Kurogi, Taichi, Okaya, Shun, Fujiwara, Hideto, Okano, Kentaro, Tokuyama, Hidetoshi
• Format: Journal Article
• Language: English
• Published: Weinheim WILEY-VCH Verlag 04.01.2016; WILEY‐VCH Verlag; Wiley; Wiley Subscription Services, Inc
• Edition: International ed. in English
• Subjects: Aldehydes; aldol reaction; alkaloids; Alkaloids - chemical synthesis; Alkaloids - chemistry; Chemical synthesis; Chemistry; Chemistry, Multidisciplinary; Construction; dithiodiketopiperazine; Fluorides; Heterocyclic Compounds, 4 or More Rings - chemical synthesis; Heterocyclic Compounds, 4 or More Rings - chemistry; macrolactones; Molecular Structure; Physical Sciences; Science & Technology; Stereoisomerism; total synthesis; aldol reaction; ASYMMETRIC-SYNTHESIS; MOLECULAR-STRUCTURE; alkaloids; MPC1001; RING-SYSTEM; MACROCYCLIC EPIDITHIODIOXOPIPERAZINE; dithiodiketopiperazine; macrolactones; FUNGAL METABOLITES; ESTERS; CHEMISTRY; GENERAL-APPROACH; total synthesis
• ISSN: 1433-7851; 1521-3773
• DOI: 10.1002/anie.201507830

The first total synthesis of an epidithiodiketopiperazine alkaloid, (+)‐MPC1001B, was accomplished. This synthesis features a tetra‐n‐butylammonium fluoride mediated intramolecular aldol reaction for forming the 15‐membered macrolactone ring, and the construction of an epidithiodiketopiperazine substructure through a stepwise sulfenylation reaction involving a novel trityl trisulfide (TrSSS)‐group transfer. Going round in circles: The first total synthesis of an epidithiodiketopiperazine alkaloid, (+)‐MPC1001B, was accomplished through a sequence involving a TBAF‐mediated intramolecular aldol reaction to form the 15‐membered macrolactone ring, and construction of an epidithiodiketopiperazine through a stepwise sulfenylation reaction involving a novel trityl trisulfide (TrSSS) group transfer.