Enantioselective Total Synthesis of (−)-Acetylaranotin, a Dihydrooxepine Epidithiodiketopiperazine
- 24 October 2011
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 134 (4), 1930-1933
- https://doi.org/10.1021/ja209354e
Abstract
The first total synthesis of the dihydrooxepine-containing epidithiodiketopiperazine (ETP) (−)-acetylaranotin (1) is reported. The key steps of the synthesis include an enantioselective azomethine ylide (1,3)-dipolar cycloaddition reaction to set the absolute and relative stereochemistry, a rhodium-catalyzed cycloisomerization/chloride elimination sequence to generate the dihydrooxepine moiety, and a stereoretentive diketopiperazine sulfenylation to install the epidisulfide. This synthesis provides access to (−)-1 in 18 steps from inexpensive, commercially available starting materials. We anticipate that the approach described herein will serve as a general strategy for the synthesis of additional members of the dihydrooxepine ETP family.This publication has 41 references indexed in Scilit:
- Total Synthesis of Epicoccin GJournal of the American Chemical Society, 2011
- Enantioselective Total Synthesis of (+)-Gliocladine C: Convergent Construction of Cyclotryptamine-Fused Polyoxopiperazines and a General Approach for Preparing Epidithiodioxopiperazines from Trioxopiperazine PrecursorsJournal of the American Chemical Society, 2011
- General Approach to Epipolythiodiketopiperazine Alkaloids: Total Synthesis of (+)-Chaetocins A and C and (+)-12,12′-Dideoxychetracin AJournal of the American Chemical Society, 2010
- A Unified Strategy Targeting the Thiodiketopiperazine Mycotoxins Exserohilone, Gliotoxin, the Epicoccins, the Epicorazines, Rostratin A and AranotinChemistry – A European Journal, 2010
- Osmium‐Catalyzed 7‐endo Heterocyclization of Aromatic Alkynols into BenzoxepinesAngewandte Chemie, 2010
- Asymmetric Synthesis of the ABC-Ring System of the Antitumor Antibiotic MPC1001The Journal of Organic Chemistry, 2008
- Structure of a novel epidithiodioxopiperazine, emethallicin A, a potent inhibitor of histamine release, from Emericella heterothallica.CHEMICAL & PHARMACEUTICAL BULLETIN, 1989
- A total synthesis of gliotoxinJournal of the American Chemical Society, 1976
- Crystal and molecular structure of LL-S88.alpha., an antiviral epidithiapiperazinedione derivative from Aspergillus terreusJournal of the American Chemical Society, 1968
- Aranotin and related metabolites. III. Configuration and conformation of acetylaranotinJournal of the American Chemical Society, 1968