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Enantioselective Total Synthesis of (—)-Acetylaranotin, a Dihydrooxepine Epidithiodiketopiperazine

Codelli, Julian A. and Puchlopek, Angela L. A. and Reisman, Sarah E. (2012) Enantioselective Total Synthesis of (—)-Acetylaranotin, a Dihydrooxepine Epidithiodiketopiperazine. Journal of the American Chemical Society, 134 (4). pp. 1930-1933. ISSN 0002-7863. PMCID PMC3271125. doi:10.1021/ja209354e. https://resolver.caltech.edu/CaltechAUTHORS:20120417-140414670

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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.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja209354eDOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja209354ePublisherArticle
https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3271125/PubMed CentralArticle
ORCID:
AuthorORCID
Reisman, Sarah E.0000-0001-8244-9300
Additional Information:© 2011 American Chemical Society. Received: October 4, 2011. Publication Date (Web): October 24, 2011. We thank Dr. Michael Day and Mr. Larry Henling for X-ray crystallographic structure determination and Dr. David Vander-Velde for assistance with NMR structure determination. We thank Prof. Brian Stoltz, Dr. Scott Virgil, and the Caltech Center for Catalysis and Chemical Synthesis for access to analytical equipment. The Bruker KAPPA APEXII X-ray diffractometer was purchased through an award to the California Institute of Technology by the National Science Foundation (NSF) CRIF program (CHE-0639094). NMR spectra were obtained on a spectrometer funded by the National Institutes of Health (NIH) (RR027690). J.A.C. was supported by the Department of Defense (DoD) through the National Defense Science & Engineering Graduate Fellowship Program and by the NSF Graduate Research Fellowship Program (Grant DGE-07032 67). Financial support from the California Institute of Technology and the NIH (NIGMS RGM097582A) is gratefully acknowledged.
Funders:
Funding AgencyGrant Number
NSFCHE-0639094
NIHRR027690
National Defense Science and Engineering Graduate (NDSEG) FellowshipUNSPECIFIED
NSF Graduate Research FellowshipDGE-0703267
CaltechUNSPECIFIED
NIHRGM097582A
Issue or Number:4
PubMed Central ID:PMC3271125
DOI:10.1021/ja209354e
Record Number:CaltechAUTHORS:20120417-140414670
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20120417-140414670
Official Citation:Enantioselective Total Synthesis of (−)-Acetylaranotin, a Dihydrooxepine Epidithiodiketopiperazine Julian A. Codelli, Angela L. A. Puchlopek, and Sarah E. Reisman Journal of the American Chemical Society 2012 134 (4), 1930-1933
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:30141
Collection:CaltechAUTHORS
Deposited By:INVALID USER
Deposited On:18 Apr 2012 14:40
Last Modified:09 Nov 2021 19:37

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