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Evolution of a Synthetic Strategy: Total Synthesis of (±)-Welwitindolinone A Isonitrile

Reisman, Sarah E. and Ready, Joseph M. and Weiss, Matthew M. and Hasuoka, Atsushi and Hirata, Makoto and Tamaki, Kazuhiko and Ovaska, Timo V. and Smith, Catherine J. and Wood, John L. (2008) Evolution of a Synthetic Strategy: Total Synthesis of (±)-Welwitindolinone A Isonitrile. Journal of the American Chemical Society, 130 (6). pp. 2087-2100. ISSN 0002-7863. http://resolver.caltech.edu/CaltechAUTHORS:20170331-150127498

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Abstract

An efficient and highly stereoselective total synthesis of the natural product (±)-welwitindolinone A isonitrile (1) is described. The bicyclo[4.2.0]octane core of 1 was established by a regio- and diastereoselective [2+2] ketene cycloaddition. The C12 quaternary center and vicinal stereogenic chlorine were installed in a single operation with excellent stereocontrol via a chloronium ion mediated semipinacol rearrangement. Described strategies for construction of the spiro-oxinole include a SmI_2−LiCl mediated reductive cyclization and a novel anionic cyclization that simultaneously constructs the spiro-oxindole and vinyl isonitrile moieties.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/ja076663zDOIArticle
http://pubs.acs.org/doi/abs/10.1021/ja076663zPublisherArticle
http://pubs.acs.org/doi/suppl/10.1021/ja076663zPublisherSupporting Information
ORCID:
AuthorORCID
Reisman, Sarah E.0000-0001-8244-9300
Additional Information:© 2008 American Chemical Society. Received September 19, 2007; Publication Date (Web): January 17, 2008. Financial support was provided by Bristol-Myers Squibb, Yamanouchi, Merck, Amgen, Pfizer, and the NIH (Grant No. 1 RO1 CA/GM 93591-01A). S.E.R. thanks Bristol-Myers Squibb for a graduate student fellowship. J.M.R. was the recipient of a NIH postdoctoral fellowship. In addition, we acknowledge and thank C.D. Incarvito for X-ray crystallographic analysis.
Funders:
Funding AgencyGrant Number
Bristol-Myers SquibbUNSPECIFIED
YamanouchiUNSPECIFIED
MerckUNSPECIFIED
AmgenUNSPECIFIED
PfizerUNSPECIFIED
NIH1 RO1 CA/GM 93591-01A
NIH Postdoctoral FellowshipUNSPECIFIED
Record Number:CaltechAUTHORS:20170331-150127498
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20170331-150127498
Official Citation:Evolution of a Synthetic Strategy:  Total Synthesis of (±)-Welwitindolinone A Isonitrile Sarah E. Reisman, Joseph M. Ready, Matthew M. Weiss, Atsushi Hasuoka, Makoto Hirata, Kazuhiko Tamaki, Timo V. Ovaska, Catherine J. Smith, and John L. Wood Journal of the American Chemical Society 2008 130 (6), 2087-2100 DOI: 10.1021/ja076663z
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:75606
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:03 Apr 2017 17:01
Last Modified:03 Apr 2017 17:01

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