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. doi:10.1021/ja076663z. https://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:

URL	URL Type	Description
http://dx.doi.org/10.1021/ja076663z	DOI	Article
http://pubs.acs.org/doi/abs/10.1021/ja076663z	Publisher	Article
http://pubs.acs.org/doi/suppl/10.1021/ja076663z	Publisher	Supporting Information

ORCID:

Author	ORCID
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 Agency	Grant Number
Bristol-Myers Squibb	UNSPECIFIED
Yamanouchi	UNSPECIFIED
Merck	UNSPECIFIED
Amgen	UNSPECIFIED
Pfizer	UNSPECIFIED
NIH	1 RO1 CA/GM 93591-01A
NIH Postdoctoral Fellowship	UNSPECIFIED

Issue or Number:

DOI:

10.1021/ja076663z

Record Number:

CaltechAUTHORS:20170331-150127498

Persistent URL:

https://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

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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:

15 Nov 2021 16:35

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