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

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 chlor...

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Published in:Journal of the American Chemical Society 2008-02, Vol.130 (6), p.2087-2100
Main Authors: Reisman, Sarah E, Ready, Joseph M, Weiss, Matthew M, Hasuoka, Atsushi, Hirata, Makoto, Tamaki, Kazuhiko, Ovaska, Timo V, Smith, Catherine J, Wood, John L
Format: Article
Language:English
Subjects:
Bridged Bicyclo Compounds - chemistry
Cyclization
Indole Alkaloids - chemical synthesis
Indole Alkaloids - chemistry
Indoles - chemical synthesis
Indoles - chemistry
Ketones - chemical synthesis
Ketones - chemistry
Molecular Conformation
Octanes - chemistry
Spiro Compounds - chemical synthesis
Spiro Compounds - chemistry
Stereoisomerism
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cited_by cdi_FETCH-LOGICAL-a417t-857fa745cad6f6c47d7fa3cd72c16827d484afb25c90e7d7e997cfa24d404f9f3
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container_title Journal of the American Chemical Society
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creator Reisman, Sarah E
Ready, Joseph M
Weiss, Matthew M
Hasuoka, Atsushi
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Wood, John L
description 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 SmI2−LiCl mediated reductive cyclization and a novel anionic cyclization that simultaneously constructs the spiro-oxindole and vinyl isonitrile moieties.
doi_str_mv 10.1021/ja076663z
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source American Chemical Society:Jisc Collections:American Chemical Society Read & Publish Agreement 2022-2024 (Reading list)
subjects Bridged Bicyclo Compounds - chemistry
Cyclization
Indole Alkaloids - chemical synthesis
Indole Alkaloids - chemistry
Indoles - chemical synthesis
Indoles - chemistry
Ketones - chemical synthesis
Ketones - chemistry
Molecular Conformation
Octanes - chemistry
Spiro Compounds - chemical synthesis
Spiro Compounds - chemistry
Stereoisomerism
title Evolution of a Synthetic Strategy:  Total Synthesis of (±)-Welwitindolinone A Isonitrile
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