Convergent and stereospecific synthesis of complex skipped polyenes and polyunsaturated fatty acids.

Nature Chemistry
Todd K Macklin, Glenn C Micalizio

Abstract

Skipped polyenes (that is, 1,4-dienes and higher homologues) are stereodefined components of a vast array of biologically important natural products, including polyunsaturated fatty acids. Although widespread in nature, these architectures are generally considered to represent significant barriers to efficient chemical synthesis. Partial reduction of skipped poly-ynes provides a pathway to a subset of such structures, but general chemical methods for the preparation of skipped polyenes that contain varied stereochemistries and substitution patterns are lacking. Here, we describe a metal-promoted reductive cross-coupling reaction between vinylcyclopropanes and alkynes (or vinylsilanes) that provides stereoselective access to a diverse array of skipped polyenes through a process that establishes one C-C bond, generates up to three stereodefined alkenes, and can be used to introduce stereogenic centres at the central positions of the skipped polyene motif. We also demonstrate the significance of the present bond construction by preparing substituted and stereodefined polyunsaturated synthetic fatty acids.

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Citations

Jul 1, 2010·Journal of the American Chemical Society·Peter S Diez, Glenn C Micalizio
Apr 12, 2011·Organic Letters·Daniel P Canterbury, Glenn C Micalizio
Sep 17, 2011·Chemical Communications : Chem Comm·Shigeki OishiTakeshi Takeda
Mar 12, 2013·Journal of the American Chemical Society·Matthew S McCammantMatthew S Sigman
Nov 4, 2015·Journal of the American Chemical Society·Souvagya BiswasT V RajanBabu
Oct 6, 2015·Journal of the American Chemical Society·David P ToddJohn Montgomery
Feb 11, 2015·Accounts of Chemical Research·Glenn C Micalizio, Sarah B Hale
Feb 13, 2018·Chemistry, an Asian Journal·Yoshiyuki NagashimaNoritaka Chida
Sep 14, 2010·Chemical Communications : Chem Comm·Philipp WinterMathias Christmann
Jul 7, 2019·Angewandte Chemie·Jie ChenTeck-Peng Loh
Aug 7, 2012·Chemistry : a European Journal·Subramaniyan Mannathan, Chien-Hong Cheng
Mar 19, 2013·Chemical Communications : Chem Comm·Yange HuangBen L Feringa
Mar 26, 2011·Chemical Science·Holly A Reichard, Glenn C Micalizio
Jun 28, 2017·Israel Journal of Chemistry·Glenn C Micalizio, Haruki Mizoguchi
Aug 16, 2013·Beilstein Journal of Organic Chemistry·Kristin D Schleicher, Timothy F Jamison
Jan 25, 2014·Angewandte Chemie·Hongli BaoUttam K Tambar
Dec 9, 2020·Angewandte Chemie·Lorenz E LöfflerAlois Fürstner
Jul 30, 2021·Journal of the American Chemical Society·Po YuanTanja Gaich
Mar 15, 2018·The Journal of Organic Chemistry·Jeffrey BruffaertsIlan Marek
May 3, 2019·Organic Letters·Catherine P McGeoughTimothy F Jamison
Jul 25, 2019·Organic Letters·Wei DingNaohiko Yoshikai
Feb 14, 2017·Journal of the American Chemical Society·Takahiro SutoNoritaka Chida

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Methods Mentioned

BETA
column chromatography

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