Palladium-catalyzed enantioselective Heck alkenylation of acyclic alkenols using a redox-relay strategy

Journal of the American Chemical Society
Harshkumar H Patel, Matthew S Sigman

Abstract

We report a highly enantioselective intermolecular Heck reaction of alkenyl triflates and acyclic primary or racemic secondary alkenols. The mild reaction conditions permit installation of a wide range of alkenyl groups at positions β, γ, or δ to a carbonyl group in high enantioselectivity. The success of this reaction is attributed to the use of electron-withdrawing alkenyl triflates, which offer selective β-hydride elimination followed by migration of the catalyst through the alkyl chain to give the alkenylated carbonyl products. The synthetic utility of the process is demonstrated by a two-step modification of a reaction product to yield a tricyclic core structure, present in various natural products.

References

Aug 1, 1996·Journal of Natural Products·A SendlM Balick
Jun 30, 2001·Organic Letters·S R Gilbertson, Z Fu
Oct 24, 2001·The Journal of Organic Chemistry·Abimael D. RodríguezSongping D. Huang
Nov 20, 2001·Chemical Reviews·L Pu, H B Yu
Dec 26, 2001·Chemical Reviews·I P Beletskaya, A V Cheprakov
Aug 14, 2003·Chemical Reviews·Tamio Hayashi, Kaori Yamasaki
Aug 14, 2003·Chemical Reviews·Amy B Dounay, Larry E Overman
Aug 28, 2004·Organic Letters·George A Kraus, Junwon Kim
Dec 8, 2004·Mini Reviews in Medicinal Chemistry·Kevin K-C LiuSubas Sakya
Jul 3, 2007·Journal of the American Chemical Society·Yoshiaki NakaoTamio Hayashi
Feb 16, 2008·Drug Discovery Today·Arvind Saklani, Samuel K Kutty
Jun 11, 2008·Organic Letters·David BabinskiDoug E Frantz
Jun 2, 2011·Journal of the American Chemical Society·Erik W Werner, Matthew S Sigman
Jun 17, 2011·Chemical Society Reviews·Dennis Mc Cartney, Patrick J Guiry
Mar 29, 2012·Journal of the American Chemical Society·Jordan P Page, T V RajanBabu
Jun 30, 2012·Journal of the American Chemical Society·Benjamin J StokesMatthew S Sigman
Jul 7, 2012·Journal of the American Chemical Society·Vaneet Saini, Matthew S Sigman
Sep 7, 2012·Journal of the American Chemical Society·Audrey G RossSamuel J Danishefsky
Dec 22, 2012·Journal of the American Chemical Society·James Y HamiltonErick M Carreira
Mar 12, 2013·Journal of the American Chemical Society·Matthew S McCammantMatthew S Sigman
Apr 24, 2013·Journal of the American Chemical Society·Tian-Sheng MeiMatthew S Sigman
Jul 31, 2013·Journal of the American Chemical Society·Jason M Stevens, David W C MacMillan
Jan 15, 2014·Journal of the American Chemical Society·Liping XuOlaf Wiest
Apr 11, 2014·Nature·Tian-Sheng MeiMatthew S Sigman
Sep 24, 2014·Journal of the American Chemical Society·Alan H Cherney, Sarah E Reisman

❮ Previous
Next ❯

Citations

Feb 20, 2016·Nature Chemistry·Alexandre VasseurIlan Marek
Jul 20, 2016·Journal of the American Chemical Society·Luqing LinClément Mazet
Nov 3, 2016·Journal of the American Chemical Society·Harshkumar H Patel, Matthew S Sigman
Oct 27, 2016·Angewandte Chemie·Stéphanie DupuyOlivier Baudoin
Feb 17, 2017·Angewandte Chemie·Sukdev BagDebabrata Maiti
Apr 26, 2018·Chemistry : a European Journal·Ilan MarekMarwan Simaan
Aug 2, 2018·Chemical Communications : Chem Comm·Santos FusteroPablo Barrio
Nov 8, 2018·Chemistry : a European Journal·Nicholas J RaceMatthew S Sigman
Jun 20, 2019·Chemistry : a European Journal·Qianjia Yuan, Matthew S Sigman
Sep 15, 2017·Beilstein Journal of Organic Chemistry·Carolina S GarcíaSandra E Martín
Mar 3, 2020·Angewandte Chemie·Xufang LiuQiang Liu
Feb 23, 2018·Chemical Society Reviews·Guoqiang Yang, Wanbin Zhang
Jan 9, 2016·Chemistry : a European Journal·Lucia CerisoliArianna Quintavalla
Aug 15, 2017·Angewandte Chemie·Xurong QinJianrong Steve Zhou
Oct 8, 2019·Chemical Science·Zhi-Min ChenMatthew S Sigman
Aug 17, 2019·Chemical Communications : Chem Comm·Qixue QinNing Jiao
Nov 21, 2017·Chemistry, an Asian Journal·Ze-Zhen JiangXue-Long Hou
Aug 4, 2020·Chemistry : a European Journal·Holly E BonfieldMarc Reid
Mar 13, 2021·Organic Letters·Samantha L KrausMatthew S Sigman
Jul 24, 2021·Organic Letters·Ying DingXianjie Fang
May 16, 2020·Journal of the American Chemical Society·Sean P RossMatthew S Sigman

❮ Previous
Next ❯

Related Concepts

Related Feeds

Cell Migration

Cell migration is involved in a variety of physiological and pathological processes such as embryonic development, cancer metastasis, blood vessel formation and remoulding, tissue regeneration, immune surveillance and inflammation. Here is the latest research.