Nickel-Catalyzed Asymmetric Alkene Hydrogenation of α,β-Unsaturated Esters: High-Throughput Experimentation-Enabled Reaction Discovery, Optimization, and Mechanistic Elucidation

Journal of the American Chemical Society
Michael ShevlinPaul J Chirik

Abstract

A highly active and enantioselective phosphine-nickel catalyst for the asymmetric hydrogenation of α,β-unsaturated esters has been discovered. The coordination chemistry and catalytic behavior of nickel halide, acetate, and mixed halide-acetate with chiral bidentate phosphines have been explored and deuterium labeling studies, the method of continuous variation, nonlinear studies, and kinetic measurements have provided mechanistic understanding. Activation of molecular hydrogen by a trimeric (Me-DuPhos)3Ni3(OAc)5I complex was established as turnover limiting followed by rapid conjugate addition of a nickel hydride and nonselective protonation to release the substrate. In addition to reaction discovery and optimization, the previously unreported utility high-throughput experimentation for mechanistic elucidation is also described.

References

Dec 20, 2002·Angewandte Chemie·Keith Fagnou, Mark Lautens
Oct 27, 2004·Bioorganic & Medicinal Chemistry Letters·Shyamali GhoshBruce E Maryanoff
Aug 25, 2007·Accounts of Chemical Research·Hans-Ulrich BlaserMarc Thommen
Oct 27, 2007·Accounts of Chemical Research·Lionel A Saudan
Jun 11, 2009·Journal of the American Chemical Society·Karl B HansenJoseph D Armstrong
Apr 23, 2010·Bioorganic & Medicinal Chemistry Letters·Prasanta GhoraiArmin Buschauer
Mar 3, 2012·Journal of the American Chemical Society·W Hill Harman, Jonas C Peters
Mar 7, 2012·Journal of the American Chemical Society·Sebastien MonfettePaul J Chirik
Nov 6, 2012·Chemistry : a European Journal·Iris R M TébékaLuiz F Silva
Jan 23, 2014·Journal of the American Chemical Society·Paraskevi O LagaditisRobert H Morris
Mar 29, 2014·Angewandte Chemie·Daniel A DiroccoMatthew Tudge
Sep 23, 2014·Nature Chemistry·Karl D CollinsFrank Glorius
Dec 20, 2014·Journal of the American Chemical Society·Carmela MolinaroDavid Lieberman
Jan 3, 2015·Science·Alexander Buitrago SantanillaSpencer D Dreher
Mar 5, 2015·Angewandte Chemie·Haiyan XuJianrong Steve Zhou
Jun 2, 2015·Journal of Agricultural and Food Chemistry·Jing XuYuanqiang Guo
Jul 1, 2015·Chemical Communications : Chem Comm·Siyu GuoJianrong Steve Zhou
Sep 18, 2015·Journal of the American Chemical Society·Ryan C Cammarota, Connie C Lu
Sep 29, 2015·Journal of the American Chemical Society·Hongming LiKevin R Campos
Oct 17, 2015·Science·Ties J KorstanjeBas de Bruin

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Citations

Jul 21, 2016·Chemical Reviews·Nathan A Eberhardt, Hairong Guan
Apr 21, 2017·Angewandte Chemie·Magnus B WidegrenMatthew L Clarke
May 2, 2017·Annual Review of Chemical and Biomolecular Engineering·Joshua A SelekmanJacob Janey
Dec 9, 2016·Chemical Communications : Chem Comm·S J Connelly Robinson, D M Heinekey
Mar 1, 2018·Chemistry : a European Journal·Alexis LatorJean-Luc Renaud
May 9, 2018·Chemical Society Reviews·Marc Renom-Carrasco, Laurent Lefort
Dec 24, 2018·Angewandte Chemie·Eric S IsbrandtStephen G Newman
Mar 29, 2019·Angewandte Chemie·Bowen LiWanbin Zhang
Jan 21, 2020·Angewandte Chemie·Yawen HuWanbin Zhang
Sep 26, 2019·Angewandte Chemie·Connor W ColeyKlavs F Jensen
Apr 19, 2019·Chemical Science·Suppachai KrajangsriPher G Andersson
Jan 17, 2017·Angewandte Chemie·Fenglin ChenShaolin Zhu
Jan 23, 2018·Organic & Biomolecular Chemistry·Wen-Jing Pan, Zhong-Xia Wang
May 13, 2020·Physical Chemistry Chemical Physics : PCCP·Katherine McCulloughJochen Lauterbach
Jun 12, 2019·Molecules : a Journal of Synthetic Chemistry and Natural Product Chemistry·Hawraz I M AminMaurizio Fagnoni
Jan 23, 2021·Chemical Society Reviews·Jialin WenXumu Zhang
Jan 21, 2021·Accounts of Chemical Research·Yao ShiJason E Hein
Mar 4, 2021·Chemical Communications : Chem Comm·M Trinidad MartínM Carmen Nicasio
Apr 24, 2021·Journal of the American Chemical Society·Patrick D ParkerVy M Dong
Feb 6, 2020·Journal of the American Chemical Society·Peter ViereckPaul J Chirik
Jun 19, 2021·Journal of the American Chemical Society·Yiting GuScott A Snyder
Oct 22, 2019·Journal of the American Chemical Society·Yujie WangQiang Liu
Jun 20, 2017·ACS Medicinal Chemistry Letters·Michael Shevlin
Feb 18, 2020·Journal of the American Chemical Society·Hongyu ZhongPaul J Chirik
Oct 19, 2017·The Journal of Organic Chemistry·Wubin ZhiYangjie Wu

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