Coordination-Induced Stereocontrol over Carbocations: Asymmetric Reductive Deoxygenation of Racemic Tertiary Alcohols

Journal of the American Chemical Society
Mayuko IsomuraErick M Carreira

Abstract

The inherent difficulty in eliciting facial control over carbocations has limited their utility as intermediates in asymmetric catalysis. We have now shown that a docking strategy involving the reversible coordination of a substrate to a chiral transition-metal catalyst can be used to enable highly stereoselective nucleophilic attack on intermediate tertiary carbocations. This approach has been implemented to achieve the first example of enantioselective reductive deoxygenation of tertiary alcohols. This reduction occurs with high enantio- (up to 96% ee) and regioselectivity (up to >50:1 rr) by applying a novel Hantzsch ester analogue as a convenient hydride source. In-depth mechanistic studies support the involvement of a tertiary carbocation that is coordinated to the iridium metal center via the key allene moiety.

References

Jan 22, 2004·Chemistry : a European Journal·Tobias C WabnitzJonathan B Spencer
Jun 30, 2005·Journal of the American Chemical Society·Friedrich MühlthauThorsten Bach
Oct 13, 2005·Journal of the American Chemical Society·Barry M TrostDiana C Dinh
Mar 24, 2006·Angewandte Chemie·Kimihiro KomeyamaKen Takaki
Jun 28, 2006·Angewandte Chemie·Yoshiaki NishibayashiMitsunobu Sato
Jun 9, 2007·Journal of the American Chemical Society·Jie Huang, Alison J Frontier
Dec 19, 2007·Accounts of Chemical Research·Stéphane G OuelletDavid W C MacMillan
Nov 19, 2008·Angewandte Chemie·Philipp RubenbauerThorsten Bach
Oct 15, 2009·Angewandte Chemie·Pierre CordierVincent Gandon
Nov 26, 2009·Chemistry : a European Journal·Marion DavoustMark Lautens
Feb 18, 2010·Tetrahedron Letters·Tsung-Hao FuStephen F Martin
May 8, 2010·Chemical Communications : Chem Comm·Guo-Xing Li, Jin Qu
Jun 17, 2010·Organic Letters·Matthew R MedeirosJohn A Porco
Jun 24, 2010·Journal of the American Chemical Society·Adam R BrownEric N Jacobsen
Nov 6, 2010·Angewandte Chemie·Giulia BergonziniPaolo Melchiorre
Mar 2, 2011·Journal of the American Chemical Society·Magnus RuepingIuliana Atodiresei
May 20, 2011·Organic Letters·Clémence LiébertMark Lautens
Oct 13, 2011·The Journal of Organic Chemistry·Jacqueline E MilneJerry A Murry
Oct 21, 2011·The Journal of Organic Chemistry·Tuan Thanh DangLukas Hintermann
Mar 2, 2012·Chemistry : a European Journal·Vera J Meyer, Meike Niggemann
Mar 17, 2012·Beilstein Journal of Organic Chemistry·Michael DobmeierBurkhard König
Jul 12, 2012·Journal of the American Chemical Society·Karavadhi Surendra, E J Corey
Sep 11, 2012·Angewandte Chemie·Baoqiang Wan, Shengming Ma
Nov 30, 2012·Angewandte Chemie·Katrien Brak, Eric N Jacobsen
Dec 22, 2012·Journal of the American Chemical Society·James Y HamiltonErick M Carreira
Feb 6, 2013·Organic & Biomolecular Chemistry·Thierry Ollevier
Jul 4, 2013·Chemical Reviews·Rajasekhar Reddy Naredla, Douglas A Klumpp
Feb 14, 2014·Journal of the American Chemical Society·James Y HamiltonErick M Carreira
Apr 8, 2015·Journal of the American Chemical Society·Simon Breitler, Erick M Carreira
May 15, 2015·Angewandte Chemie·James Y HamiltonErick M Carreira
Apr 6, 2016·Journal of the American Chemical Society·Xi-Jie Dai, Chao-Jun Li
May 5, 2016·Organic & Biomolecular Chemistry·Chad N UngareanDavid Sarlah

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Citations

Sep 30, 2020·Nature Chemistry·Roberta ProperziBenjamin List
Mar 2, 2021·Journal of the American Chemical Society·Mayuko IsomuraErick M Carreira
Jun 28, 2019·Accounts of Chemical Research·Simon L RösslerErick M Carreira
Jan 6, 2021·Journal of the American Chemical Society·Pinglu ZhangBenjamin List
Dec 4, 2021·Chemical Reviews·Jennifer L KennemurBenjamin List

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