Palladium-catalyzed decarboxylative asymmetric allylic alkylation of enol carbonates.

Journal of the American Chemical Society
Barry M TrostThomas Schmidt

Abstract

Palladium-catalyzed decarboxylative asymmetric allylic alkylation (DAAA) of allyl enol carbonates as a highly chemo-, regio-, and enantioselective process for the synthesis of ketones bearing either a quaternary or a tertiary alpha-stereogenic center has been investigated in detail. Chiral ligand L4 was found to be optimal in the DAAA of a broad scope of cyclic and acyclic ketones including simple aliphatic ketones with more than one enolizable proton. The allyl moiety of the carbonates has been extended to a variety of cyclic or acyclic disubstituted allyl groups. Our mechanistic studies reveal that, similar to the direct allylation of lithium enolates, the DAAA reaction proceeds through an "outer sphere" S(N)2 type of attack on the pi-allylpalladium complex by the enolate. An important difference between the DAAA reaction and the direct allylation of lithium enolates is that in the DAAA reaction, the nucleophile and the electrophile were generated simultaneously. Since the pi-allylpalladium cation must serve as the counterion for the enolate, the enolate probably exists as a tight-ion-pair. This largely prevents the common side reactions of enolates associated with the equilibrium between different enolates. The much milder r...Continue Reading

References

Feb 5, 2002·Chemical & Pharmaceutical Bulletin·Barry M Trost
Feb 1, 1996·Chemical Reviews·Barry M. Trost, David L. Van Vranken
Sep 26, 2002·Angewandte Chemie·Barry M TrostJesper Kristensen
Aug 14, 2003·Chemical Reviews·Barry M Trost, Matthew L Crawley
Jan 15, 2004·Journal of the American Chemical Society·Nicola Vignola, Benjamin List
Oct 22, 2004·Organic Letters·Erin C Burger, Jon A Tunge
Oct 30, 2004·Chemistry : a European Journal·Barry M Trost, Gretchen M Schroeder
Nov 19, 2004·Journal of the American Chemical Society·Douglas C Behenna, Brian M Stoltz
Mar 3, 2005·Journal of the American Chemical Society·Barry M Trost, Jiayi Xu
Mar 5, 2005·The Journal of Antibiotics·Won Keun OhJong Seog Ahn
Sep 21, 2005·Angewandte Chemie·Xiao-Xia YanXue-Long Hou
Oct 10, 2006·Angewandte Chemie·Manfred Braun, Thorsten Meier
Mar 31, 2007·Science·Teresa D BeesonDavid W C Macmillan
May 15, 2007·Journal of the American Chemical Society·Hye-Young JangDavid W C MacMillan
May 26, 2007·Angewandte Chemie·Takashi Ooi, Keiji Maruoka
Jun 27, 2007·Organic Letters·Barry M Trost, Dylan T Stiles
Sep 11, 2007·Journal of the American Chemical Society·John A KeithWilliam A Goddard
Oct 16, 2007·Chemistry, an Asian Journal·Justin T Mohr, Brian M Stoltz
Dec 13, 2007·Chemical Reviews·Takuya Hashimoto, Keiji Maruoka
Dec 22, 2007·Journal of the American Chemical Society·Hahn Kim, David W C MacMillan
Jan 25, 2008·Angewandte Chemie·Kai ZhangYun-Dong Wu

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Citations

Dec 11, 2013·Organic Letters·Nicolas GermainAlexandre Alexakis
Jan 18, 2011·Chemical Reviews·Jimmie D WeaverJon A Tunge
Jun 23, 2010·Journal of the American Chemical Society·Robert R P TorregrosaJon A Tunge
Jun 17, 2010·Journal of the American Chemical Society·Barry M TrostAndreas K Buckl
Aug 19, 2010·Journal of the American Chemical Society·Jimmie D WeaverJon A Tunge
Aug 5, 2010·Journal of the American Chemical Society·Ping ZhangJames P Morken
Sep 30, 2010·Journal of the American Chemical Society·Rui ShangLei Liu
Oct 30, 2010·Journal of the American Chemical Society·Ilya D GridnevTakao Ikariya
Oct 22, 2010·Journal of the American Chemical Society·Barry M Trost, Lara C Czabaniuk
Aug 13, 2011·Journal of the American Chemical Society·Alexander J Grenning, Jon A Tunge
Nov 4, 2011·Journal of the American Chemical Society·Jiadi ZhangPatrick J Walsh
Jun 19, 2012·Journal of the American Chemical Society·Philipp C RoosenMilton R Smith
Mar 29, 2011·The Journal of Organic Chemistry·Sarah E HavlikJeffrey B Johnson
Aug 16, 2012·The Journal of Organic Chemistry·Camille LescotPhilippe Dauban
Jun 6, 2013·The Journal of Organic Chemistry·Alexander J GrenningJon A Tunge
Jun 11, 2010·Organic Letters·Kalicharan ChattopadhyayJon A Tunge
Jul 23, 2011·Organic Letters·Vilius FranckevičiusRichard J K Taylor
Mar 4, 2014·Journal of the American Chemical Society·Fiene HoreischiBernd Plietker
Mar 15, 2014·Chemical Communications : Chem Comm·Shaohua XiangXue-Wei Liu
Sep 1, 2015·The Journal of Organic Chemistry·Megumi OkadaIlhyong Ryu
Dec 21, 2016·Organic Letters·Marllon Nascimento de OliveiraJanine Cossy
Feb 28, 2017·Journal of the American Chemical Society·Han ZhouSanzhong Luo
May 20, 2017·The Journal of Organic Chemistry·Stuart C D KenningtonMercè Font-Bardia
May 20, 2017·Chemical Communications : Chem Comm·Tonghao Zhu, Shengming Ma
Mar 17, 2017·Chemical Communications : Chem Comm·Hui YangWen-Hua Zheng
Apr 5, 2016·Chemical Communications : Chem Comm·Changkun LiBernhard Breit
Jan 8, 2015·Chemical Communications : Chem Comm·Fiene HoreischiBernd Plietker
Nov 10, 2017·Organic & Biomolecular Chemistry·Jingke FuWanbin Zhang

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