推进对映选择性钯催化烯烃双官能化反应的机理理解。
Advancing the mechanistic understanding of an enantioselective palladium-catalyzed alkene difunctionalization reaction.
机构信息
Department of Chemistry, University of Utah, 315 South 1400 East, Salt Lake City, Utah 84112, USA.
出版信息
J Am Chem Soc. 2010 Dec 15;132(49):17471-82. doi: 10.1021/ja108106h. Epub 2010 Nov 17.
Abstract
The mechanism of an enantioselective palladium-catalyzed alkene difunctionalization reaction has been investigated. Kinetic analysis provides evidence of turnover-limiting attack of a proposed quinone methide intermediate with MeOH and suggests that copper is involved in productive product formation, not just catalyst turnover. Through examination of substrate electronic effects, a Jaffé relationship was observed correlating rate to electronic perturbation at two positions of the substrate. Ligand effects were evaluated to provide evidence of rapid ligand exchange between palladium and copper as well as a correlation between ligand electronic nature and enantioselectivity.
摘要
本研究考察了手性钯催化烯烃双官能化反应的机理。动力学分析为提出的醌甲醚中间体与甲醇的限速进攻提供了证据，并表明铜不仅参与了催化剂的循环，还参与了产物的生成。通过考察底物的电子效应，观察到了与底物两个位置的电子扰动相关的 Jaffé 关系，该关系与反应速率相关联。配体效应的评估为钯和铜之间快速配体交换以及配体电子性质与对映选择性之间的相关性提供了证据。
相似文献
1
Advancing the mechanistic understanding of an enantioselective palladium-catalyzed alkene difunctionalization reaction.
J Am Chem Soc. 2010 Dec 15;132(49):17471-82. doi: 10.1021/ja108106h. Epub 2010 Nov 17.
2
Palladium-catalyzed enantioselective addition of two distinct nucleophiles across alkenes capable of quinone methide formation.
J Am Chem Soc. 2009 Dec 2;131(47):17074-5. doi: 10.1021/ja909030c.
3
Synthesis and preliminary biological studies of 3-substituted indoles accessed by a palladium-catalyzed enantioselective alkene difunctionalization reaction.
J Am Chem Soc. 2010 Jun 16;132(23):7870-1. doi: 10.1021/ja103472a.
4
Mechanistic Model for Enantioselective Intramolecular Alkene Cyanoamidation via Palladium-Catalyzed C-CN Bond Activation.
J Org Chem. 2017 Apr 7;82(7):3721-3726. doi: 10.1021/acs.joc.7b00196. Epub 2017 Mar 15.
5
Mechanistic studies of Wacker-type amidocyclization of alkenes catalyzed by (IMes)Pd(TFA)2(H2O): kinetic and stereochemical implications of proton transfer.
J Org Chem. 2013 Mar 1;78(5):2083-90. doi: 10.1021/jo302266t. Epub 2012 Nov 30.
6
Palladium(II)-catalyzed aerobic hydroalkoxylation of styrenes containing a phenol.
J Am Chem Soc. 2006 Mar 8;128(9):2794-5. doi: 10.1021/ja0585533.
7
Mechanistic analysis and optimization of the copper-catalyzed enantioselective intramolecular alkene aminooxygenation.
J Org Chem. 2013 Jan 18;78(2):506-15. doi: 10.1021/jo3023632. Epub 2012 Dec 28.
8
Mechanistic studies of a palladium-catalyzed intramolecular hydroamination of unactivated alkenes: protonolysis of a stable palladium alkyl complex is the turnover-limiting step.
J Am Chem Soc. 2008 Mar 5;130(9):2786-92. doi: 10.1021/ja0734997. Epub 2008 Feb 7.
9
Mechanism of the cobalt oxazoline palladacycle (COP)-catalyzed asymmetric synthesis of allylic esters.
J Am Chem Soc. 2010 Nov 3;132(43):15192-203. doi: 10.1021/ja106688j.
10
A Cu/Pd Cooperative Catalysis for Enantioselective Allylboration of Alkenes.
J Am Chem Soc. 2015 Nov 4;137(43):13760-3. doi: 10.1021/jacs.5b09146. Epub 2015 Oct 22.
引用本文的文献
1
Tailored chiral phosphoramidites support highly enantioselective Pd catalysts for asymmetric aminoalkylative amination.
Nat Commun. 2024 Dec 2;15(1):10477. doi: 10.1038/s41467-024-54328-5.
2
Mechanistic study on the side arm effect in a palladium/Xu-Phos-catalyzed enantioselective alkoxyalkenylation of γ-hydroxyalkenes.
Nat Commun. 2023 Nov 22;14(1):7611. doi: 10.1038/s41467-023-43202-5.
3
Copper-Catalyzed Enantioselective Aerobic Alkene Aminooxygenation and Dioxygenation: Access to 2-Formyl Saturated Heterocycles and Unnatural Proline Derivatives.
J Am Chem Soc. 2023 Jun 28;145(25):13715-13729. doi: 10.1021/jacs.3c01985. Epub 2023 Jun 16.
4
Construction of azaheterocycles via Pd-catalyzed migratory cycloannulation reaction of unactivated alkenes.
Nat Commun. 2022 Aug 27;13(1):5059. doi: 10.1038/s41467-022-32726-x.
5
High-throughput screening of α-chiral-primary amines to determine yield and enantiomeric excess.
Tetrahedron. 2021 Aug 13;94. doi: 10.1016/j.tet.2021.132315. Epub 2021 Jul 5.
6
Enantio- and Regioselective Palladium(II)-Catalyzed Dioxygenation of (Aza-)Alkenols.
Angew Chem Int Ed Engl. 2021 Sep 27;60(40):21723-21727. doi: 10.1002/anie.202109312. Epub 2021 Sep 6.
7
Alkene Difunctionalization Using Hypervalent Iodine Reagents: Progress and Developments in the Past Ten Years.
Molecules. 2019 Jul 19;24(14):2634. doi: 10.3390/molecules24142634.
8
Preparation of ()--ButylPyOx and Palladium-catalyzed Asymmetric Conjugate Addition of Arylboronic Acids.
Organic Synth. 2016;92. doi: 10.1002/0471264229.os092.19. Epub 2016 Mar 4.
9
Metal-free Chlorothiolation of Alkenes using HCl and Sulfoxides.
European J Org Chem. 2018 Sep 16;2018(34):4705-4708. doi: 10.1002/ejoc.201800973. Epub 2018 Jul 19.
10
Benzoate Cyclometalation Enables Oxidative Addition of Haloarenes at a Ru(II) Center.
J Am Chem Soc. 2018 Sep 19;140(37):11836-11847. doi: 10.1021/jacs.8b08150. Epub 2018 Sep 5.
本文引用的文献
1
Metal-catalysed 1,2-diamination reactions.
Nat Chem. 2009 Jul;1(4):269-75. doi: 10.1038/nchem.256. Epub 2009 Jun 22.
2
Experimental and computational study of a direct O2-coupled Wacker oxidation: water dependence in the absence of Cu salts.
J Am Chem Soc. 2010 Sep 1;132(34):11872-4. doi: 10.1021/ja1057218.
3
Synthesis and preliminary biological studies of 3-substituted indoles accessed by a palladium-catalyzed enantioselective alkene difunctionalization reaction.
J Am Chem Soc. 2010 Jun 16;132(23):7870-1. doi: 10.1021/ja103472a.
4
Pd(II)-catalyzed oxidative 1,1-diarylation of terminal olefins.
Org Lett. 2010 Jun 18;12(12):2848-51. doi: 10.1021/ol1009575.
5
Efficient diacetoxylation of alkenes via Pd(II)/Pd(IV) process with peracetic acid and acetic anhydride.
Org Lett. 2010 Jun 4;12(11):2450-2. doi: 10.1021/ol1001686.
6
Synthetic and mechanistic studies on Pd(0)-catalyzed diamination of conjugated dienes.
J Am Chem Soc. 2010 Mar 17;132(10):3523-32. doi: 10.1021/ja909459h.
7
Palladium-catalyzed intermolecular aminofluorination of styrenes.
J Am Chem Soc. 2010 Mar 10;132(9):2856-7. doi: 10.1021/ja909716k.
8
Pd(II)/(t)Bu-quinolineoxazoline: an air-stable and modular chiral catalyst system for enantioselective oxidative cascade cyclization.
Org Lett. 2009 Dec 17;11(24):5626-8. doi: 10.1021/ol902348t.
9
Palladium-catalyzed enantioselective addition of two distinct nucleophiles across alkenes capable of quinone methide formation.
J Am Chem Soc. 2009 Dec 2;131(47):17074-5. doi: 10.1021/ja909030c.
10
Palladium-catalyzed carboamination of alkenes promoted by N-fluorobenzenesulfonimide via C-H activation of arenes.
J Am Chem Soc. 2009 Jul 15;131(27):9488-9. doi: 10.1021/ja9031659.
Zotero 插件