通过钌催化吡咯与末端炔烃的偶联反应，涉及 C-H 键活化，区域选择性地形成 α-乙烯基吡咯。
Regioselective formation of alpha-vinylpyrroles from the ruthenium-catalyzed coupling reaction of pyrroles and terminal alkynes involving C-H bond activation.
机构信息
Department of Chemistry, Marquette University, Milwaukee, Wisconsin 53201-1881, USA.
出版信息
J Org Chem. 2010 May 7;75(9):3144-6. doi: 10.1021/jo100269y.
Abstract
The cationic ruthenium catalyst Ru(3)(CO)(12)/NH(4)PF(6) was found to be highly effective for the intermolecular coupling reaction of pyrroles and terminal alkynes to give gem-selective alpha-vinylpyrroles. The carbon isotope effect on the alpha-pyrrole carbon and the Hammett correlation from a series of para-substituted N-arylpyrroles (rho = -0.90) indicate a rate-limiting C-C bond formation step of the coupling reaction.
摘要
研究发现，阳离子钌催化剂 Ru(3)(CO)(12)/NH(4)PF(6) 对于吡咯和末端炔烃的分子间偶联反应非常有效，可生成高立体选择性的α-乙烯基吡咯。α-吡咯碳的碳同位素效应和一系列对取代 N-芳基吡咯的哈米特相关性（rho = -0.90）表明，该偶联反应的速率限制步骤是 C-C 键形成。
相似文献
1
Regioselective formation of alpha-vinylpyrroles from the ruthenium-catalyzed coupling reaction of pyrroles and terminal alkynes involving C-H bond activation.
J Org Chem. 2010 May 7;75(9):3144-6. doi: 10.1021/jo100269y.
2
Scope and mechanistic study of the ruthenium-catalyzed ortho-C-H bond activation and cyclization reactions of arylamines with terminal alkynes.
J Am Chem Soc. 2005 Dec 7;127(48):17000-6. doi: 10.1021/ja055608s.
3
Ruthenium-catalyzed pyrrole synthesis via oxidative annulation of enamides and alkynes.
Org Lett. 2013 Jan 4;15(1):136-9. doi: 10.1021/ol303159h. Epub 2012 Dec 12.
4
Ru(II)-catalyzed C-H bond activation for the synthesis of substituted isoquinolinium salts from benzaldehydes, amines, and alkynes.
Org Lett. 2012 Jul 6;14(13):3478-81. doi: 10.1021/ol301445r. Epub 2012 Jun 11.
5
Ruthenium-catalyzed regioselective C2 alkenylation of indoles and pyrroles via C-H bond functionalization.
J Org Chem. 2013 Sep 20;78(18):9345-53. doi: 10.1021/jo401579m. Epub 2013 Sep 11.
6
Catalytic synthesis of tricyclic quinoline derivatives from the regioselective hydroamination and C-H bond activation reaction of benzocyclic amines and alkynes.
J Am Chem Soc. 2005 Apr 27;127(16):5782-3. doi: 10.1021/ja042318n.
7
Formation of bicyclic pyrroles from the catalytic coupling reaction of 2,5-disubstituted pyrroles with terminal alkynes, involving the activation of multiple C-H bonds.
Chem Commun (Camb). 2008 May 28(20):2349-51. doi: 10.1039/b804263b. Epub 2008 Apr 21.
8
Oxidative alkenylation of aromatic esters by ruthenium-catalyzed twofold C-H bond cleavages.
Org Lett. 2012 Aug 17;14(16):4110-3. doi: 10.1021/ol301759v. Epub 2012 Jul 31.
9
Alkynes as allylmetal equivalents in redox-triggered C-C couplings to primary alcohols: (Z)-homoallylic alcohols via ruthenium-catalyzed propargyl C-H oxidative addition.
J Am Chem Soc. 2014 Aug 27;136(34):11902-5. doi: 10.1021/ja505962w. Epub 2014 Jul 30.
10
Versatile pyrrole synthesis through ruthenium(II)-catalyzed alkene C-H bond functionalization on enamines.
Org Lett. 2013 Jan 4;15(1):176-9. doi: 10.1021/ol303224e. Epub 2012 Dec 20.
本文引用的文献
1
Highly regioselective palladium-catalyzed oxidative coupling of indolizines and vinylarenes via C-H bond cleavage.
Org Lett. 2009 Dec 17;11(24):5606-9. doi: 10.1021/ol902315w.
2
Palladium-catalyzed alkenylation of quinoline-N-oxides via C-H activation under external-oxidant-free conditions.
J Am Chem Soc. 2009 Oct 7;131(39):13888-9. doi: 10.1021/ja902762a.
3
Palladium(II)-catalyzed regioselective direct C2 alkenylation of indoles and pyrroles assisted by the N-(2-pyridyl)sulfonyl protecting group.
Angew Chem Int Ed Engl. 2009;48(35):6511-5. doi: 10.1002/anie.200902802.
4
Rhodium-catalyzed C-C bond formation via heteroatom-directed C-H bond activation.
Chem Rev. 2010 Feb 10;110(2):624-55. doi: 10.1021/cr900005n.
5
Fast and highly regioselective allylation of indole and pyrrole compounds by allyl alcohols using Ru-sulfonate catalysts.
J Am Chem Soc. 2008 Sep 3;130(35):11604-5. doi: 10.1021/ja804379k. Epub 2008 Aug 6.
6
Formation of bicyclic pyrroles from the catalytic coupling reaction of 2,5-disubstituted pyrroles with terminal alkynes, involving the activation of multiple C-H bonds.
Chem Commun (Camb). 2008 May 28(20):2349-51. doi: 10.1039/b804263b. Epub 2008 Apr 21.
7
Regioselective C-H functionalization directed by a removable carboxyl group: palladium-catalyzed vinylation at the unusual position of indole and related heteroaromatic rings.
Org Lett. 2008 Mar 20;10(6):1159-62. doi: 10.1021/ol8000602. Epub 2008 Feb 16.
8
Elements of regiocontrol in palladium-catalyzed oxidative arene cross-coupling.
J Am Chem Soc. 2007 Oct 10;129(40):12072-3. doi: 10.1021/ja0745862. Epub 2007 Sep 19.
9
Hydroheteroarylation of alkynes under mild nickel catalysis.
J Am Chem Soc. 2006 Jun 28;128(25):8146-7. doi: 10.1021/ja0623459.
10
Catalytic C-H arylation of SEM-protected azoles with palladium complexes of NHCs and phosphines.
Org Lett. 2006 May 11;8(10):1979-82. doi: 10.1021/ol053021c.
Zotero 插件