Iron-catalyzed alkynylation of tertiary aliphatic amines with 1-iodoalkynes to synthesize propargylamines

A method of alkynylation of tertiary aliphatic amines with 1-iodoalkynes has been developed in the presence of FeCl2 as a catalyst and tert-butyl hydroperoxide as an oxidant. With this method, a variety of propargylamines were obtained in good to excellent yields from inexpensive and readily available reagents. The studies on the possible reaction pathway suggest that this reaction proceeds through a radical process.

[1]  Chao‐Jun Li,et al.  Transition-Metal-Free Alkynylation of 2-Oxindoles through Radical-Radical Coupling. , 2017, The Journal of organic chemistry.

[2]  L. E. Kaim,et al.  Piperazine as Leaving Group in A3 Adducts: Fast Access to Alkynyl Indoles , 2016 .

[3]  F. Alonso,et al.  Cross-Dehydrogenative Coupling of Tertiary Amines and Terminal Alkynes Catalyzed by Copper Nanoparticles on Zeolite , 2015 .

[4]  J. Xie,et al.  A Highly Efficient Gold-Catalyzed Photoredox α-C(sp(3))-H Alkynylation of Tertiary Aliphatic Amines with Sunlight. , 2015, Angewandte Chemie.

[5]  E. Benvenutti,et al.  Covalently immobilized indium(III) composite (In/SiO2) as highly efficient reusable catalyst for A3-coupling of aldehydes, alkynes and amines under solvent-free conditions , 2015 .

[6]  R. Hua,et al.  Au(I)-Catalyzed Annulation of Propargyl Amine with Aldehydes: One-Pot Cascade Synthesis of 2,5-Dimethylpyrazines , 2015, International journal of molecular sciences.

[7]  Chao‐Jun Li,et al.  Efficient merging of copper and photoredox catalysis for the asymmetric cross-dehydrogenative-coupling of alkynes and tetrahydroisoquinolines. , 2015, Organic & biomolecular chemistry.

[8]  D. Dutta,et al.  Efficient one-pot synthesis of propargylamines catalysed by gold nanocrystals stabilized on montmorillonite , 2014 .

[9]  N. Mizuno,et al.  Aerobic cross-dehydrogenative coupling of terminal alkynes and tertiary amines by a combined catalyst of Zn2+ and OMS-2 , 2014 .

[10]  E. Gallo,et al.  [Silver(I)(pyridine-containing ligand)] complexes as unusual catalysts for A(3)-coupling reactions. , 2014, The Journal of organic chemistry.

[11]  Zhiping Li,et al.  Iron-catalyzed/mediated oxidative transformation of C–H bonds , 2014 .

[12]  S. Yin,et al.  Efficient synthesis of propargylamines from terminal alkynes, dichloromethane and tertiary amines over silver catalysts. , 2014, Organic & biomolecular chemistry.

[13]  A. IJzerman,et al.  Removal of human ether-à-go-go related gene (hERG) K+ channel affinity through rigidity: a case of clofilium analogues. , 2013, Journal of medicinal chemistry.

[14]  M. Koketsu,et al.  Synthesis of indole-2-, 3-, or 5-substituted propargylamines via gold(III)-catalyzed three component reaction of aldehyde, alkyne, and amine in aqueous medium , 2013 .

[15]  Zhiping Li,et al.  Amide bond formation through iron-catalyzed oxidative amidation of tertiary amines with anhydrides. , 2013, The Journal of organic chemistry.

[16]  M. Yus,et al.  Alkenes as azido precursors for the one-pot synthesis of 1,2,3-triazoles catalyzed by copper nanoparticles on activated carbon. , 2013, The Journal of organic chemistry.

[17]  M. Yus,et al.  Synthesis of indolizines and heterocyclic chalcones catalyzed by supported copper nanoparticles. , 2013, Chemistry.

[18]  Zhiping Li,et al.  Iron-catalyzed oxidative amidation of tertiary amines with aldehydes. , 2013, Chemistry.

[19]  Hao‐Li Zhang,et al.  A one-step method to produce graphene–Fe3O4 composites and their excellent catalytic activities for three-component coupling of aldehyde, alkyne and amine , 2013 .

[20]  Irene Bolea,et al.  Propargylamine-derived multitarget-directed ligands: fighting Alzheimer’s disease with monoamine oxidase inhibitors , 2013, Journal of Neural Transmission.

[21]  Ying He,et al.  A simple procedure for polymer-supported N-heterocyclic carbene silver complex via click chemistry: an efficient and recyclable catalyst for the one-pot synthesis of propargylamines. , 2012, Dalton transactions.

[22]  K. Ding,et al.  Organic Chemistry - Breakthroughs and Perspectives: Ding/Organic Chemistry - Breakthroughs and Perspectives , 2012 .

[23]  M. Yus,et al.  Three‐Component Coupling of Aldehydes, Amines, and Alkynes Catalyzed by Oxidized Copper Nanoparticles on Titania , 2012 .

[24]  M. Sanford,et al.  Merging visible-light photocatalysis and transition-metal catalysis in the copper-catalyzed trifluoromethylation of boronic acids with CF3I. , 2012, Journal of the American Chemical Society.

[25]  Vsevolod A. Peshkov,et al.  A walk around the A3-coupling. , 2012, Chemical Society reviews.

[26]  David C. Fabry,et al.  Dual catalysis: combination of photocatalytic aerobic oxidation and metal catalyzed alkynylation reactions--C-C bond formation using visible light. , 2012, Chemistry.

[27]  A. Corma,et al.  Heterogenized Gold Complexes: Recoverable Catalysts for Multicomponent Reactions of Aldehydes, Terminal Alkynes, and Amines , 2012 .

[28]  Corey R J Stephenson,et al.  Functionally diverse nucleophilic trapping of iminium intermediates generated utilizing visible light. , 2012, Organic letters.

[29]  Y. Nishihara,et al.  Iron-catalyzed oxidation of tertiary amines: synthesis of β-1,3-dicarbonyl aldehydes by three-component C-C couplings. , 2011, Organic letters.

[30]  Zhanwei Xu,et al.  Propargylamine synthesis by copper-catalyzed oxidative coupling of alkynes and tertiary amine N-oxides. , 2011, The Journal of organic chemistry.

[31]  M. Yus,et al.  Homocoupling of Terminal Alkynes Catalysed by Ultrafine Copper Nanoparticles on Titania , 2011 .

[32]  C. Yeung,et al.  Catalytic dehydrogenative cross-coupling: forming carbon-carbon bonds by oxidizing two carbon-hydrogen bonds. , 2011, Chemical reviews.

[33]  C. Che,et al.  Highly efficient oxidative carbon-carbon coupling with SBA-15-support iron terpyridine catalyst. , 2010, Chemical communications.

[34]  Caroline J. Scheuermann.  Beyond traditional cross couplings: the scope of the cross dehydrogenative coupling reaction. , 2010, Chemistry, an Asian journal.

[35]  Chao‐Jun Li.  The development of catalytic nucleophilic additions of terminal alkynes in water. , 2010, Accounts of chemical research.

[36]  M. Yus,et al.  Impregnated copper on magnetite: an efficient and green catalyst for the multicomponent preparation of propargylamines under solvent free conditions. , 2010, Organic & biomolecular chemistry.

[37]  K. Pitchumani,et al.  Nickel-Catalyzed Solvent-Free Three-Component Coupling of Aldehyde, Alkyne and Amine , 2010 .

[38]  S. Mandel,et al.  Propargylamine containing compounds as modulators of proteolytic cleavage of amyloid-beta protein precursor: involvement of MAPK and PKC activation. , 2010, Journal of Alzheimer's Disease.

[39]  C. Mukhopadhyay,et al.  Nanopowder zinc titanate in aqueous medium: An expeditious catalyst for the synthesis of propargylamines via C–H bond activation , 2009 .

[40]  Haijun Li,et al.  Iron-catalyzed selective oxidation of N-methyl amines: highly efficient synthesis of methylene-bridged bis-1,3-dicarbonyl compounds. , 2009, Organic letters.

[41]  T. C. Johnstone,et al.  Hydrogen-bonding asymmetric metal catalysis with alpha-amino acids: a simple and tunable approach to high enantioinduction. , 2009, Journal of the American Chemical Society.

[42]  Chandra M. R. Volla,et al.  Chemoselective C-H bond activation: ligand and solvent free iron-catalyzed oxidative C-C cross-coupling of tertiary amines with terminal alkynes. Reaction scope and mechanism. , 2009, Organic letters.

[43]  Chao‐Jun Li.  Cross-dehydrogenative coupling (CDC): exploring C-C bond formations beyond functional group transformations. , 2009, Accounts of chemical research.

[44]  Xiaonian Li,et al.  Copper/diethyl azodicarboxylate mediated regioselective alkynylation of unactivated aliphatic tertiary methylamine with terminal alkyne. , 2009, Organic letters.

[45]  Haijun Li,et al.  Iron-catalyzed C-C bond formation by direct functionalization of C-H bonds adjacent to heteroatoms. , 2008, Angewandte Chemie.

[46]  Chao‐Jun Li,et al.  Functionalizing glycine derivatives by direct C-C bond formation. , 2008, Angewandte Chemie.

[47]  Hua Fu,et al.  Copper-catalyzed coupling of tertiary aliphatic amines with terminal alkynes to propargylamines via C-H activation. , 2008, The Journal of organic chemistry.

[48]  Chao‐Jun Li,et al.  Efficient ruthenium and copper cocatalzyed five-component coupling to form dipropargyl amines under mild conditions in water. , 2007, Organic & biomolecular chemistry.

[49]  Chao‐Jun Li,et al.  Cu-catalyzed cross-dehydrogenative coupling: a versatile strategy for C-C bond formations via the oxidative activation of sp(3) C-H bonds. , 2006, Proceedings of the National Academy of Sciences of the United States of America.

[50]  Chao‐Jun Li,et al.  Studies on Cu-catalyzed asymmetric alkynylation of tetrahydroisoquinoline derivatives , 2006 .

[51]  L. Zani,et al.  Dimethylzinc-mediated alkynylation of imines. , 2006, The Journal of organic chemistry.

[52]  W. Lei,et al.  Mercurous Chloride Catalyzed Mannich Condensation of Terminal Alkynes with Secondary Amines and Aldehydes , 2005 .

[53]  Yoshihiko Yamamoto,et al.  Domino coupling relay approach to polycyclic pyrrole-2-carboxylates. , 2005, Journal of the American Chemical Society.

[54]  K. Bielawski,et al.  Inhibition of collagen and DNA biosynthesis by a novel amidine analogue of chlorambucil is accompanied by deregulation of β(1)-integrin and IGF-I receptor signaling in MDA-MB 231 cells. , 2005, Environmental toxicology and pharmacology.

[55]  Qun Xu,et al.  Asymmetric synthesis of trans-3,4-dialkyl-gamma-butyrolactones via an acyl-Claisen and iodolactonization route. , 2005, Organic letters.

[56]  Chao‐Jun Li,et al.  Catalytic enantioselective alkynylation of prochiral sp3 C-H bonds adjacent to a nitrogen atom. , 2004, Organic letters.

[57]  P. Knochel,et al.  Practical highly enantioselective synthesis of terminal propargylamines. An expeditious synthesis of (S)-(+)-coniine. , 2004, Chemical communications.

[58]  Chao‐Jun Li,et al.  CuBr-catalyzed efficient alkynylation of sp3 C-H bonds adjacent to a nitrogen atom. , 2004, Journal of the American Chemical Society.

[59]  T. Kubo,et al.  Iridium-catalyzed coupling of simple primary or secondary amines, aldehydes and trimethylsilylacetylene: preparation of propargylic amines. , 2004, Chemical communications.

[60]  B. Jiang,et al.  Highly enantioselective construction of fused pyrrolidine systems that contain a quaternary stereocenter: concise formal synthesis of (+)-conessine. , 2004, Angewandte Chemie.

[61]  P. Mátyus,et al.  Semicarbazide-sensitive amine oxidase: current status and perspectives. , 2004, Current medicinal chemistry.

[62]  P. Knochel,et al.  Enantioselective synthesis of propargylamines by copper-catalyzed addition of alkynes to enamines. , 2002, Angewandte Chemie.

[63]  Chao‐Jun Li,et al.  Enantioselective direct-addition of terminal alkynes to imines catalyzed by copper(I)pybox complex in water and in toluene. , 2002, Journal of the American Chemical Society.

[64]  U. Holzgrabe,et al.  Muscarinic receptor agonists and antagonists , 1999 .

[65]  E. Grabowski,et al.  Lithium Alkoxides of Cinchona Alkaloids as Chiral Controllers for Enantioselective Acetylide Addition to Cyclic N-Acyl Ketimines , 1995 .

[66]  M. Miura,et al.  Iron-catalyzed oxidation of 4-substituted N,N-dimethylanilines with molecular oxygen in the presence of benzoyl cyanide , 1993 .

[67]  J. V. Greenhill,et al.  Amidines and guanidines in medicinal chemistry. , 1993, Progress in medicinal chemistry.

[68]  W. Moos,et al.  Cholinergic agents: aldehyde, ketone, and oxime analogues of the muscarinic agonist UH5 , 1992 .

[69]  U. Hacksell,et al.  Phenyl-substituted analogues of oxotremorine as muscarinic antagonists. , 1992, Journal of medicinal chemistry.

[70]  Toshikazu Oki,et al.  Crystal and molecular structure of dynemicin A: a novel 1,5-diyn-3-ene antitumor antibiotic , 1990 .

[71]  Y. Takata,et al.  Anodic cyanation of tertiary aliphatic and heterocyclic amines , 2002 .

[72]  Jean-Baptiste Santamaria,et al.  Oxydation photochimique D'amines tertiaires et D'alcaloïdes—VIII: Oxydation photochimique d'alcaloïdes indolinoindolizidiniques, vincadifformine, tabersonine, n(a)-acétyl dihydro-2,16 vincadifformine et n(a)-acétyl dihydro-2,16 tabersonine , 1977 .