Cooperative Catalysis of Copper, Silver, and Brønsted Acid for Three‐Component Carboamination of Arylalkenes with Allylic Alcohols and Nitriles

The cooperative catalysis of copper, silver, and Brønsted acid is presented as a new strategy for the intermolecular carboamination of arylalkenes. The catalytic regio‐ and chemoselective intermolecular carboamination of arylalkenes with allylic alcohols and nitriles provided a straightforward and efficient approach for preparing N‐acyl 4,5‐unsaturated amines. These amines can be used as synthetic organic synthons for the preparation of nitrogen‐containing five‐ and six‐membered heterocycles. During the functionalization reaction, synthetically useful functional groups, such as Cl, Br, and chloromethyl, remained intact.

[1]  A. Studer,et al.  Intermolecular radical carboamination of alkenes. , 2020, Chemical Society reviews.

[2]  S. Zhang,et al.  Direct Carbohydroxylation of Arylalkenes with Allylic Alcohols: Cooperative Catalysis of Copper, Silver, and a Brønsted Acid. , 2019, Angewandte Chemie.

[3]  C. Feng,et al.  Intermolecular Carboamination of Unactivated Alkenes. , 2018, Journal of the American Chemical Society.

[4]  L. Gong,et al.  α-Quaternary Chiral Aldehydes from Styrenes, Allylic Alcohols, and Syngas via Multi-catalyst Relay Catalysis , 2018 .

[5]  P. Kalck,et al.  Tandem Hydroaminomethylation Reaction to Synthesize Amines from Alkenes. , 2018, Chemical reviews.

[6]  Kami L. Hull,et al.  Cu-Catalyzed Three-Component Carboamination of Alkenes. , 2018, Journal of the American Chemical Society.

[7]  M. Akita,et al.  New Horizons of Photocatalytic Fluoromethylative Difunctionalization of Alkenes , 2017 .

[8]  Florian Medina,et al.  Recent metal-catalysed asymmetric hydroaminations of alkenes , 2017 .

[9]  Xiaotai Wang,et al.  Enantioselective Tandem Cyclization of Alkyne-Tethered Indoles Using Cooperative Silver(I)/Chiral Phosphoric Acid Catalysis. , 2017, Angewandte Chemie.

[10]  Xinhao Zhang,et al.  Iron-Catalyzed Carboamination of Olefins: Synthesis of Amines and Disubstituted β-Amino Acids. , 2017, Journal of the American Chemical Society.

[11]  Yajun Li,et al.  γ-Amino Butyric Acid (GABA) Synthesis Enabled by Copper-Catalyzed Carboamination of Alkenes. , 2017, Organic letters.

[12]  Fei Wang,et al.  Asymmetric Copper-Catalyzed Intermolecular Aminoarylation of Styrenes: Efficient Access to Optical 2,2-Diarylethylamines. , 2017, Journal of the American Chemical Society.

[13]  S. Luo,et al.  Oxidative 1,2-carboamination of alkenes with alkyl nitriles and amines toward γ-amino alkyl nitriles , 2017, Nature Communications.

[14]  G. Zhong,et al.  Enantioselective Dearomatization of Naphthol Derivatives with Allylic Alcohols by Cooperative Iridium and Brønsted Acid Catalysis. , 2017, Angewandte Chemie.

[15]  Jérôme Hannedouche,et al.  First-Row Late Transition Metals for Catalytic (Formal) Hydroamination of Unactivated Alkenes , 2016, Synthesis.

[16]  F. Glorius,et al.  Unnatural Amino Acid Synthesis Enabled by the Regioselective Cobalt(III)-Catalyzed Intermolecular Carboamination of Alkenes. , 2016, Angewandte Chemie.

[17]  Pu-Sheng Wang,et al.  Highly Enantioselective Allylic C-H Alkylation of Terminal Olefins with Pyrazol-5-ones Enabled by Cooperative Catalysis of Palladium Complex and Brønsted Acid. , 2016, Journal of the American Chemical Society.

[18]  Guosheng Liu,et al.  Palladium(II)-Catalyzed Oxidative Difunctionalization of Alkenes: Bond Forming at a High-Valent Palladium Center. , 2016, Accounts of chemical research.

[19]  H. Ohmiya,et al.  Copper-Catalyzed Enantioselective Allyl-Allyl Coupling between Allylic Boronates and Phosphates with a Phenol/N-Heterocyclic Carbene Chiral Ligand. , 2016, Angewandte Chemie.

[20]  J. Wolfe,et al.  Asymmetric Palladium-Catalyzed Alkene Carboamination Reactions for the Synthesis of Cyclic Sulfamides. , 2016, Chemistry.

[21]  Xiaofeng Tong,et al.  Rhodium(III) Catalyzed Carboamination of Alkenes Triggered by C-H Activation of N-Phenoxyacetamides under Redox-Neutral Conditions. , 2016, Organic letters.

[22]  Michael T. Pirnot,et al.  Kupferhydrid‐katalysierte Hydroaminierung von Alkenen und Alkinen , 2016 .

[23]  S. Buchwald,et al.  Copper Hydride Catalyzed Hydroamination of Alkenes and Alkynes. , 2015, Angewandte Chemie.

[24]  M. Heinrich,et al.  Base-Induced Radical Carboamination of Nonactivated Alkenes with Aryldiazonium Salts. , 2015, Organic letters.

[25]  T. Rovis,et al.  Rh-Catalyzed Intermolecular Syn-Carboamination of Alkenes via a Transient Directing Group , 2015, Nature.

[26]  M. Mellah,et al.  Recent advances in metal free- and late transition metal-catalysed hydroamination of unactivated alkenes , 2015 .

[27]  Pinhong Chen,et al.  Palladium-catalyzed intermolecular aminocarbonylation of alkenes: efficient access of β-amino acid derivatives. , 2015, Journal of the American Chemical Society.

[28]  J. Wolfe,et al.  Enantioselective Synthesis of Tetrahydroquinolines, Tetrahydroquinoxalines, and Tetrahydroisoquinolines via Pd-Catalyzed Alkene Carboamination Reactions. , 2014, Chemical science.

[29]  Zhi‐Min Chen,et al.  Copper-catalyzed intermolecular azidocyanation of aryl alkenes. , 2014, Chemical communications.

[30]  G. Masson,et al.  Photoredox-induced three-component azido- and aminotrifluoromethylation of alkenes. , 2014, Organic letters.

[31]  J. Wolfe,et al.  Influence of catalyst structure and reaction conditions on anti- versus syn-aminopalladation pathways in Pd-catalyzed alkene carboamination reactions of N-allylsulfamides. , 2014, Chemistry.

[32]  X. Cong,et al.  Iron-catalyzed, chelation-induced remote C-H allylation of quinolines via 8-amido assistance. , 2014, Organic letters.

[33]  S. Denmark,et al.  Lewis Base Catalyzed, Enantioselective, Intramolecular Sulfenoamination of Olefins , 2014, Journal of the American Chemical Society.

[34]  Thorsten H. Wöste,et al.  Vicinal difunctionalization of alkenes with iodine(III) reagents and catalysts. , 2014, Chemistry, an Asian journal.

[35]  Fei Wang,et al.  Copper-catalyzed intermolecular trifluoromethylazidation of alkenes: convenient access to CF3 -containing alkyl azides. , 2014, Angewandte Chemie.

[36]  Durga Prasad Hari,et al.  The photoredox-catalyzed Meerwein addition reaction: intermolecular amino-arylation of alkenes. , 2014, Angewandte Chemie.

[37]  Justin M. Pierson,et al.  Palladium(II)-catalyzed intramolecular hydroamination of 1,3-dienes to give homoallylic amines. , 2013, Angewandte Chemie.

[38]  G. Fumagalli,et al.  Oxyarylation and aminoarylation of styrenes using photoredox catalysis. , 2013, Organic letters.

[39]  M. Akita,et al.  Intermolecular aminotrifluoromethylation of alkenes by visible-light-driven photoredox catalysis. , 2013, Organic letters.

[40]  Q. Zhang,et al.  Copper-catalyzed intermolecular aminocyanation and diamination of alkenes. , 2013, Angewandte Chemie.

[41]  L. Krimen,et al.  The Ritter Reaction , 2011 .

[42]  B. Feringa,et al.  Iridium-catalyzed asymmetric intramolecular allylic amidation: enantioselective synthesis of chiral tetrahydroisoquinolines and saturated nitrogen heterocycles. , 2011, Angewandte Chemie.

[43]  M. Stradiotto,et al.  Rhodium‐ and Iridium‐Catalyzed Hydroamination of Alkenes , 2010 .

[44]  S. Chemler,et al.  Diastereo- and enantioselective copper-catalyzed intramolecular carboamination of alkenes for the synthesis of hexahydro-1H-benz[f]indoles. , 2010, Organic letters.

[45]  Paul A. Sibbald,et al.  Palladium-catalyzed carboamination of alkenes promoted by N-fluorobenzenesulfonimide via C-H activation of arenes. , 2009, Journal of the American Chemical Society.

[46]  J. Royer.  Asymmetric synthesis of Nitrogen heterocycles , 2009 .

[47]  M. Heinrich,et al.  Radical Carbodiazenylation – A Convenient and Effective Method to Achieve Carboamination of Non-Activated Olefins , 2008 .

[48]  J. Collin,et al.  Asymmetric hydroamination of non-activated carbon-carbon multiple bonds. , 2007, Dalton transactions.

[49]  W. Zeng,et al.  Copper(II)-catalyzed enantioselective intramolecular carboamination of alkenes. , 2007, Journal of the American Chemical Society.

[50]  C. Amatore,et al.  Rate and mechanism of the reaction of alkenes with aryl palladium complexes ligated by a bidentate P,P ligand in Heck reactions. , 2007, Chemistry.

[51]  J. Wolfe.  Palladium-Catalyzed Carboetherification and Carboamination Reactions of γ-Hydroxy- and γ-Aminoalkenes for the Synthesis of Tetrahydrofurans and Pyrrolidines. , 2007, European journal of organic chemistry.

[52]  J. Wolfe.  Stereoselective Synthesis of Saturated Heterocycles via Pd-Catalyzed Alkene Carboetherification and Carboamination Reactions. , 2008, Synlett : accounts and rapid communications in synthetic organic chemistry.

[53]  Kenneth M. Johnson,et al.  Further structure-activity relationship studies of piperidine-based monoamine transporter inhibitors: effects of piperidine ring stereochemistry on potency. Identification of norepinephrine transporter selective ligands and broad-spectrum transporter inhibitors. , 2005, Journal of medicinal chemistry.

[54]  K. C. Nicolaou,et al.  Strategic applications of named reactions in organic synthesis: background and detailed mechanisms , 2005 .

[55]  J. Liddell.  Pyrrolizidine alkaloids , 2002, Natural product reports.

[56]  J. Bäckvall,et al.  Experimental evidence supporting a CuIII intermediate in cross-coupling reactions of allylic esters with diallylcuprate species. , 2001, Chemistry.

[57]  Nakagawa,et al.  Acid-catalyzed cyclization of vinylsilanes bearing an amino group. Stereoselective synthesis of pyrrolidines , 2000, Organic letters.

[58]  D. O'Hagan.  Pyrrole, pyrrolidine, pyridine, piperidine and tropane alkaloids (1998 to 1999) , 2000 .

[59]  J. Ritter,et al.  A new reaction of nitriles; amides from alkenes and mononitriles. , 1948, Journal of the American Chemical Society.

[60]  J. Ritter,et al.  A new reaction of nitriles; synthesis of t-carbinamines. , 1948, Journal of the American Chemical Society.