Carbonylative Formal Cycloaddition between Alkylarenes and Aldimines Enabled by Palladium-Catalyzed Double C-H Bond Activation.

Double C-H bond activation can enable an expeditious reaction pathway to cyclic compounds, offering an efficient tool to synthesize valuable molecules. However, cyclization reaction enabled by double C-H bond activation at one carbon atom is nearly unknown. Herein, we report a carbonylative formal cycloaddition of alkylarenes with imines via double benzylic C-H bond activation at one carbon atom, allowing a straightforward synthesis of β-lactams from readily accessible alkylarenes and imines, which paves the way for developing an annulation reaction through double C-H bond activation at one carbon atom.

[1]  Wei Zhang,et al.  Nickel-Catalyzed Oxidative Carbonylation of Alkylarenes to Arylacetic Acids. , 2022, Organic letters.

[2]  S. Stahl,et al.  Electrochemical PINOylation of Methylarenes: Improving the Scope and Utility of Benzylic Oxidation through Mediated Electrolysis. , 2022, Journal of the American Chemical Society.

[3]  H. Pang,et al.  Experimental and Theoretical Study of NiII‐ and PdII‐Promoted Double Geminal C(sp3)−H Bond Activation Providing Facile Access to NHC Pincer Complexes: Isolated Intermediates and Mechanism , 2022, Chemistry.

[4]  Hanmin Huang,et al.  Carbonylative cycloaddition of alkenes and imines to β-lactams enabled by resolving the acid-base paradox , 2022, Chem Catalysis.

[5]  Magnus J. Johansson,et al.  C–H activation , 2021, Nature Reviews Methods Primers.

[6]  Hanmin Huang,et al.  Catalytic Benzylation Reactions: From C—H Bond Activation to C—N Bond Activation , 2020 .

[7]  jin-quan yu,et al.  Rapid Construction of Tetralin, Chromane, and Indane Motifs via Cyclative C-H/C-H Coupling: Four-Step Total Synthesis of (±)-Russujaponol F. , 2020, Journal of the American Chemical Society.

[8]  T. Toriumi,et al.  Selective Double CH Activation at a Methylene Carbon in Methylenediphenol Derivatives to Generate Carbene-Bridged Dinuclear Iridium Complexes , 2020 .

[9]  Nelson Yuen Sum Lam,et al.  Advancing the logic of chemical synthesis: C-H activation as strategic and tactical disconnections for C-C bond construction. , 2020, Angewandte Chemie.

[10]  jin-quan yu,et al.  Palladium-Catalyzed [3+2] Cycloaddition via Two-Fold 1,3-C(sp3)-H Activation. , 2020, Journal of the American Chemical Society.

[11]  M. Murakami,et al.  Dehydrogenative Coupling of Benzylic and Aldehydic C-H Bonds. , 2020, Journal of the American Chemical Society.

[12]  Yusuke Masuda,et al.  Carboxylation of Benzylic and Aliphatic C-H Bonds with CO2 Induced by Light/Ketone/Nickel. , 2019, Journal of the American Chemical Society.

[13]  R. Yazaki,et al.  Recent strategic advances for the activation of benzylic C–H bonds for the formation of C–C bonds , 2019, Tetrahedron Letters.

[14]  T. Ritter,et al.  Synthesis of Benzylic Alcohols by C–H Oxidation , 2019, Journal of the American Chemical Society.

[15]  J. Carretero,et al.  Rhodium-Catalyzed Copper-Assisted Intermolecular Domino C-H Annulation of 1,3-Diynes with Picolinamides: Access to Pentacyclic π-Extended Systems. , 2019, Chemistry.

[16]  P. Walsh,et al.  One-pot aminobenzylation of aldehydes with toluenes , 2018, Nature Communications.

[17]  D. Paley,et al.  Ir(III)-Catalyzed Carbocarbation of Alkynes through Undirected Double C-H Bond Activation of Anisoles. , 2018, Journal of the American Chemical Society.

[18]  S. Gobec,et al.  Antibacterial and β‐Lactamase Inhibitory Activity of Monocyclic β‐Lactams , 2018, Medicinal research reviews.

[19]  S. Stahl,et al.  Feedstocks to Pharmacophores: Cu-Catalyzed Oxidative Arylation of Inexpensive Alkylarenes Enabling Direct Access to Diarylalkanes. , 2017, Journal of the American Chemical Society.

[20]  W. N. Palmer,et al.  Benzyltriboronates: Building Blocks for Diastereoselective Carbon-Carbon Bond Formation. , 2017, Journal of the American Chemical Society.

[21]  S. Takemoto,et al.  Ruthenium-Sulfonamide-Catalyzed Direct Dehydrative Condensation of Benzylic C-H Bonds with Aromatic Aldehydes. , 2016, Journal of the American Chemical Society.

[22]  Fei Wang,et al.  Enantioselective cyanation of benzylic C–H bonds via copper-catalyzed radical relay , 2016, Science.

[23]  D. Spasyuk,et al.  Ligand Attachment Chemistry in the Preparation of PCsp3P and PCsp2P Complexes of Rhodium , 2016 .

[24]  N. Chatani,et al.  Chelation-Assisted Nickel-Catalyzed Oxidative Annulation via Double C-H Activation/Alkyne Insertion Reaction. , 2016, Chemistry.

[25]  W. N. Palmer,et al.  Cobalt-Catalyzed Benzylic Borylation: Enabling Polyborylation and Functionalization of Remote, Unactivated C(sp(3))-H Bonds. , 2016, Journal of the American Chemical Society.

[26]  Hanmin Huang,et al.  Palladium-catalyzed oxidative aminocarbonylation: a new entry to amides via C-H activation. , 2013, Organic letters.

[27]  H. W. Lam,et al.  Functionalization of Csp3-H and Csp2-H bonds: synthesis of spiroindenes by enolate-directed ruthenium-catalyzed oxidative annulation of alkynes with 2-aryl-1,3-dicarbonyl compounds. , 2012, Angewandte Chemie.

[28]  Hanmin Huang,et al.  Palladium-catalyzed oxidative carbonylation of benzylic C-H bonds via nondirected C(sp3)-H activation. , 2012, Journal of the American Chemical Society.

[29]  Andrew J. S. Knox,et al.  Synthesis, biochemical and molecular modelling studies of antiproliferative azetidinones causing microtubule disruption and mitotic catastrophe. , 2011, European journal of medicinal chemistry.

[30]  C. Che,et al.  Selective functionalisation of saturated C-H bonds with metalloporphyrin catalysts. , 2011, Chemical Society reviews.

[31]  Xiaokun Zhao,et al.  Pd-catalyzed carbonylation of diazo compounds at atmospheric pressure: a catalytic approach to ketenes. , 2011, Journal of the American Chemical Society.

[32]  T. Hiyama,et al.  Dehydrogenative [4 + 2] cycloaddition of formamides with alkynes through double C-H activation. , 2011, Journal of the American Chemical Society.

[33]  K. I. Goldberg,et al.  Insertion of molecular oxygen into a palladium(II) methyl bond: a radical chain mechanism involving palladium(III) intermediates. , 2009, Journal of the American Chemical Society.

[34]  N. Jiao,et al.  A palladium-catalyzed oxidative cycloaromatization of biaryls with alkynes using molecular oxygen as the oxidant. , 2009, Angewandte Chemie.

[35]  L. Troisi,et al.  Stereoselective synthesis of 3,4-diaryl β-lactams , 2009 .

[36]  M. Kaneko,et al.  Indium-catalyzed annulation of 2-aryl- and 2-heteroarylindoles with propargyl ethers: concise synthesis and photophysical properties of diverse aryl- and heteroaryl-annulated[a]carbazoles. , 2008, Journal of the American Chemical Society.

[37]  D. Mindiola,et al.  Addition of ammonia, water, and dihydrogen across a single Pd-Pd bond. , 2007, Journal of the American Chemical Society.

[38]  Chun-Hsing Chen,et al.  Palladium Complexes of a P2C Ligand Containing a Central Carbene Moiety , 2007 .

[39]  P. Guiry,et al.  The asymmetric synthesis of β-lactams: HETPHOX/Cu(I) mediated synthesis via the Kinugasa reaction , 2007 .

[40]  S. Parkin,et al.  Double C−H Activation Results in Ruthenium Complexes of a Neutral PCP Ligand with a Central Carbene Moiety , 2006 .

[41]  M. Kaneko,et al.  Easy access to aryl- and heteroaryl-annulated[a]carbazoles by the indium-catalyzed reaction of 2-arylindoles with propargyl ethers. , 2005, Angewandte Chemie.

[42]  G. Singh Beta-lactams in the new millennium. Part-I: monobactams and carbapenems. , 2004, Mini reviews in medicinal chemistry.

[43]  G. Singh β-Lactams in the New Millennium. Part-II: Cephems, Oxacephems, Penams and Sulbactam , 2003 .

[44]  Ayusman Sen,et al.  A warning on the use of radical traps as a test for radical mechanisms: they react with palladium hydrido complexes. , 2002, Journal of the American Chemical Society.

[45]  P. Stavropoulos,et al.  The gif paradox. , 2001, Accounts of chemical research.

[46]  L. Hegedus,et al.  Friedel−Crafts Acylation of Chromium-Carbene-Complex-Derived Ketenes , 1998 .

[47]  H. Berke,et al.  FUNCTIONALIZED IRON KETENE COMPLEXES FROM CARBONYL COUPLING REACTIONS , 1998 .

[48]  M. C. Baird,et al.  Formation of [(η3-CPh3)PdCl]2 via the Reaction of Pd(COD)Cl2 with the Trityl Radical , 1997 .

[49]  H. Werner,et al.  Carbenerhodium Complexes with Diaryl‐ and Aryl(alkyl)carbenes as Ligands: The Missing Link in the Series of the Double Bond Systems trans‐[RhCl{ C(C)nRR′}(L)2] Where n 0, 1, and 2 , 1993 .

[50]  J. Collman The organometallic chemistry of transition-metal porphyrin complexes , 1986 .

[51]  A. Cutler,et al.  Formation of a stable (.eta.2-C,C) ketene compound dicarbonyl(cyclopentadienyl)keteneiron hexafluorophosphate [(C5H5)Fe(CO)2(CH2CO)+ PF6-] by carbonylation of an iron-methylidene complex. A novel entry into carbonyl-derived C2 chemistry , 1983 .

[52]  W. Herrmann,et al.  High‐Pressure Carbonylation of Metal‐Coordinated Carbenes and Hydrogenolysis of the Ketene Complexes , 1978 .

[53]  B. Shaw,et al.  Synthesis and X-ray structure of an unusual iridium ylide or carbene complex , 1978 .

[54]  E. Lewis,et al.  Isotope effects in hydrogen atom transfer. VII. Benzylic hydrogen abstraction by tert-butoxy and other radicals , 1976 .

[55]  G. J. Gleicher,et al.  Steric effects in hydrogen atom abstractions , 1969 .

[56]  K. Ingold,et al.  REACTIONS OF ALKOXY RADICALS: I. HYDROGEN ATOM ABSTRACTION FROM SUBSTITUTED TOLUENES , 1966 .