Co(III)-Catalyzed Synthesis of Quinazolines via C-H Activation of N-Sulfinylimines and Benzimidates.

C-H activation of arenes has been established as an important strategy for heterocycle synthesis via annulations between arenes and unsaturated coupling partners. However, nitriles failed to act as such a coupling partner. Dioxazolones have been employed as a synthon of nitriles, and subsequent coupling with arenes such as N-sulfinylimines and benzimidates bearing a functionalizable directing group provided facile access to two classes of quinazolines under Co(III)-catalysis.

[1]  B. Heller,et al.  The fascinating construction of pyridine ring systems by transition metal-catalysed [2 + 2 + 2] cycloaddition reactions. , 2007, Chemical Society reviews.

[2]  Ji Young Kim,et al.  Recent advances in the transition metal-catalyzed twofold oxidative C-H bond activation strategy for C-C and C-N bond formation. , 2011, Chemical Society reviews.

[3]  L. Tran,et al.  Directed amination of non-acidic arene C-H bonds by a copper-silver catalytic system. , 2013, Angewandte Chemie.

[4]  Hui Xu,et al.  Cu-Catalyzed Direct Amidation of Aromatic C–H Bonds: An Access to Arylamines , 2014, The Journal of organic chemistry.

[5]  O. Daugulis,et al.  Cobalt-promoted dimerization of aminoquinoline benzamides. , 2015, Organic letters.

[6]  J. Wang,et al.  Copper-catalyzed C(sp2)-H amidation with azides as amino sources. , 2014, Organic letters.

[7]  O. Daugulis,et al.  Cobalt-catalyzed, aminoquinoline-directed C(sp²)-H bond alkenylation by alkynes. , 2014, Angewandte Chemie.

[8]  Shangze Wu,et al.  Rhodium-catalyzed C–H functionalization-based approach to eight-membered lactams , 2015, Chemical science.

[9]  M. Kanai,et al.  Cp*Co(III) Catalyzed Site-Selective C-H Activation of Unsymmetrical O-Acyl Oximes: Synthesis of Multisubstituted Isoquinolines from Terminal and Internal Alkynes. , 2015, Angewandte Chemie.

[10]  jin-quan yu,et al.  Cu(II)-mediated C-H amidation and amination of arenes: exceptional compatibility with heterocycles. , 2014, Journal of the American Chemical Society.

[11]  Fen Wang,et al.  C-C, C-O and C-N bond formation via rhodium(III)-catalyzed oxidative C-H activation. , 2012, Chemical Society reviews.

[12]  S. Buchwald,et al.  Palladium-catalyzed N-monoarylation of amidines and a one-pot synthesis of quinazoline derivatives. , 2012, Organic letters.

[13]  F. Glorius,et al.  Rh(III)/Cu(II)-cocatalyzed synthesis of 1H-indazoles through C-H amidation and N-N bond formation. , 2013, Journal of the American Chemical Society.

[14]  M. Kanai,et al.  Pyrroloindolone synthesis via a Cp*Co(III)-catalyzed redox-neutral directed C-H alkenylation/annulation sequence. , 2014, Journal of the American Chemical Society.

[15]  Lin Dong,et al.  Highly functionalized pyridines synthesis from N-sulfonyl ketimines and alkynes using the N-S bond as an internal oxidant. , 2014, Organic letters.

[16]  L. Ackermann,et al.  Cobalt-Catalyzed C―H Activation , 2016 .

[17]  Xiaobo Huang,et al.  Unexpected copper-catalyzed cascade synthesis of quinazoline derivatives. , 2013, The Journal of organic chemistry.

[18]  F. Glorius,et al.  Mild rhodium(III)-catalyzed C-H activation and intermolecular annulation with allenes. , 2012, Angewandte Chemie.

[19]  E. Nakamura,et al.  Synthesis of anthranilic acid derivatives through iron-catalyzed ortho amination of aromatic carboxamides with N-chloroamines. , 2014, Journal of the American Chemical Society.

[20]  Hongwei Zhang,et al.  Copper-catalyzed annulation of amidines for quinazoline synthesis. , 2013, Chemical communications.

[21]  Simon Duttwyler,et al.  Highly diastereoselective synthesis of tetrahydropyridines by a C-H activation-cyclization-reduction cascade. , 2012, Journal of the American Chemical Society.

[22]  L. Ackermann,et al.  Cobalt-catalyzed C-H arylations with weakly-coordinating amides and tetrazoles: expedient route to angiotensin-II-receptor blockers. , 2015, Chemistry.

[23]  M. Kanai,et al.  A Cp*CoI2-dimer as a precursor for cationic Co(III)-catalysis: application to C-H phosphoramidation of indoles. , 2015, Chemical communications.

[24]  F. Glorius,et al.  Rh(III)-catalyzed synthesis of multisubstituted isoquinoline and pyridine N-oxides from oximes and diazo compounds. , 2013, Journal of the American Chemical Society.

[25]  Pitambar Patel,et al.  Cobalt(III)-Catalyzed C–H Amidation of Arenes using Acetoxycarbamates as Convenient Amino Sources under Mild Conditions , 2015 .

[26]  L. Ackermann.  Carboxylate-assisted ruthenium-catalyzed alkyne annulations by C-H/Het-H bond functionalizations. , 2014, Accounts of chemical research.

[27]  Sukbok Chang,et al.  Comparative Catalytic Activity of Group 9 [Cp*M(III)] Complexes: Cobalt-Catalyzed C-H Amidation of Arenes with Dioxazolones as Amidating Reagents. , 2015, Angewandte Chemie.

[28]  K. Parthasarathy,et al.  Rhodium-Catalyzed One-Pot Synthesis of Substituted Pyridine Derivatives from α,β-Unsaturated Ketoximes and Alkynes , 2008 .

[29]  M. Kanai,et al.  A cationic high-valent Cp*Co(III) complex for the catalytic generation of nucleophilic organometallic species: directed C-H bond activation. , 2013, Angewandte Chemie.

[30]  M. Kanai,et al.  Air‐Stable Carbonyl(pentamethylcyclopentadienyl)cobalt Diiodide Complex as a Precursor for Cationic (Pentamethylcyclopentadienyl)cobalt(III) Catalysis: Application for Directed C‐2 Selective CH Amidation of Indoles , 2014 .

[31]  Michael Wiese,et al.  Investigation of quinazolines as inhibitors of breast cancer resistance protein (ABCG2). , 2013, Bioorganic & medicinal chemistry.

[32]  F. Glorius,et al.  Cobalt(III)-catalyzed directed C-H coupling with diazo compounds: straightforward access towards extended π-systems. , 2015, Angewandte Chemie.

[33]  M. Gaunt,et al.  Recent developments in natural product synthesis using metal-catalysed C-H bond functionalisation. , 2011, Chemical Society reviews.

[34]  Xingwei Li,et al.  Substrate activation strategies in rhodium(III)-catalyzed selective functionalization of arenes. , 2015, Accounts of chemical research.

[35]  M. Sanford,et al.  Controlling site selectivity in palladium-catalyzed C-H bond functionalization. , 2012, Accounts of chemical research.

[36]  D. Spring,et al.  Arene C-H functionalisation using a removable/modifiable or a traceless directing group strategy. , 2014, Chemical Society reviews.

[37]  F. Glorius,et al.  Efficient synthesis of pyrazoles: oxidative C-C/N-N bond-formation cascade. , 2010, Angewandte Chemie.

[38]  Huanfeng Jiang,et al.  Transition metal-catalyzed C-H functionalization of N-oxyenamine internal oxidants. , 2015, Chemical Society reviews.

[39]  N. Jiao,et al.  Cationic Cobalt(III)-Catalyzed Aryl and Alkenyl C-H Amidation: A Mild Protocol for the Modification of Purine Derivatives. , 2015, Chemistry.

[40]  S. Maiti,et al.  Anti-cancer therapeutic potential of quinazoline based small molecules via global upregulation of miRNAs. , 2014, Chemical communications.

[41]  L. Ackermann,et al.  Cobalt-catalyzed C-H cyanation of arenes and heteroarenes. , 2015, Angewandte Chemie.

[42]  Lingheng Kong,et al.  Redox-Neutral Couplings between Amides and Alkynes via Cobalt(III)-Catalyzed C-H Activation. , 2016, Organic letters.

[43]  Zhangjie Shi,et al.  Exploration of earth-abundant transition metals (Fe, Co, and Ni) as catalysts in unreactive chemical bond activations. , 2015, Accounts of chemical research.

[44]  K. Vollhardt.  Cobalt-vermittelte [2+2+2]-Cycloadditionen: eine ausgereifte Synthesestrategie , 1984 .

[45]  Lutz Ackermann,et al.  Cobalt(II)-Catalyzed Oxidative C–H Alkenylations: Regio- and Site-Selective Access to Isoindolin-1-one , 2015 .

[46]  J. Hartwig,et al.  On the interpretation of deuterium kinetic isotope effects in C-H bond functionalizations by transition-metal complexes. , 2012, Angewandte Chemie.

[47]  T. Satoh,et al.  Oxidative coupling of aromatic substrates with alkynes and alkenes under rhodium catalysis. , 2010, Chemistry.

[48]  K. Vollhardt,et al.  Cobalt‐Mediated [2 + 2 + 2]‐Cycloadditions: A Maturing Synthetic Strategy [New Synthetic Methods (43)] , 1984 .

[49]  O. Daugulis,et al.  Direct Conversion of Carbon-Hydrogeninto Carbon-Carbon Bonds by First-Row Transition-MetalCatalysis , 2009 .

[50]  J. Ellman,et al.  Synthesis of dihydropyridines and pyridines from imines and alkynes via C-H activation. , 2008, Journal of the American Chemical Society.

[51]  F. Glorius,et al.  Co(III)-catalyzed C-H activation/formal SN-type reactions: selective and efficient cyanation, halogenation, and allylation. , 2014, Journal of the American Chemical Society.

[52]  Sukbok Chang,et al.  Mechanistic studies on the Rh(III)-mediated amido transfer process leading to robust C-H amination with a new type of amidating reagent. , 2015, Journal of the American Chemical Society.

[53]  Junichiro Yamaguchi,et al.  C-H bond functionalization: emerging synthetic tools for natural products and pharmaceuticals. , 2012, Angewandte Chemie.

[54]  M. Kanai,et al.  Dehydrative Direct C-H Allylation with Allylic Alcohols under [Cp*Co(III)] Catalysis. , 2015, Angewandte Chemie.

[55]  T. Rovis,et al.  A coupling of benzamides and donor/acceptor diazo compounds to form γ-lactams via Rh(III)-catalyzed C-H activation. , 2013, Journal of the American Chemical Society.

[56]  Sukbok Chang,et al.  Cobalt-catalyzed C-H cyanation of (hetero)arenes and 6-arylpurines with N-cyanosuccinimide as a new cyanating agent. , 2015, Organic letters.

[57]  Yuhong Zhang,et al.  Transition metal-catalyzed C–H bond functionalizations by the use of diverse directing groups , 2015 .

[58]  F. Glorius,et al.  Beyond directing groups: transition-metal-catalyzed C-H activation of simple arenes. , 2012, Angewandte Chemie.

[59]  L. Ackermann,et al.  Cobalt(III)-Catalyzed Aryl and Alkenyl C-H Aminocarbonylation with Isocyanates and Acyl Azides. , 2015, Angewandte Chemie.

[60]  J. Ellman,et al.  Cobalt(III)-Catalyzed Synthesis of Indazoles and Furans by C–H Bond Functionalization/Addition/Cyclization Cascades , 2014, Journal of the American Chemical Society.

[61]  L. Ackermann,et al.  Cobalt(III)-Catalyzed C-H Alkynylation with Bromoalkynes under Mild Conditions. , 2015, Organic letters.

[62]  Chunfang Jiang,et al.  Cp*Co(III)-Catalyzed Annulations of 2-Alkenylphenols with CO: Mild Access to Coumarin Derivatives. , 2015, Organic letters.

[63]  jin-quan yu,et al.  Palladium(II)-catalyzed C-H activation/C-C cross-coupling reactions: versatility and practicality. , 2009, Angewandte Chemie.

[64]  B. Liu,et al.  Cobalt(III)-Catalyzed C2-Selective C-H Alkynylation of Indoles. , 2015, Organic letters.

[65]  F. Glorius,et al.  Formal SN‐Type Reactions in Rhodium(III)‐Catalyzed CH Bond Activation , 2014 .

[66]  Xingwei Li,et al.  Rhodium(III)-Catalyzed Amidation of Unactivated C(sp(3) )-H Bonds. , 2015, Angewandte Chemie.

[67]  N. Chatani,et al.  Catalytic functionalization of C(sp2)-H and C(sp3)-H bonds by using bidentate directing groups. , 2013, Angewandte Chemie.

[68]  T. Mei,et al.  Weak coordination as a powerful means for developing broadly useful C-H functionalization reactions. , 2012, Accounts of chemical research.

[69]  Chang-Liang Sun,et al.  Direct C-H transformation via iron catalysis. , 2011, Chemical reviews.

[70]  N. Shakya,et al.  Synthesis and biological evaluation of novel 4-(hetero) aryl-2-piperazino quinazolines as anti-leishmanial and anti-proliferative agents. , 2009, Bioorganic & medicinal chemistry letters.

[71]  C. Bruneau,et al.  Ruthenium(II)-catalyzed C-H bond activation and functionalization. , 2012, Chemical reviews.

[72]  J. Ellman,et al.  Rhodium-catalyzed C-C bond formation via heteroatom-directed C-H bond activation. , 2010, Chemical reviews.

[73]  F. Glorius,et al.  Cobalt(III)-Catalyzed Directed C-H Allylation. , 2015, Organic letters.