Silver-catalyzed C(sp2)-H functionalization/C-O cyclization reaction at room temperature.

Silver-catalyzed C(sp(2))-H functionalization/C-O cyclization has been developed. The scalable reaction proceeds at room temperature in an open flask. The present method exhibits good functional-group compatibility because of the mild reaction conditions. Using a AgNO3 catalyst and a (NH4)2S2O8 oxidant in CH2Cl2/H2O solvent, various lactones are obtained in good to excellent yields. A kinetic isotope effect (KIE) study indicates that the reaction may occur via a radical process.

[1]  Xueqiang Wang,et al.  Mild ArI-catalyzed C(sp²)-H or C(sp³)-H functionalization/C-O formation: an intriguing catalyst-controlled selectivity switch. , 2014, Angewandte Chemie.

[2]  P. Baran,et al.  Simple sulfinate synthesis enables C-H trifluoromethylcyclopropanation. , 2014, Angewandte Chemie.

[3]  T. Fukuyama,et al.  Synthesis of fluorenones through rhodium-catalyzed intramolecular acylation of biarylcarboxylic acids. , 2014, Organic letters.

[4]  Martin D. Eastgate,et al.  A Mild, Ferrocene-Catalyzed C–H Imidation of (Hetero)Arenes , 2014, Journal of the American Chemical Society.

[5]  P. Baran,et al.  C–H Methylation of Heteroarenes Inspired by Radical SAM Methyl Transferase , 2014, Journal of the American Chemical Society.

[6]  R. Peng,et al.  Synthesis of [60]fullerene-fused tetrahydrobenzooxepine and isochroman derivatives via hydroxyl-directed C-H activation/C-O cyclization. , 2014, Organic letters.

[7]  Wei-Ming Zhao,et al.  Silver catalyzed decarboxylative direct C2-alkylation of benzothiazoles with carboxylic acids. , 2014, Chemical communications.

[8]  H. Niu,et al.  Radical route for the alkylation of purine nucleosides at C6 via Minisci reaction. , 2014, Organic letters.

[9]  V. Gevorgyan,et al.  General and practical carboxyl-group-directed remote C-H oxygenation reactions of arenes. , 2013, Chemistry.

[10]  Dong Liu,et al.  Nickel-catalyzed aromatic C-H alkylation with secondary or tertiary alkyl-bromine bonds for the construction of indolones. , 2013, Organic letters.

[11]  Zhangjie Shi,et al.  Synthesis of dibenzopyranones through palladium-catalyzed directed C-H activation/carbonylation of 2-arylphenols. , 2013, Angewandte Chemie.

[12]  D. Blackmond,et al.  Radical-based regioselective C-H functionalization of electron-deficient heteroarenes: scope, tunability, and predictability. , 2013, Journal of the American Chemical Society.

[13]  J. Kadokawa,et al.  Ruthenium-catalyzed carbonylative C-H cyclization of 2-arylphenols: a novel synthetic route to 6H-dibenzo[b,d]pyran-6-ones. , 2013, Organic letters.

[14]  N. Yoshikai,et al.  Cobalt-catalyzed ortho alkylation of aromatic imines with primary and secondary alkyl halides. , 2013, Journal of the American Chemical Society.

[15]  Rúben Martín,et al.  Cu-catalyzed mild C(sp2)-H functionalization assisted by carboxylic acids en route to hydroxylated arenes. , 2013, Journal of the American Chemical Society.

[16]  Jian-Yong Wang,et al.  Pd-catalyzed C-H lactonization for expedient synthesis of biaryl lactones and total synthesis of cannabinol. , 2013, Organic letters.

[17]  P. Baran,et al.  Convergent synthesis and structural confirmation of phellodonin and sarcodonin ε. , 2013, Organic letters.

[18]  Raju Singha,et al.  Palladium-catalyzed one-pot Suzuki–Miyaura cross coupling followed by oxidative lactonization: a novel and efficient route for the one-pot synthesis of benzo[c]chromene-6-ones , 2013 .

[19]  L. Ackermann,et al.  Ruthenium-catalyzed C-H oxygenation on aryl Weinreb amides. , 2013, Organic letters.

[20]  jin-quan yu,et al.  Pd(II)-catalyzed enantioselective C-H activation/C-O bond formation: synthesis of chiral benzofuranones. , 2013, Journal of the American Chemical Society.

[21]  F. Kwong,et al.  Palladium-catalyzed ortho-CH-bond oxygenation of aromatic ketones. , 2013, Organic letters.

[22]  F. Glorius,et al.  Synthesis of fluorenones via quaternary ammonium salt-promoted intramolecular dehydrogenative arylation of aldehydes , 2013 .

[23]  Yao Fu,et al.  Palladium-catalyzed C-H activation/cross-coupling of pyridine N-oxides with nonactivated secondary alkyl bromides. , 2013, Journal of the American Chemical Society.

[24]  Guangbin Dong,et al.  Synthesis of ortho-acylphenols through the palladium-catalyzed ketone-directed hydroxylation of arenes. , 2012, Angewandte Chemie.

[25]  Xinglin Yang,et al.  Pd-catalyzed C-H oxygenation with TFA/TFAA: expedient access to oxygen-containing heterocycles and late-stage drug modification. , 2012, Angewandte Chemie.

[26]  L. Ackermann,et al.  Ruthenium-catalyzed C-H bond oxygenations with weakly coordinating ketones. , 2012, Organic letters.

[27]  A. M. Riel,et al.  Donor–acceptor biaryl lactones: pH induced molecular switches with intramolecular charge transfer modulation , 2012 .

[28]  N. Sach,et al.  Practical and innate C–H functionalization of heterocycles , 2012, Nature.

[29]  Peng Ren,et al.  Nickel-catalyzed diastereoselective alkyl-alkyl Kumada coupling reactions. , 2012, Organic letters.

[30]  M. Greaney,et al.  Protodecarboxylation of benzoic acids under radical conditions. , 2012, Chemical communications.

[31]  T. Mei,et al.  Activation of remote meta-C–H bonds assisted by an end-on template , 2012, Nature.

[32]  Yu Rao,et al.  Ruthenium(II)-catalyzed synthesis of hydroxylated arenes with ester as an effective directing group. , 2012, Organic letters.

[33]  M. Greaney,et al.  Decarboxylative C-H arylation of benzoic acids under radical conditions. , 2012, Organic letters.

[34]  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.

[35]  D. Blackmond,et al.  A new reagent for direct difluoromethylation. , 2012, Journal of the American Chemical Society.

[36]  P. Novák,et al.  Synergistic palladium-catalyzed C(sp3)-H activation/C(sp3)-O bond formation: a direct, step-economical route to benzolactones. , 2011, Angewandte Chemie.

[37]  Chunhui Huang,et al.  Synthesis of catechols from phenols via Pd-catalyzed silanol-directed C-H oxygenation. , 2011, Journal of the American Chemical Society.

[38]  G. Deng,et al.  Efficient One‐Pot Synthesis of Dibenzopyranones via a Decarboxylative Cross‐Coupling and Lactonization Sequence , 2011 .

[39]  Ye Wei,et al.  Oxidative cyclization of 2-arylphenols to dibenzofurans under Pd(II)/peroxybenzoate catalysis. , 2011, Organic letters.

[40]  P. Baran,et al.  Practical radical cyclizations with arylboronic acids and trifluoroborates. , 2011, Organic letters.

[41]  F. Glorius,et al.  Towards mild metal-catalyzed C-H bond activation. , 2011, Chemical Society reviews.

[42]  S. Takizawa,et al.  Enantioselective cyclization of 4-alkenoic acids via an oxidative allylic C-H esterification. , 2011, Organic letters.

[43]  Lei Liu,et al.  Synthesis of dibenzofurans via palladium-catalyzed phenol-directed C-H activation/C-O cyclization. , 2011, Journal of the American Chemical Society.

[44]  A. Lei,et al.  Transition-metal catalyzed oxidative cross-coupling reactions to form C-C bonds involving organometallic reagents as nucleophiles. , 2011, Chemical Society reviews.

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

[46]  V. Ananikov,et al.  Transition-metal-catalyzed C-S, C-Se, and C-Te bond formation via cross-coupling and atom-economic addition reactions. , 2011, Chemical reviews.

[47]  R. Jana,et al.  Advances in transition metal (Pd, Ni, Fe)-catalyzed cross-coupling reactions using alkyl-organometallics as reaction partners. , 2011, Chemical reviews.

[48]  A. Lei,et al.  Bond formations between two nucleophiles: transition metal catalyzed oxidative cross-coupling reactions. , 2011, Chemical reviews.

[49]  P. Baran,et al.  Practical C-H functionalization of quinones with boronic acids. , 2011, Journal of the American Chemical Society.

[50]  D. Trauner,et al.  Synthetic studies toward A-74528. , 2011, Organic letters.

[51]  A. Makriyannis,et al.  Novel and efficient one-step parallel synthesis of dibenzopyranones via Suzuki-Miyaura cross coupling. , 2010, Journal of combinatorial chemistry.

[52]  F. Glorius,et al.  Palladium-catalyzed intermolecular decarboxylative coupling of 2-phenylbenzoic acids with alkynes via C-H and C-C bond activation. , 2010, Journal of the American Chemical Society.

[53]  P. Baran,et al.  Direct C-H arylation of electron-deficient heterocycles with arylboronic acids. , 2010, Journal of the American Chemical Society.

[54]  jin-quan yu,et al.  Pd(II)-catalyzed hydroxyl-directed C-H activation/C-O cyclization: expedient construction of dihydrobenzofurans. , 2010, Journal of the American Chemical Society.

[55]  Melanie S Sanford,et al.  Palladium-catalyzed ligand-directed C-H functionalization reactions. , 2010, Chemical reviews.

[56]  J. Hartwig,et al.  C-H activation for the construction of C-B bonds. , 2010, Chemical reviews.

[57]  Zhangjie Shi,et al.  Organopalladium(IV) chemistry. , 2010, Chemical Society reviews.

[58]  jin-quan yu,et al.  Transition metal-catalyzed C-H activation reactions: diastereoselectivity and enantioselectivity. , 2009, Chemical Society reviews.

[59]  O. Daugulis,et al.  Palladium- and copper-catalyzed arylation of carbon-hydrogen bonds. , 2009, Accounts of chemical research.

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

[61]  V. Snieckus,et al.  Combined directed ortho and remote metalation-Suzuki cross-coupling strategies. Efficient synthesis of heteroaryl-fused benzopyranones from biaryl O-carbamates. , 2009, The Journal of organic chemistry.

[62]  I. Chatterjee,et al.  Novel and rapid palladium-assisted 6pi electrocyclic reaction affording 9,10-dihydrophenanthrene and its analogues. , 2008, Organic letters.

[63]  H. Nagasawa,et al.  Synthesis of 2-arylbenzoxazoles by copper-catalyzed intramolecular oxidative C-O coupling of benzanilides. , 2008, Angewandte Chemie.

[64]  M. White,et al.  A chiral Lewis acid strategy for enantioselective allylic C-H oxidation. , 2008, Angewandte Chemie.

[65]  S. Ruchirawat,et al.  Copper(I)-mediated and microwave-assisted C(aryl)-O(carboxylic) coupling: synthesis of benzopyranones and isolamellarin alkaloids. , 2007, The Journal of organic chemistry.

[66]  O. Daugulis,et al.  Two methods for direct ortho-arylation of benzoic acids. , 2007, Journal of the American Chemical Society.

[67]  Kenji Watanabe,et al.  A new mechanism for benzopyrone formation in aromatic polyketide biosynthesis. , 2007, Journal of the American Chemical Society.

[68]  P. Langer,et al.  Synthesis of dibenzo[b,d]pyran-6-ones based on [3 + 3] cyclizations of 1,3-bis(silyl enol ethers) with 3-silyloxy-2-en-1-ones. , 2007, The Journal of organic chemistry.

[69]  N. A. Bumagin,et al.  An improved protocol for ligandless Suzuki–Miyaura coupling in water , 2006 .

[70]  P. Langer,et al.  Domino reactions of 1,3-bis-silyl enol ethers with benzopyrylium triflates: efficient synthesis of fluorescent 6H-benzo[c]chromen-6-ones, dibenzo[c,d]chromen-6-ones, and 2,3-dihydro-1H-4,6-dioxachrysen-5-ones. , 2006, Chemistry.

[71]  R. Dolle,et al.  10-hydroxy-10,9-boroxarophenanthrenes: versatile synthetic intermediates to 3,4-benzocoumarins and triaryls. , 2004, The Journal of organic chemistry.

[72]  D. Sames,et al.  Selective functionalization of amino acids in water: a synthetic method via catalytic C-H bond activation. , 2001, Journal of the American Chemical Society.

[73]  Norio Miyaura,et al.  Palladium-Catalyzed Cross-Coupling Reactions of Organoboron Compounds , 1995 .

[74]  H. Togo,et al.  Remote functionalization (1): Synthesis of γ- and δ-lactones from aromatic carboxylic acids , 1995 .

[75]  F. Fontana,et al.  Homolytic acylation of protonated pyridines and pyrazines with .alpha.-keto acids: the problem of monoacylation , 1991 .

[76]  S. Amin,et al.  Oxidation of polynuclear aromatic hydrocarbons with ceric ammonium sulfate: preparation of quinones and lactones , 1988 .

[77]  S. Golding,et al.  Intramolecular cyclisations of biphenyl-2-carboxyl radicals: evidence for a II-state aroyloxyl radical , 1981 .

[78]  J. Devlin 6H-Dibenzo[b,d]pyrans. I. Synthesis , 1975 .

[79]  F. Minisci,et al.  Nucleophilic character of alkyl radicals—VI : A new convenient selective alkylation of heteroaromatic bases , 1971 .

[80]  C. Rees,et al.  883. A novel intramolecular nucleophilic displacement , 1962 .