Site-selective azaindole arylation at the azine and azole rings via N-oxide activation.

Subjection of N-methyl 6- and 7-azaindole N-oxides to a Pd(OAc)2/DavePhos catalyst system enables regioselective direct arylation of the azine ring. Following deoxygenation, 7-azaindole substrates undergo an additional regioselective azole direct arylation event in good yield.

[1]  L. Ackermann,et al.  Palladium-catalyzed direct arylations of heteroarenes with tosylates and mesylates. , 2009, Angewandte Chemie.

[2]  T. Hiyama,et al.  Nickel-catalyzed alkenylation and alkylation of fluoroarenes via activation of C-H bond over C-F bond. , 2008, Journal of the American Chemical Society.

[3]  Ji Zhang,et al.  Iron-mediated direct arylation of unactivated arenes. , 2008, Angewandte Chemie.

[4]  L. Ackermann,et al.  Dehydrative direct arylations of arenes with phenols via ruthenium-catalyzed C-H and C-OH bond functionalizations. , 2008, Organic letters.

[5]  O. Daugulis,et al.  A general method for copper-catalyzed arylation of arene C-H bonds. , 2008, Journal of the American Chemical Society.

[6]  J. Ellman,et al.  Rh(I)-catalyzed direct arylation of pyridines and quinolines. , 2008, Journal of the American Chemical Society.

[7]  Louis-Charles Campeau,et al.  Palladium-catalyzed direct arylation of nitro-substituted aromatics with aryl halides. , 2008, Organic letters.

[8]  K. Fagnou,et al.  Palladium-Catalyzed Intramolecular Coupling of Arenes and Unactivated Alkanes in Air , 2008 .

[9]  Wenjun Lu,et al.  Phosphine-free palladium(II)-catalyzed arylation of naphthalene and benzene with aryl iodides. , 2008, The Journal of organic chemistry.

[10]  S. Buchwald,et al.  Biaryl phosphane ligands in palladium-catalyzed amination. , 2008, Angewandte Chemie.

[11]  J. Ellman,et al.  Direct functionalization of nitrogen heterocycles via Rh-catalyzed C-H bond activation. , 2008, Accounts of chemical research.

[12]  K. Itami,et al.  Copper-mediated C-H bond arylation of arenes with arylboronic acids. , 2008, Organic letters.

[13]  V. Snieckus,et al.  Palladium-catalyzed direct heck arylation of dual pi-deficient/pi-excessive heteroaromatics. Synthesis of C-5 arylated imidazo[1,5-a]pyrazines. , 2008, Organic letters.

[14]  R. Noyori,et al.  Direct coupling of arenes and iodoarenes catalyzed by a rhodium complex with a strongly π-accepting phosphite ligand , 2008 .

[15]  David Lapointe,et al.  Mild and efficient palladium-catalyzed intramolecular direct arylation reactions , 2008 .

[16]  R. Rossi,et al.  Direct palladium-catalyzed C-3 arylation of free (NH)-indoles with aryl bromides under ligandless conditions. , 2008, The Journal of organic chemistry.

[17]  Robert J. Phipps,et al.  Cu(II)-catalyzed direct and site-selective arylation of indoles under mild conditions. , 2008, Journal of the American Chemical Society.

[18]  David R. Stuart,et al.  Intramolecular Pd(II)-catalyzed oxidative biaryl synthesis under air: reaction development and scope. , 2008, The Journal of organic chemistry.

[19]  M. Greaney,et al.  Direct arylation of oxazoles at C2. A concise approach to consecutively linked oxazoles. , 2008, Organic letters.

[20]  C. Hoarau,et al.  Direct C-2 arylation of alkyl 4-thiazolecarboxylates: new insights in synthesis of heterocyclic core of thiopeptide antibiotics. , 2008, Organic letters.

[21]  N. Fujii,et al.  Palladium-catalyzed sp(3) CH activation of simple alkyl groups: direct preparation of indoline derivatives from N-alkyl-2-bromoanilines. , 2008, Organic letters.

[22]  L. Ackermann,et al.  Palladium‐Catalyzed Direct Arylations of 1,2,3‐Triazoles with Aryl Chlorides using Conventional Heating , 2008 .

[23]  J. Mousseau,et al.  Palladium-catalyzed benzylic C-H insertion of 2-substituted N-iminopyridinium ylides. , 2008, Organic letters.

[24]  Elisia Villemure,et al.  C2, C5, and C4 azole N-oxide direct arylation including room-temperature reactions. , 2008, Journal of the American Chemical Society.

[25]  J. Ellman,et al.  Rh(I)-catalyzed arylation of heterocycles via C-H bond activation: expanded scope through mechanistic insight. , 2008, Journal of the American Chemical Society.

[26]  Louis-Charles Campeau,et al.  Site-selective sp2 and benzylic sp3 palladium-catalyzed direct arylation. , 2008, Journal of the American Chemical Society.

[27]  I. Larrosa,et al.  Room temperature and phosphine free palladium catalyzed direct C-2 arylation of indoles. , 2008, Journal of the American Chemical Society.

[28]  Chang-Liang Sun,et al.  Palladium-catalyzed direct arylation of (hetero)arenes with aryl boronic acids. , 2008, Angewandte Chemie.

[29]  J. Mousseau,et al.  Palladium-catalyzed direct C-h arylation of N-iminopyridinium ylides: application to the synthesis of (+/-)-anabasine. , 2008, Journal of the American Chemical Society.

[30]  O. Daugulis,et al.  Copper-catalyzed arylation and alkenylation of polyfluoroarene C-H bonds. , 2008, Journal of the American Chemical Society.

[31]  Keith Fagnou,et al.  High-yielding palladium-catalyzed intramolecular alkane arylation: reaction development and mechanistic studies. , 2007, Journal of the American Chemical Society.

[32]  R. Ferraccioli,et al.  Recent Developments in Catalytic Aryl Coupling Reactions , 2007 .

[33]  L. Ackermann,et al.  Ruthenium(IV) alkylidenes as precatalysts for direct arylations of alkenes with aryl chlorides and an application to sequential catalysis. , 2007, Angewandte Chemie.

[34]  A. Echavarren,et al.  Palladium catalyzed arylation for the synthesis of polyarenes. , 2007, Organic & biomolecular chemistry.

[35]  Fabrice Gallou,et al.  Organometallic methods for the synthesis and functionalization of azaindoles. , 2007, Chemical Society reviews.

[36]  V. Gevorgyan,et al.  Direct transition metal-catalyzed functionalization of heteroaromatic compounds. , 2007, Chemical Society reviews.

[37]  T. Satoh,et al.  Catalytic Direct Arylation of Heteroaromatic Compounds , 2007 .

[38]  D. Sames,et al.  Phosphine-free palladium-catalyzed C-H bond arylation of free (N-H)-indoles and pyrroles. , 2007, The Journal of organic chemistry.

[39]  Mark E. Scott,et al.  Aryl-aryl bond formation by transition-metal-catalyzed direct arylation. , 2007, Chemical reviews.

[40]  K. Fagnou,et al.  Palladium-catalyzed benzene arylation: incorporation of catalytic pivalic acid as a proton shuttle and a key element in catalyst design. , 2006, Journal of the American Chemical Society.

[41]  K. Fagnou,et al.  Palladium-catalyzed cross-coupling reactions of diazine N-oxides with aryl chlorides, bromides, and iodides. , 2006, Angewandte Chemie.

[42]  L. Ackermann,et al.  Catalytic arylation reactions by C-H bond activation with aryl tosylates. , 2006, Angewandte Chemie.

[43]  M. Sanford,et al.  Room temperature palladium-catalyzed 2-arylation of indoles. , 2006, Journal of the American Chemical Society.

[44]  Louis-Charles Campeau,et al.  Palladium-catalyzed direct arylation of simple arenes in synthesis of biaryl molecules. , 2006, Chemical communications.

[45]  R. Rossi,et al.  Palladium‐ and Copper‐Mediated Direct C‐2 Arylation of Azoles — Including Free (NH)‐Imidazole, ‐Benzimidazole and ‐Indole — Under Base‐Free and Ligandless Conditions , 2006 .

[46]  P. Molina,et al.  Synthesis and cytotoxic evaluation of new derivatives of the marine alkaloid variolin B. , 2006, Journal of medicinal chemistry.

[47]  Sophie A. L. Rousseaux,et al.  A solution to the 2-pyridyl organometallic cross-coupling problem: regioselective catalytic direct arylation of pyridine N-oxides. , 2005, Journal of the American Chemical Society.

[48]  L. Yakhontov,et al.  Chemistry of the azaindoles (review) , 1994, Pharmaceutical Chemistry Journal.

[49]  D. Sames,et al.  Direct C-H bond arylation: selective palladium-catalyzed C2-arylation of N-substituted indoles. , 2004, Organic letters.

[50]  Pablo Cironi,et al.  Synthesis of Polyheterocyclic Nitrogen-Containing Marine Natural Products , 2004 .

[51]  K. Soundararajan.  Omega results for the divisor and circle problems , 2003, math/0302010.

[52]  John P. Wolfe,et al.  A Highly Active Catalyst for Palladium-Catalyzed Cross-Coupling Reactions: Room-Temperature Suzuki Couplings and Amination of Unactivated Aryl Chlorides , 1998 .

[53]  A. Ohta,et al.  Facile and Efficient Deoxygenation of Aromatic N-Oxides with Zinc and Aqueous Ammonium Chloride , 1997 .

[54]  L. Yakhontov.  The Chemistry of Azaindoles [Pyrrolo[2,3]pyridines] , 1968 .