Synthesis of fused 1-aminoindole polycycles by a sequence of palladium-catalyzed N–H and C(sp2)–H arylations.

An efficient Pd-catalyzed selective intramolecular arylation of functionalized N,N′-substituted 1-aminoindoles has been reported. In all cases, the reactions take place rapidly in DMA and efficiently proceed in the presence of a Pd(OAc)2/Dpephos catalytic system, furnishing the fused indolo[2,1-a]phthalazines in high yields. Additionally, the one-pot double C–H arylation at positions C-2 and C-3 of N,N′-substituted 1-aminoindoles is effective and leads to unknown complex scaffolds of biological interest.

[1]  S. Messaoudi,et al.  Palladium(II)-catalyzed oxidative arylation of quinoxalin-2(1H)-ones with arylboronic acids. , 2013, Organic letters.

[2]  S. Messaoudi,et al.  Synthesis of 3,4‐Disubstituted Quinolin‐2‐(1H)‐ones via Palladium‐Catalyzed Decarboxylative Arylation Reactions , 2013 .

[3]  J. Peyrat,et al.  Palladium-Catalyzed Cross-Coupling of 1-Aminoazoles with Aryl Chlorides: Application to the Synthesis of Unsymmetrical N,N′-Diaryl-1-aminoindoles , 2012 .

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

[5]  P. Baran,et al.  Innate and guided C-H functionalization logic. , 2012, Accounts of chemical research.

[6]  S. Messaoudi,et al.  Palladium-catalyzed decarboxylative coupling of quinolinone-3-carboxylic acids and related heterocyclic carboxylic acids with (hetero)aryl halides. , 2012, Organic letters.

[7]  S. Messaoudi,et al.  Palladium‐Catalyzed Direct Benzylation of Xanthines , 2011 .

[8]  L. Ackermann.  Carboxylate-assisted transition-metal-catalyzed C-H bond functionalizations: mechanism and scope. , 2011, Chemical reviews.

[9]  S. Messaoudi,et al.  Transition-Metal-Catalyzed Direct C–H Alkenylation, Alkynylation, Benzylation, and Alkylation of (Hetero)arenes , 2010 .

[10]  L. Djakovitch,et al.  "On Water" Direct and Site-Selective Pd-Catalysed CH Arylation of (NH)-Indoles , 2010 .

[11]  K. Ueda,et al.  A general catalyst for the β-selective C-H bond arylation of thiophenes with iodoarenes. , 2010, Angewandte Chemie.

[12]  S. Messaoudi,et al.  Pd/Cu‐Catalyzed Direct Alkenylation of Azole Heterocycles with Alkenyl Halides , 2010 .

[13]  S. Messaoudi,et al.  A site selective C-H arylation of free-(NH2) adenines with aryl chlorides: application to the synthesis of 6,8-disubstituted adenines. , 2009, Organic & biomolecular chemistry.

[14]  L. Djakovitch,et al.  Transition Metal‐Catalysed, Direct and Site‐Selective N1‐, C2‐ or C3‐Arylation of the Indole Nucleus: 20 Years of Improvements , 2009 .

[15]  J. Peyrat,et al.  Microwave-assisted Pd(OH)2-catalyzed direct C−H arylation of free-(NH2) adenines with aryl halides , 2008 .

[16]  B. Hugon,et al.  Pyrrolocarbazoles as checkpoint 1 kinase inhibitors. , 2008, Anti-cancer agents in medicinal chemistry.

[17]  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.

[18]  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.

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

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

[21]  Zhiqiang Zhang,et al.  Direct palladium-catalyzed C-3 arylation of indoles , 2007 .

[22]  R. Noyori,et al.  Direct C-H arylation of (hetero)arenes with aryl iodides via rhodium catalysis. , 2006, Journal of the American Chemical Society.

[23]  Jeffrey T. Kuethe,et al.  Practical methodologies for the synthesis of indoles. , 2006, Chemical reviews.

[24]  L. Djakovitch,et al.  Heterogeneous Palladium Catalysts Applied to the Synthesis of 2- and 2,3-Functionalised Indoles , 2006 .

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

[26]  B. Pfeiffer,et al.  Synthesis of bridged aza-rebeccamycin analogues , 2005 .

[27]  R. Heck.  Palladium‐Catalyzed Vinylation of Organic Halides , 2005 .

[28]  B. Pfeiffer,et al.  Synthesis of granulatimide bis-imide analogues , 2005 .

[29]  M. Brown,et al.  Direct palladium-catalyzed C-2 and C-3 arylation of indoles: a mechanistic rationale for regioselectivity. , 2005, Journal of the American Chemical Society.

[30]  John M. Brown,et al.  Directed palladation: fine tuning permits the catalytic 2-alkenylation of indoles. , 2005, Chemical communications.

[31]  D. Sames,et al.  Direct C-arylation of free (NH)-indoles and pyrroles catalyzed by Ar-Rh(III) complexes assembled in situ. , 2005, Journal of the American Chemical Society.

[32]  Y. Naruta,et al.  Reactivity of the indole ring in palladium(II) complexes of 2N1O-donor ligands: cyclopalladation and pi-cation radical formation. , 2004, Journal of the American Chemical Society.

[33]  M. Lautens,et al.  Synthesis of novel tetracycles via an intramolecular Heck reaction with anti-hydride elimination. , 2003, Organic letters.

[34]  C. Cho,et al.  Ag+ mediated deaminations of N-Boc aryl hydrazines for the efficient synthesis of N-Boc aryl amines , 2002 .

[35]  T. Satoh,et al.  Palladium-catalyzed multiple arylation of thiophenes. , 2002, Journal of the American Chemical Society.

[36]  Jennifer S. Gibson,et al.  The scope and limitations of deuteration mediated by Crabtree's catalyst , 2001 .

[37]  M. Yus,et al.  Reduction of Hydrazines, Azo and Azoxy Compounds, and Amine N-Oxides with the NiCl2·2H2O–Li–DTBB (cat.) Combination , 2000 .

[38]  M. Lounasmaa,et al.  Simple indole alkaloids and those with a nonrearranged monoterpenoid unit. , 2000, Natural product reports.

[39]  Lee,et al.  Synthesis and properties of 9-alkyl- and 9-Arylcyclopenta , 2000, Organic letters.

[40]  T. Yakura,et al.  Synthesis of Heterocycles Using the Intramolecular Heck Reaction Involving a 'Foraml' Anti-elimination Process , 1999 .

[41]  G. Palmisano,et al.  Cyclometallation of indole derivatives: cyclopalladation of gramine and 1-methyl gramine and CO insertion , 1997 .

[42]  T. Jeffery.  ON THE EFFICIENCY OF TETRAALKYLAMMONIUM SALTS IN HECK TYPE REACTIONS , 1996 .

[43]  A. Kozikowski,et al.  Palladium catalyzed synthesis of annelated indoles , 1991 .

[44]  H. Doucet,et al.  Benzenesulfonyl chlorides: new reagents for access to alternative regioisomers in palladium-catalysed direct arylations of thiophenes , 2014 .

[45]  K. Maeda,et al.  Competing Regiochemical Pathways in the Heck Arylation of 1,2‐Dihydronaphthalene , 2002 .

[46]  P. Melnyk,et al.  Heck reaction to a new heterocyclic system: pyrido[2′,3′-dt́]pyridazino[2,3-a]indole , 1993 .

[47]  R. Grigg,et al.  The synthesis of fused ring nitrogen heterocycles via regiospecific intramolecular heck reactions , 1990 .