Organocatalytic Enantioselective Friedel–Crafts Alkylation/Lactonization Reaction of Hydroxyindoles with Methyleneoxindoles

Functionalization of the indole benzene ring was achieved by using an organocatalytic enantioselective Friedel–Crafts alkylation/lactonization reaction of hydroxyindoles with a variety of substituted methyleneoxindoles. This reaction was applicable to indoles substituted with the hydroxy group at different positions of the benzene ring, and the corresponding pyrrolodihydrocoumarins were obtained in moderate to high yields (37–99%) with high stereoselectivities (up to 99% ee and >20:1 dr) in most cases. A scale-up reaction and derivatization of the representative products were also carried out to investigate the usefulness of this protocol.

[1]  Y. Wang,et al.  Regioselective Direct C-4 Functionalization of Indole: Total Syntheses of (-)-Agroclavine and (-)-Elymoclavine. , 2017, Organic letters.

[2]  Liang Zhao,et al.  Access to dihydropyridinones and spirooxindoles: application of N-heterocyclic carbene-catalyzed [3+3] annulation of enals and oxindole-derived enals with 2-aminoacrylates. , 2017, Chemical communications.

[3]  C. Vila,et al.  Hydroxy-Directed Enantioselective Hydroxyalkylation in the Carbocyclic Ring of Indoles. , 2017, Organic letters.

[4]  Long-Sheng Wang,et al.  Organocatalytic Friedel-Crafts Alkylation/Lactonization Reaction of Naphthols with 3-Trifluoroethylidene Oxindoles: The Asymmetric Synthesis of Dihydrocoumarins. , 2017, Angewandte Chemie.

[5]  Gang Zhao,et al.  Enantioselective Construction of Spirocyclic Oxindoles via Tandem Michael/Michael Reactions Catalyzed by Multifunctional Quaternary Phosphonium Salt. , 2016, The Journal of organic chemistry.

[6]  C. Vila,et al.  Organocatalytic Enantioselective Friedel–Crafts Aminoalkylation of Indoles in the Carbocyclic Ring , 2016 .

[7]  Jian-rong Gao,et al.  Enantioselective Friedel-Crafts Alkylation Reactions of 3-Substituted Indoles with Electron-Deficient Alkenes. , 2016, The Journal of organic chemistry.

[8]  Yue Zhao,et al.  Palladium-Catalyzed C-H Arylation of Indoles at the C7 Position. , 2016, Journal of the American Chemical Society.

[9]  L. Tan,et al.  Rhodium-Catalyzed Regioselective C7-Functionalization of N-Pivaloylindoles. , 2016, Angewandte Chemie.

[10]  C. Vila,et al.  Organocatalytic Enantioselective Friedel-Crafts Alkylation of 1-Naphthol Derivatives and Activated Phenols with Ethyl Trifluoropyruvate , 2015 .

[11]  P. Baran,et al.  Total Synthesis of Verruculogen and Fumitremorgin A Enabled by Ligand-Controlled C-H Borylation. , 2015, Journal of the American Chemical Society.

[12]  F. Jensen,et al.  Organocatalytic Asymmetric 1,6-Addition/1,4-Addition Sequence to 2,4-Dienals for the Synthesis of Chiral Chromans. , 2015, Angewandte Chemie.

[13]  C. Vila,et al.  Organocatalytic asymmetric addition of naphthols and electron-rich phenols to isatin-derived ketimines: highly enantioselective construction of tetrasubstituted stereocenters. , 2015, Angewandte Chemie.

[14]  Renato Dalpozzo,et al.  Strategies for the asymmetric functionalization of indoles: an update. , 2015, Chemical Society reviews.

[15]  Bo Bi,et al.  Chiral phosphoric acid catalyzed highly enantioselective Friedel-Crafts alkylation reaction of C3-substituted indoles to β,γ-unsaturated α-ketimino esters. , 2015, Organic letters.

[16]  C. Schneider,et al.  Chiral Brønsted acid-catalyzed Friedel-Crafts alkylation of electron-rich arenes with in situ-generated ortho-quinone methides: highly enantioselective synthesis of diarylindolylmethanes and triarylmethanes. , 2015, Chemical communications.

[17]  G. Yedid,et al.  Antioxidant and antitumor activities of 4-arylcoumarins and 4-aryl-3,4-dihydrocoumarins. , 2014, Biochimie.

[18]  F. Shi,et al.  Organocatalytic arylation of 3-indolylmethanols via chemo- and regiospecific C6-functionalization of indoles. , 2014, The Journal of organic chemistry.

[19]  A. Palmieri,et al.  Synthetic approaches to 3-(2-nitroalkyl) indoles and their use to access tryptamines and related bioactive compounds. , 2014, Chemical reviews.

[20]  Hua Liu,et al.  Catalytic C6 functionalization of 2,3-disubstituted indoles by scandium triflate. , 2014, The Journal of organic chemistry.

[21]  P. Tien,et al.  Enantioselective inhibition of reverse transcriptase (RT) of HIV-1 by non-racemic indole-based trifluoropropanoates developed by asymmetric catalysis using recyclable organocatalysts. , 2013, Organic & biomolecular chemistry.

[22]  M. Lombardo,et al.  Organocatalytic conjugate addition of nitroalkanes to 3-ylidene oxindoles: a stereocontrolled diversity oriented route to oxindole derivatives. , 2013, The Journal of organic chemistry.

[23]  Lili Lin,et al.  Enantioselective Friedel-Crafts alkylation for synthesis of 2-substituted indole derivatives. , 2013, Chemical communications.

[24]  Qiang Liu,et al.  Direct olefination at the C-4 position of tryptophan via C-H activation: application to biomimetic synthesis of clavicipitic acid. , 2013, Organic letters.

[25]  Jillian E. Spangler,et al.  Catalytic asymmetric synthesis of pyrroloindolines via a rhodium(II)-catalyzed annulation of indoles. , 2013, Journal of the American Chemical Society.

[26]  W. Xiao,et al.  Highly enantioselective Friedel-Crafts alkylation/N-hemiacetalization cascade reaction with indoles. , 2013, Angewandte Chemie.

[27]  Wei Zhang,et al.  Katalytische asymmetrische Desaromatisierungen , 2012 .

[28]  Wei Zhang,et al.  Catalytic asymmetric dearomatization reactions. , 2012, Angewandte Chemie.

[29]  C. Hertweck,et al.  Bacterial synthesis of diverse indole terpene alkaloids by an unparalleled cyclization sequence. , 2012, Angewandte Chemie.

[30]  Renato Dalpozzo,et al.  Recent advances in organocatalytic methods for the synthesis of disubstituted 2- and 3-indolinones. , 2012, Chemical Society reviews.

[31]  M. Shiri,et al.  Indoles in multicomponent processes (MCPs). , 2012, Chemical reviews.

[32]  S. You,et al.  Enantioselective synthesis of spiro cyclopentane-1,3'-indoles and 2,3,4,9-tetrahydro-1H-carbazoles by iridium-catalyzed allylic dearomatization and stereospecific migration. , 2012, Angewandte Chemie.

[33]  Shoulei Wang,et al.  Highly enantioselective Friedel-Crafts alkylation reaction catalyzed by rosin-derived tertiary amine-thiourea: synthesis of modified chromanes with anticancer potency. , 2012, Chemical communications.

[34]  C. Wolf,et al.  Asymmetric Friedel–Crafts Reaction of Indoles with Ethyl Trifluoropyruvate Using a Copper(I)‐Bisoxazolidine Catalyst , 2011 .

[35]  K. Noguchi,et al.  Entropy-controlled catalytic asymmetric 1,4-type Friedel-Crafts reaction of phenols using conformationally flexible guanidine/bisthiourea organocatalyst. , 2010, Angewandte Chemie.

[36]  Marco Bandini,et al.  Katalytische Funktionalisierung von Indolen in einer neuen Dimension , 2009 .

[37]  M. Bandini,et al.  Catalytic functionalization of indoles in a new dimension. , 2009, Angewandte Chemie.

[38]  M. Zeng,et al.  Chiral Brønsted acid catalyzed Friedel-Crafts alkylation reactions. , 2009, Chemical Society reviews.

[39]  C. Drennan,et al.  Divergent pathways in the biosynthesis of bisindole natural products. , 2009, Chemistry & biology.

[40]  D. Hadjipavlou-Litina,et al.  Synthesis and biological evaluation of novel angular fused Pyrrolocoumarins , 2008 .

[41]  Shou‐Fei Zhu,et al.  Chiral Brønsted acid catalyzed enantioselective Friedel-Crafts reaction of indoles and alpha-aryl enamides: construction of quaternary carbon atoms. , 2007, Angewandte Chemie.

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

[43]  W. Dhooge,et al.  Regioselective synthesis and estrogenicity of (+/-)-8-alkyl-5,7-dihydroxy-4-(4-hydroxyphenyl)-3,4-dihydrocoumarins. , 2005, European journal of medicinal chemistry.

[44]  G. Fabrizi,et al.  Synthesis and functionalization of indoles through palladium-catalyzed reactions. , 2005, Chemical reviews.

[45]  Douglas A. Horton,et al.  The combinatorial synthesis of bicyclic privileged structures or privileged substructures. , 2003, Chemical reviews.

[46]  A. El-Agrody,et al.  Synthesis of halogen derivatives of benzo[h]chromene and benzo[a]anthracene with promising antimicrobial activities. , 2002, Farmaco.

[47]  D. Gottschling,et al.  Identification of a small molecule inhibitor of Sir2p , 2001, Proceedings of the National Academy of Sciences of the United States of America.

[48]  J. Bonjoch,et al.  Synthesis of Strychnine. , 2000, Chemical reviews.

[49]  J. Cook,et al.  The Pictet-Spengler condensation: a new direction for an old reaction , 1995 .

[50]  F. Troxler,et al.  Synthesen von Mannich‐Basen von Hydroxy‐indolen. 3. Mitteilung über synthetische Indol‐Verbindungen [1] , 1968 .

[51]  J. Gloer,et al.  The structure of tubingensin B: A cytotoxic carbazole alkaloid from the sclerotia of Aspergillus tubingensis , 1989 .

[52]  W. Hull,et al.  Tremorgenic mycotoxins from Penicillium crustosum: isolation of penitrems A–F and the structure elucidation and absolute configuration of penitrem A , 1983 .