Silver-mediated oxidative annulation of N-arylthio succinimides with alkynes: direct access to benzo[b]thiophenes

A convenient synthetic route to 2,3-diarylbenzo[b]thiophene derivatives via Ag-catalyzed intermolecular oxidative cyclization between bench-stable N-arylthio succinimides and unactivated internal alkynes is demonstrated herein. The reaction indicates a broad scope, facilitating the construction of diverse arrays of π-conjugated 2,3-diaryl substituted benzothiophenes. The method involves oxidative cleavage of the S–N bond and annulation of alkynes with the concurrent 1,2-S-migration to yield benzo[b]thiophenes.

[1]  J. You,et al.  Radical Cyclization of Arenesulfonyl Chlorides and Alkynes: A Rapid Access to π‐Conjugated Benzothio­phenes , 2016 .

[2]  Zhi Zhou,et al.  Rhodium(III)‐Catalyzed Redox‐Neutral CH Annulation of Arylnitrones and Alkynes for the Synthesis of Indole Derivatives , 2015 .

[3]  Chen Yu,et al.  A Convenient Catalytic Procedure for Direct Synthesis of Arylselanyl Anilines , 2015, Synlett : Accounts and Rapid Communications in Synthetic Organic Chemistry.

[4]  Laijin Tian,et al.  Facile Access to Benzothiophenes through Metal-Free Iodine-Catalyzed Intermolecular Cyclization of Thiophenols and Alkynes , 2015, Synlett : Accounts and Rapid Communications in Synthetic Organic Chemistry.

[5]  Gunaganti Naresh,et al.  Silver(I)-Catalyzed Regioselective Construction of Highly Substituted α-Naphthols and Its Application toward Expeditious Synthesis of Lignan Natural Products. , 2015, Organic letters.

[6]  M. Jeganmohan,et al.  Ruthenium-catalyzed highly regio- and stereoselective hydroarylation of aromatic sulfoxides with alkynes via C-H bond activation. , 2014, Chemical communications.

[7]  Laijin Tian,et al.  Metal-free n-Et4NBr-catalyzed radical cyclization of disulfides and alkynes leading to benzothiophenes under mild conditions , 2014 .

[8]  C. Fu,et al.  Copper(I) Iodide Mediated Synthesis of Carbohydrate-Based Terminal Allenes by ATA Reaction , 2014, Synthesis.

[9]  L. Ackermann,et al.  Silver-Mediated Alkyne Annulations by C–H/P–H Functionalizations: Step-Economical Access to Benzophospholes , 2014, Synthesis.

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

[11]  K. Hirano,et al.  Rhodium(III)-catalyzed ortho-alkenylation through C-H bond cleavage directed by sulfoxide groups. , 2014, Organic letters.

[12]  K. Hirano,et al.  An approach to benzophosphole oxides through silver- or manganese-mediated dehydrogenative annulation involving C-C and C-P bond formation. , 2013, Angewandte Chemie.

[13]  F. Glorius,et al.  Indole synthesis by rhodium(III)-catalyzed hydrazine-directed C-H activation: redox-neutral and traceless by N-N bond cleavage. , 2013, Angewandte Chemie.

[14]  Wei-Liang Duan,et al.  Silver-mediated oxidative C-H/P-H functionalization: an efficient route for the synthesis of benzo[b]phosphole oxides. , 2013, Journal of the American Chemical Society.

[15]  C. Bruneau,et al.  Phosphine-free palladium-catalysed direct C2-arylation of benzothiophenes with aryl bromides , 2013 .

[16]  Zhangjie Shi,et al.  Benzofuran synthesis via copper-mediated oxidative annulation of phenols and unactivated internal alkynes , 2013 .

[17]  W. Zeng,et al.  Facile synthesis of benzofurans via copper-catalyzed aerobic oxidative cyclization of phenols and alkynes. , 2013, Chemical communications.

[18]  Zhi Zhou,et al.  Rhodium(III)-catalyzed redox-neutral coupling of N-phenoxyacetamides and alkynes with tunable selectivity. , 2013, Angewandte Chemie.

[19]  A. Sahoo,et al.  Direct access to benzo[b]furans through palladium-catalyzed oxidative annulation of phenols and unactivated internal alkynes. , 2013, Angewandte Chemie.

[20]  B. Shen,et al.  Direct benzothiophene formation via oxygen-triggered intermolecular cyclization of thiophenols and alkynes assisted by manganese/PhCOOH. , 2013, Organic letters.

[21]  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.

[22]  Benhur Godoi,et al.  Synthesis of heterocycles via electrophilic cyclization of alkynes containing heteroatom. , 2011, Chemical reviews.

[23]  T. Kurahashi,et al.  Nickel-catalyzed cycloadditions of thiophthalic anhydrides with alkynes. , 2011, Organic letters.

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

[25]  K. Hirano,et al.  Synthesis of 2,3‐Diarylbenzo[b]thiophenes via Nickel‐Catalyzed Suzuki–Miyaura Cross‐Coupling and Palladium‐Catalyzed Decarboxylative Arylation , 2009 .

[26]  David R. Stuart,et al.  Indole synthesis via rhodium catalyzed oxidative coupling of acetanilides and internal alkynes. , 2008, Journal of the American Chemical Society.

[27]  T. Doi,et al.  Palladium-catalysed direct synthesis of benzo[b]thiophenes from thioenols. , 2008, Chemical communications.

[28]  J. Bolton,et al.  Benzothiophene selective estrogen receptor modulators with modulated oxidative activity and receptor affinity. , 2007, Journal of medicinal chemistry.

[29]  A. Zanelli,et al.  V‐Shaped Thiophene‐Based Oligomers with Improved Electroluminescence Properties , 2005 .

[30]  J. Aaron,et al.  Polythienobenzothiophenes, a new family of electroactive polymers: electrosynthesis, spectral characterization and modelling , 2004 .

[31]  M. Hashimoto,et al.  An efficient novel synthesis of β-(azuleno[1,2-b]benzothienyl)- and β-(azuleno[2,1-b]benzothienyl)-α,β-unsaturated ketones by the tropylium ion-mediated intramolecular furan ring-opening reaction and X-ray investigation of methyl ketone derivative , 2004 .

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

[33]  E. Hamel,et al.  One-pot synthesis of benzo[b]furan and indole inhibitors of tubulin polymerization. , 2002, Journal of medicinal chemistry.

[34]  U. Schopfer,et al.  Toward selective ERbeta agonists for central nervous system disorders: synthesis and characterization of aryl benzthiophenes. , 2002, Journal of medicinal chemistry.

[35]  P. N. Kumar,et al.  A Facile Synthesis of 7,8-DI Aryl Coumarino and Flavano Benzo-Thiophenes , 2002 .

[36]  M. Malamas,et al.  Novel benzofuran and benzothiophene biphenyls as inhibitors of protein tyrosine phosphatase 1B with antihyperglycemic properties. , 2000, Journal of medicinal chemistry.

[37]  J. Goodby,et al.  Synthesis, transition temperatures, and opticalproperties of various 2,6-disubstituted naphthalenes and related 1-benzothiopheneswith butylsulfanyl and cyano or isothiocyanato terminal groups , 2000 .

[38]  T. Alessi,et al.  Antihyperglycemic activity of novel substituted 3H-1,2,3,5-oxathiadiazole 2-oxides. , 1992, Journal of Medicinal Chemistry.

[39]  P. Montevecchi,et al.  Free-radical reactions of benzenethiol and diphenyl disulphide with alkynes. Chemical reactivity of intermediate 2-(phenylthio)vinyl radicals , 1991 .

[40]  A. Couture,et al.  Photoreactivite de systemes hexatrieniques heterocycliques. Aryl-2 et 3 benzo[b]thiophene , 1981 .