Metal-Free Intermolecular Aminoarylation of Alkynes.

A metal-free aminoarylation of internal alkynes is described, yielding tetrasubstituted enaminoates. The transformation proceeds in good to excellent yields through a tandem conjugate addition/Smiles rearrangement involving aryl and heteroaryl sulfonamides. Substrate scope is very broad under simple, user-friendly conditions, and the reaction can be used to easily access biologically active phenethylamine derivatives.

[1]  Ian A. Tonks,et al.  Ti-Catalyzed Multicomponent Oxidative Carboamination of Alkynes with Alkenes and Diazenes. , 2016, Journal of the American Chemical Society.

[2]  S. Canesi,et al.  Use of the Nosyl Group as a Functional Protecting Group in Applications of a Michael/Smiles Tandem Process. , 2016, Organic letters.

[3]  R. Shenvi,et al.  Synthesis of the Privileged 8-Arylmenthol Class by Radical Arylation of Isopulegol. , 2016, Organic letters.

[4]  Q. Zhang,et al.  Copper-Catalyzed Hydroxyl-Directed Aminoarylation of Alkynes , 2016 .

[5]  M. Niggemann,et al.  Metal free carboamination of internal alkynes--an easy access to polysubstituted quinolines. , 2016, Chemical communications.

[6]  M. Greaney,et al.  Metal Free Bi(hetero)aryl Synthesis: A Benzyne Truce–Smiles Rearrangement , 2016, Angewandte Chemie.

[7]  Corey R J Stephenson,et al.  A Visible-Light-Mediated Radical Smiles Rearrangement and its Application to the Synthesis of a Difluoro-Substituted Spirocyclic ORL-1 Antagonist. , 2015, Angewandte Chemie.

[8]  W. Ou,et al.  Aza-Knoevenagel-type condensation of secondary amides: direct access to N-monosubstituted β,β-difunctionalized enamines , 2015 .

[9]  I. Hardcastle,et al.  Aryne generation vs. Truce-Smiles and fries rearrangements during the Kobayashi fragmentation reaction: a new bi-aryl synthesis. , 2015, Organic & biomolecular chemistry.

[10]  K. Goossen,et al.  Late transition metal-catalyzed hydroamination and hydroamidation. , 2015, Chemical reviews.

[11]  C. Nevado,et al.  Stereoselective synthesis of highly functionalized indanes and dibenzocycloheptadienes through complex radical cascade reactions. , 2015, Angewandte Chemie.

[12]  C. Nevado,et al.  Cyclization cascades via N-amidyl radicals toward highly functionalized heterocyclic scaffolds. , 2015, Journal of the American Chemical Society.

[13]  Xuan Zhang,et al.  Rh(III)-catalyzed regioselective functionalization of C-H bonds of naphthylcarbamates for oxidative annulation with alkynes. , 2014, Organic letters.

[14]  Nicholas R. Babij,et al.  Synthesis of Substituted 2-Aminoimidazoles via Pd-Catalyzed Alkyne Carboamination Reactions. Application to the Synthesis of Preclathridine Natural Products , 2014, Organic letters.

[15]  Y. Leblanc,et al.  A practical synthesis of indoles via a Pd-catalyzed C-N ring formation. , 2014, Organic letters.

[16]  C. Nájera,et al.  Chemicals from alkynes with palladium catalysts. , 2014, Chemical reviews.

[17]  C. Nevado,et al.  Copper-catalyzed one-pot trifluoromethylation/aryl migration/desulfonylation and C(sp2)-N bond formation of conjugated tosyl amides. , 2013, Journal of the American Chemical Society.

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

[19]  I. Marco,et al.  DABCO-bis(sulfur dioxide), DABSO, as a convenient source of sulfur dioxide for organic synthesis: utility in sulfonamide and sulfamide preparation. , 2011, Organic letters.

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

[21]  Zhidan Liang,et al.  Simple conversion of enamines to 2H-azirines and their rearrangements under thermal conditions. , 2009, Organic letters.

[22]  T. Snape A truce on the Smiles rearrangement: revisiting an old reaction--the Truce-Smiles rearrangement. , 2008, Chemical Society reviews.

[23]  Yeeman K. Ramtohul,et al.  Direct C-Arylation of β-Enamino Esters and Ketones with Arynes , 2007 .

[24]  Yunfei Du,et al.  Synthesis of N-substituted indole derivatives via PIFA-mediated intramolecular cyclization. , 2006, Organic letters.

[25]  A. Fürstner,et al.  Heterocycles by PtCl2-catalyzed intramolecular carboalkoxylation or carboamination of alkynes. , 2005, Journal of the American Chemical Society.

[26]  R. Larock,et al.  Synthesis of Heterocycles via Palladium π-Olefin and π-Alkyne Chemistry , 2004 .

[27]  B. Stanovnik,et al.  Synthesis of heterocycles from alkyl 3-(dimethylamino)propenoates and related enaminones. , 2004, Chemical reviews.

[28]  M. Cheung,et al.  3- AND 4-NITROBENZENESULFONAMIDES : EXCEPTIONALLY VERSATILE MEANS FOR PREPARATION OF SECONDARY AMINES AND PROTECTION OF AMINES , 1995 .

[29]  Rolf Putter,et al.  Biaryls, Stilbenes, Benzo [c]cinnolines, and Dibenz [c,mn] acridines from Sulfonamides , 1972 .

[30]  Rolf Putter,et al.  Biaryle, Stilbene, Benzo[c]cinnoline und Dibenz[c,mn] acridine aus Sulfonamiden , 1972 .

[31]  R. Adams,et al.  THE USE OF THE OXIDES OF PLATINUM FOR THE CATALYTIC REDUCTION OF ORGANIC COMPOUNDS. I , 1922 .

[32]  W. Motherwell,et al.  A novel route to biaryls via intramolecular free radical ipso substitution reactions , 1991 .

[33]  W. Speckamp,et al.  A novel 1,4 arylradical rearrangement.☆ , 1972 .