Pd-NHC-Catalyzed Alkynylation of General Aryl Sulfides with Alkynyl Grignard Reagents.

Cross-coupling reactions of unactivated aryl sulfides with alkynylmagnesium chloride have been invented to afford 1-aryl-1-alkynes with the aid of a palladium/N-heterocyclic carbene complex. This reaction has by far the widest scope of all transformations utilizing aryl sulfides and alkynes, while known cross-coupling alkynylations of aryl-sulfur electrophiles require activated azaaryl sulfides, thiolactams, or arenesulfonyl chlorides. The alkynylation of aryl sulfides is compatible with typical protecting functional groups. The alkynylation is applied to the synthesis of benzofuran-based fluorescent molecules by taking advantage of characteristic organosulfur chemistry.

[1]  A. Osuka,et al.  α-Arylation of Ketimines with Aryl Sulfides at a Low Palladium Catalyst Loading. , 2016, Angewandte Chemie.

[2]  A. Osuka,et al.  Palladium-Catalyzed Zinc-Amide-Mediated C-H Arylation of Fluoroarenes and Heteroarenes with Aryl Sulfides. , 2015, Chemistry.

[3]  A. Osuka,et al.  Palladium-assisted "aromatic metamorphosis" of dibenzothiophenes into triphenylenes. , 2015, Angewandte Chemie.

[4]  F. Suzenet,et al.  Palladium-catalyzed desulfurative Sonogashira cross-coupling reaction of 3-cyano assisted thioamide-type quinolone derivatives with alkynes , 2015 .

[5]  Xi‐Cun Wang,et al.  Chemo‐Controlled Cross‐Coupling of Di(hetero)aryl Disulfides with Grignard Reagents: CC vs. CS Bond Formation , 2015 .

[6]  A. Osuka,et al.  Palladium‐Catalyzed Amination of Aryl Sulfides with Aliphatic Amines , 2015 .

[7]  A. Osuka,et al.  Nickel–NHC-Catalyzed Cross-Coupling of 2-Methylsulfanylbenzofurans with Alkyl Grignard Reagents , 2014, Synlett.

[8]  A. Osuka,et al.  Palladium-catalyzed cross-coupling of unactivated aryl sulfides with arylzinc reagents under mild conditions. , 2014, Chemistry.

[9]  A. Osuka,et al.  Two-Step, Practical, and Diversity-Oriented Synthesis of Multisubstituted Benzofurans from Phenols through Pummerer Annulation Followed by Cross-coupling , 2014 .

[10]  A. Osuka,et al.  Palladium-catalyzed amination of aryl sulfides with anilines. , 2014, Angewandte Chemie.

[11]  A. Osuka,et al.  Practical, modular, and general synthesis of benzofurans through extended Pummerer annulation/cross-coupling strategy. , 2014, Angewandte Chemie.

[12]  Yi‐chen Liu,et al.  Transition-metal-catalyzed C-S bond coupling reaction. , 2014, Chemistry, an Asian journal.

[13]  A. Pöthig,et al.  Synthesis of Soai aldehydes for asymmetric autocatalysis by desulfurative cross-coupling. , 2014, Organic letters.

[14]  Cory Valente,et al.  Carbon–Heteroatom Coupling Using Pd-PEPPSI Complexes , 2014 .

[15]  Zhangjie Shi,et al.  Recent Advances in Transition-Metal-Catalyzed C–S Activation: From Thioester to (Hetero)aryl Thioether , 2014 .

[16]  H. Liu,et al.  Transfer of sulfur: from simple to diverse. , 2013, Chemistry, an Asian journal.

[17]  Jun Liu,et al.  Pd-catalyzed C-S activation for [3 + 3] annulation of 2-(methylthio)benzofuran-3-carboxylates and 2-hydroxyphenylboronic acids: synthesis of coumestan derivatives. , 2013, The Journal of organic chemistry.

[18]  E. V. Van der Eycken,et al.  Transition metal-catalyzed C-C bond formation via C-S bond cleavage: an overview. , 2013, Chemical Society reviews.

[19]  O. Kwon,et al.  Synthesis of nitrodienes, nitrostyrenes, and nitrobiaryls through palladium-catalyzed couplings of β-nitrovinyl and o-nitroaryl thioethers , 2013 .

[20]  S. Enthaler,et al.  Nickel-catalyzed C(sp2)–C(sp2) Cross Coupling Reactions of Sulfur-Functionalities and Grignard Reagents , 2013, Catalysis Letters.

[21]  M. Willis,et al.  Carbon–carbon bond construction using boronic acids and aryl methyl sulfides: orthogonal reactivity in Suzuki-type couplings , 2013 .

[22]  Zhangjie Shi,et al.  Cross coupling of thioethers with aryl boroxines to construct biaryls via Rh catalyzed C–S activation , 2013 .

[23]  Zhengkun Yu,et al.  Transition-metal mediated carbon-sulfur bond activation and transformations. , 2013, Chemical Society reviews.

[24]  A. Osuka,et al.  Synthesis of a library of fluorescent 2-aryl-3-trifluoromethylnaphthofurans from naphthols by using a sequential pummerer-annulation/cross-coupling strategy and their photophysical properties. , 2012, Chemistry.

[25]  Wangqing Kong,et al.  Exclusive 1,2-Aryl Shift in Platinum(II) Chloride-Catalyzed Cyclization of 1-(Indol-2-yl)-2,3-allenols , 2012 .

[26]  P. Bisseret,et al.  Near Room Temperature Cross‐Coupling Reactions of Arene Boronic Acids with a Quinoxaline 1,4‐Dioxide Benzylsulfanyl Derivative , 2012 .

[27]  Cory Valente,et al.  Die Entwicklung raumerfüllender Palladium‐NHC‐Komplexe für anspruchsvollste Kreuzkupplungsreaktionen , 2012 .

[28]  Ka Hou Hoi,et al.  The development of bulky palladium NHC complexes for the most-challenging cross-coupling reactions. , 2012, Angewandte Chemie.

[29]  D. Procter,et al.  Nucleophilic ortho allylation of aryl and heteroaryl sulfoxides. , 2011, Organic letters.

[30]  M. Mihovilovic,et al.  Regioselective Syntheses of 2,3‐Substituted Pyridines by Orthogonal Cross‐Coupling Strategies , 2011 .

[31]  V. Ananikov,et al.  Transition-metal-catalyzed C-S, C-Se, and C-Te bond formation via cross-coupling and atom-economic addition reactions. , 2011, Chemical reviews.

[32]  P. Knochel,et al.  Pd- and Ni-catalyzed cross-coupling reactions of functionalized organozinc reagents with unsaturated thioethers. , 2011, Chemistry.

[33]  E. V. Van der Eycken,et al.  An expeditious route toward pyrazine-containing nucleoside analogues. , 2011, The Journal of organic chemistry.

[34]  H. Yorimitsu,et al.  Synthesis of 3-trifluoromethylbenzo[b]furans from phenols via direct ortho functionalization by extended Pummerer reaction. , 2010, Journal of the American Chemical Society.

[35]  J. Ying,et al.  Rational exploration of N-heterocyclic carbene (NHC) palladacycle diversity: a highly active and versatile precatalyst for Suzuki-Miyaura coupling reactions of deactivated aryl and alkyl substrates. , 2010, Chemistry.

[36]  Xavier Guinchard,et al.  Total synthesis of the antiproliferative macrolide (+)-neopeltolide. , 2009, Organic letters.

[37]  E. V. Van der Eycken,et al.  Mild room-temperature palladium-catalyzed C3-arylation of 2(1H)-pyrazinones via a desulfitative Kumada-type cross-coupling reaction. , 2009, The Journal of organic chemistry.

[38]  C. Kappe,et al.  Die C‐C‐Kreuzkupplung nach Liebeskind und Srogl , 2009 .

[39]  C. Kappe,et al.  The Liebeskind-Srogl C-C cross-coupling reaction. , 2009, Angewandte Chemie.

[40]  B. Shook,et al.  Microwave-assisted Sonogashira-type cross couplings of various heterocyclic methylthioethers , 2009 .

[41]  J. Stambuli,et al.  Nickel-catalyzed synthesis of oxazoles via C-S activation. , 2009, Organic letters.

[42]  S. Nolan,et al.  Well-defined N-heterocyclic carbenes-palladium(II) precatalysts for cross-coupling reactions. , 2008, Accounts of chemical research.

[43]  J. Takaya,et al.  Synthesis of N-fused tricyclic indoles by a tandem [1,2] Stevens-type rearrangement/1,2-alkyl migration of metal-containing ammonium ylides. , 2008, Angewandte Chemie.

[44]  C. Kappe,et al.  Kupferkatalysierte C‐C‐Kupplung von Thiolestern und Boronsäuren unter aeroben Bedingungen , 2008 .

[45]  C. Kappe,et al.  Copper-catalyzed C-C coupling of thiol esters and boronic acids under aerobic conditions. , 2008, Angewandte Chemie.

[46]  E. V. Van der Eycken,et al.  The first palladium-catalyzed desulfitative Sonogashira-type cross-coupling of (hetero)aryl thioethers with terminal alkynes. , 2008, Organic letters.

[47]  F. Suzenet,et al.  Oxazolinethiones and oxazolidinethiones for the first copper-catalyzed desulfurative cross-coupling reaction and first sonogashira applications. , 2008, Organic letters.

[48]  H. Yorimitsu,et al.  Synthesis of benzo[b]thiophenes by cyclization of arylketene dithioacetal monoxides under pummerer-like conditions. , 2007, Organic letters.

[49]  C. Nájera,et al.  The Sonogashira reaction: a booming methodology in synthetic organic chemistry. , 2007, Chemical reviews.

[50]  Henri Doucet,et al.  Palladium‐Katalysatorsysteme für die Synthese von konjugierten Eninen durch Sonogashira‐Kupplungen und verwandte Alkinylierungen , 2007 .

[51]  Jean‐Cyrille Hierso,et al.  Palladium-based catalytic systems for the synthesis of conjugated enynes by sonogashira reactions and related alkynylations. , 2007, Angewandte Chemie.

[52]  Kouki Matsubara,et al.  Synthesis and Structures of Nickel Halide Complexes Bearing Mono- and Bis-coordinated N-Heterocyclic Carbene Ligands, Catalyzing Grignard Cross-Coupling Reactions , 2006 .

[53]  J. Takaya,et al.  Pt(II)- or Au(III)-catalyzed [3+2] cycloaddition of metal-containing azomethine ylides: highly efficient synthesis of the mitosene skeleton. , 2006, Organic letters.

[54]  Srinivas Reddy Dubbaka,et al.  Organoschwefelverbindungen: elektrophile Reagentien für übergangsmetallkatalysierte C-C-Verknüpfungen , 2005 .

[55]  P. Vogel,et al.  Organosulfur compounds: electrophilic reagents in transition-metal-catalyzed carbon-carbon bond-forming reactions. , 2005, Angewandte Chemie.

[56]  K. Nicolaou,et al.  Palladiumkatalysierte Kreuzkupplungen in der Totalsynthese , 2005 .

[57]  K. Nicolaou,et al.  Palladium-catalyzed cross-coupling reactions in total synthesis. , 2005, Angewandte Chemie.

[58]  P. Vogel,et al.  Palladium-catalyzed desulfitative Sonogashira-Hagihara cross-couplings of arenesulfonyl chlorides and terminal alkynes , 2004 .

[59]  A. Fürstner,et al.  Synthesis of phenanthrenes and polycyclic heteroarenes by transition-metal catalyzed cycloisomerization reactions. , 2004, Chemistry.

[60]  L. Brandsma.  Transition Metals-Catalysed Couplings of Acetylenes with sp 2 -Halides , 2004 .

[61]  K. Sonogashira.  Palladium‐Catalyzed Alkynylation: Sonogashira Alkyne Synthesis , 2003 .

[62]  E. Negishi,et al.  Palladium-catalyzed alkynylation. , 2003, Chemical reviews.

[63]  Rik R. Tykwinski.  Palladium‐katalysierte Kreuzkupplungen zwischen sp‐ und sp2‐hybridisierten Kohlenstoffatomen , 2003 .

[64]  R. Tykwinski.  Evolution in the palladium-catalyzed cross-coupling of sp- and sp2-hybridized carbon atoms. , 2003, Angewandte Chemie.

[65]  A. Fürstner,et al.  Flexible synthesis of phenanthrenes by a PtCl(2)-catalyzed cycloisomerization reaction. , 2002, The Journal of organic chemistry.

[66]  K. Sonogashira,et al.  Development of Pd–Cu catalyzed cross-coupling of terminal acetylenes with sp2-carbon halides , 2002 .

[67]  T. Mitsudo,et al.  Metal-catalyzed carbon-sulfur bond formation. , 2000 .

[68]  K. Daasbjerg.  Estimation of bond dissociation Gibbs energies for carbon–halogen bonds in anion radicals of some aryl halides and substituted benzyl halides , 1994 .

[69]  H. Sugimura,et al.  SYNTHESIS OF ALKYL- OR ARYL-SUBSTITUTED HETELOCYCLES: NICKEL COMPLEX CATALYZED COUPLING REACTION OF HETEROCYCLIC SULFIDES AND THIOLS WITH GRIGNARD REAGENTS , 1979 .

[70]  H. Okamura,et al.  Nickel-phosphine complex catalyzed coupling reaction of grignard reagents with alkenyl or aryl sulfides , 1979 .

[71]  E. Michelotti,et al.  Nickel-induced conversion of carbon–sulphur into carbon–carbon bonds. One-step transformations of enol sulphides into olefins and benzenethiol derivatives into alkylarenes and biaryls , 1979 .

[72]  S. Benson.  Thermochemistry and kinetics of sulfur-containing molecules and radicals , 1978 .

[73]  Y. Tohda,et al.  A convenient synthesis of acetylenes: catalytic substitutions of acetylenic hydrogen with bromoalkenes, iodoarenes and bromopyridines , 1975 .