Advertisement

Ruthenium-bipyridine complex catalyzed C–H alkenylation of arylpyrazole derivatives

  • Sanchari Shome
  • Surya Prakash Singh
Regular Article
  • 84 Downloads

Abstract

Direct dehydrogenative alkenylation of N-arylpyrazoles by acrylates has proven to be efficient under Ru(II) carboxylate complexes SPS-BPY and SPS-DB-BPY catalyst along with \(\hbox {Cu(OAc)}_{2}{\cdot }\hbox {H}_{2}\hbox {O}\) as an oxidant. The reaction was found to be atom-economical and was characterized by a number of substituted N-arylpyrazoles with excellent chemoselectivity. The reaction allowed a direct alkenylation to be performed under the eco-friendly solvent system. The diverse functional group tolerance of this protocol opened up a new insight to the use of ruthenium(II) bipyridine complexes as a productive method for the oxidative heterocoupling of N-arylpyrazole.

Graphical Abstract

Synopsis Ruthenium(II)-Bipyridine catalyst was used for directive C–C alkenylation of arylpyrazoles and aryloxazolines under additive- and co-catalyst-free mild conditions. The comprehensive substrate scope and high chemoselectivity make the protocol versatile. The method prevents the formation of homo-coupled byproducts thereby challenging the traditional alkenylation reactions and opens up a new genre in ruthenium catalysis.

Keywords

Ru(II) bipyridine alcoholic solvent dialkenylation alkenylarylpyrazoles chemoselectivity acrylate 

Notes

Acknowledgements

SPS and SS thank DST Fast Track Young Scientist Project (CS-83/2012) for funding. SS also thanks AcSIR for PhD registration.

Supplementary material

12039_2018_1478_MOESM1_ESM.pdf (727 kb)
Supplementary material 1 (pdf 727 KB)

References

  1. 1.
    Heck R F 1967 Alkyl- and Acylcobalt Carbonyls Containing Olefinic Unsaturation. II. Cyclization of 5-Hexenoylcobalt Tetracarbonyl and Nonterminal Olefin Complexes J. Am. Chem. Soc. 89 5518CrossRefGoogle Scholar
  2. 2.
    Lewis L N and Smith J F 1986 Catalytic carbon-carbon bond formation via ortho-metalated complexes J. Am. Chem. Soc. 108 2728CrossRefGoogle Scholar
  3. 3.
    Arockiam P B, Bruneau C and Dixneuf P H 2012 Ruthenium(II)-Catalyzed C–H Bond Activation and Functionalization Chem. Rev. 112 5879Google Scholar
  4. 4.
    (a) Fujiwara Y Moritani I Matsuda M and Teranishi S 1968 Cationic Pd(II)-Catalyzed Fujiwara-Moritani Reactions at Room Temperature in Water Tetrahedron Lett. 9 3863; (b) Fujiwara Y, Noritani I, Danno, S Asano R and Teranishi S 1969 Aromatic substitution of olefins. VI. Arylation of olefins with palladium(II) acetate J. Am. Chem. Soc. 91 7166; (c) Kakiuchi F and Murai S 2002 Catalytic C-H/Olefin Coupling Acc. Chem. Res. 35 826Google Scholar
  5. 5.
    Suzuki C, Morimoto K, Hirano K, Satoh T and Miura M 2014 Ruthenium- and Rhodium-Catalyzed Dehydrogenative ortho-Alkenylation of Benzylamines via Free Amino Group Directed C-H Bond Cleavage Adv. Synth. Catal. 356 1521CrossRefGoogle Scholar
  6. 6.
    Murai S, Kakiuchi F, Sekine S, Tanaka Y, Kamatani A, Sonoda M and Chatani N 1993 Efficient catalytic addition of aromatic carbon-hydrogen bonds to olefins Nature 366 529CrossRefGoogle Scholar
  7. 7.
    Cheng K, Yao B, Zhao J and Zhang Y 2008 \(\text{ RuCl }_{3}\)-Catalyzed Alkenylation of Aromatic C-H Bonds with Terminal Alkynes Org. Lett. 10 5309Google Scholar
  8. 8.
    Patureau F W, Besset T, Kuhl N and Glorius F 2011 Diverse Strategies toward Indenol and Fulvene Derivatives: Rh-Catalyzed C-H Activation of Aryl Ketones Followed by Coupling with Internal Alkynes J. Am. Chem. Soc. 133 2154CrossRefPubMedGoogle Scholar
  9. 9.
    Tsukada N, Mitsuboshi T, Setoguchi H and Inoue Y 2003 Stereoselective cis-Addition of Aromatic C-H Bonds to Alkynes Catalyzed by Dinuclear Palladium Complexes J. Am. Chem. Soc. 125 12102CrossRefPubMedGoogle Scholar
  10. 10.
    Satoh T, Nishinaka Y, Miura M and Nomura M 1999 Iridium-Catalyzed Regioselective Reaction of 1-Naphthols with Alkynes at the peri-Position Chem. Lett. 28 615Google Scholar
  11. 11.
    Kuninobu Y, Kawata A and Takai K 2005 Rhenium-Catalyzed Formation of Indene Frameworks via C-H Bond Activation: [3+2] Annulation of Aromatic Aldimines and Acetylenes J. Am. Chem. Soc. 127 13498Google Scholar
  12. 12.
    Nakao Y, Kanyiva K S, Oda S and Hiyama T 2006 Hydroheteroarylation of Alkynes under Mild Nickel Catalysis J. Am. Chem. Soc. 128 8146CrossRefPubMedGoogle Scholar
  13. 13.
    Gao K, Lee P S, Fujita T and Yoshikai N 2010 Cobalt-Catalyzed Hydroarylation of Alkynes through Chelation-Assisted C-H Bond Activation J. Am. Chem. Soc. 132 12249CrossRefPubMedGoogle Scholar
  14. 14.
    Cho S H, Hwang S J and Chang S 2008 Palladium-Catalyzed C-H Functionalization of Pyridine N-Oxides: Highly Selective Alkenylation and Direct Arylation with Unactivated Arenes J. Am. Chem. Soc. 29 9254CrossRefGoogle Scholar
  15. 15.
    Shome S and Singh S P 2015 Solvent-Free Ru(II)-Catalyzed C-H Activation: Synthesis of Alkenyl Arylpyrazole Derivatives Eur. J. Org. 6025Google Scholar
  16. 16.
    Liu B, Fan Y, Gao Y, Sun C, Xu C and Zhu J 2013 Rhodium(III)-Catalyzed N-Nitroso-Directed C–H Olefination of Arenes. High-Yield, Versatile Coupling under Mild Conditions J. Am. Chem. Soc. 135 468CrossRefPubMedGoogle Scholar
  17. 17.
    Dong W, Wang L, Parthasarathy K, Pan F and Bolm C 2013 Rhodium-Catalyzed Oxidative Annulation of Sulfoximines and Alkynes as an Approach to 1,2-Benzothiazines Angew. Chem. Int. Ed. 52 11573CrossRefGoogle Scholar
  18. 18.
    Chary B C, Kim S, Park Y, Kim J and Lee P H 2013 Palladium-Catalyzed C–H Arylation Using Phosphoramidate as a Directing Group at Room Temperature Org. Lett. 15 2692Google Scholar
  19. 19.
    Gandeepan P and Cheng C H 2012 Allylic Carbon–Carbon Double Bond Directed Pd-Catalyzed Oxidative ortho-Olefination of Arenes J. Am. Chem. Soc. 134 5738CrossRefPubMedGoogle Scholar
  20. 20.
    (a) Kumar V and Shaw A K 2008 First total synthesis of (+)-varitriol J. Org. Chem. 73 7526; (b) Ioset J R, Marston A, Gupta M P and Hostettmann K 2001 Five New Prenylated Stilbenes from the Root Bark of Lonchocarpus chiricanus J. Nat. Prod. 64 710Google Scholar
  21. 21.
    Zhou C and Larock R C 2005 Regio- and Stereoselective Route to Tetrasubstituted Olefins by the Palladium-Catalyzed Three-Component Coupling of Aryl Iodides, Internal Alkynes, and Arylboronic Acids J. Org. Chem. 70 3765CrossRefPubMedGoogle Scholar
  22. 22.
    Guis M, Marra C and Farina A 2002 A new efficient resveratrol synthesis Tetrahedron Lett. 43 597CrossRefGoogle Scholar
  23. 23.
    (a) Patureau F W and Glorius F 2010 Rh catalyzed olefination and vinylation of unactivated acetanilides J. Am. Chem. Soc. 132 9982; (b) Brasse M, Cámpora J, Ellman J A and Bergman R G 2013 Mechanistic study of the oxidative coupling of styrene with 2-phenylpyridine derivatives catalyzed by cationic Rhodium (III) via C–H activation J. Am. Chem. Soc. 135 6427Google Scholar
  24. 24.
    (a) Padala K and Jeganmohan M 2011 Ruthenium-Catalyzed Ortho-Alkenylation of Aromatic Ketones with Alkenes by C–H Bond Activation Org. Lett. 13 6144; (b) Padala K and Jeganmohan M 2012 Highly Regio- and Stereoselective Ruthenium(II)-Catalyzed Direct ortho-Alkenylation of Aromatic and Heteroaromatic Aldehydes with Activated Alkenes under Open Atmosphere Org. Lett. 14 1134Google Scholar
  25. 25.
    Manikandan R and Jeganmohan M 2017 Recent advances in the ruthenium(II)-catalyzed chelation-assisted C–H olefination of substituted aromatics, alkenes and heteroaromatics with alkenes via the deprotonation pathway Chem. Commun. 53 8931Google Scholar
  26. 26.
    Wang D H, Engle K M, Shi B F and Yu J Q 2010 Ligand-enabled reactivity and selectivity in a synthetically versatile aryl C–H olefination Science 327 315Google Scholar
  27. 27.
    Hu X H, Zhang J, Yang X F, Xu Y H and Loh T P 2015 Stereo- and Chemoselective Cross-Coupling between Two Electron-Deficient Acrylates: An Efficient Route to (Z,E)-Muconate Derivatives J. Am. Chem. Soc. 137 3169CrossRefPubMedGoogle Scholar
  28. 28.
    Shome S and Singh S P 2017 Design and synthesis of ruthenium bipyridine catalyst: An approach towards low-cost hydroxylation of arenes and heteroarenes Tetrahedron Lett. 58 3743Google Scholar
  29. 29.
    Dyson P J and Jessop P G 2016 Solvent effects in catalysis: rational improvements of catalysts via manipulation of solvent interactions Catal. Sci. Technol. 6 3302Google Scholar
  30. 30.
    Li B, Devaraj K, Darcel C and Dixneuf P H 2012 Catalytic C–H bond arylation of aryl imines and oxazolines in water with ruthenium(II)-acetate catalyst Tetrahedron 68 5179CrossRefGoogle Scholar

Copyright information

© Indian Academy of Sciences 2018

Authors and Affiliations

  1. 1.Polymers and Functional Materials DivisionCSIR-Indian Institute of Chemical TechnologyHyderabadIndia
  2. 2.Academy of Scientific and Innovative Research (AcSIR New Delhi)New DelhiIndia

Personalised recommendations