JoVE Logo
Faculty Resource Center
Authors
Librarians
High Schools
About

Sign In

Summary

Abstract

Introduction

Protocol

Representative Results

Discussion

Acknowledgements

Materials

References

Chemistry

Preparazione di un Hexahelicene corannulene-funzionalizzati da rame (I) -catalyzed Acetilene-azide cicloaddizione di unità non planare policiclici aromatici

Published: September 18th, 2016

DOI:

10.3791/53954

1GIR MIOMeT, IU CINQUIMA, Área de Química Inorgánica, Universidad de Valladolid

Qui, vi presentiamo un protocollo per sintetizzare un complesso composto organico composto da tre unità poliaromatici non planari, montato facilmente con rendimenti ragionevoli.

The main purpose of this video is to show 6 reaction steps of a convergent synthesis and prepare a complex molecule containing up to three nonplanar polyaromatic units, which are two corannulene moieties and a racemic hexahelicene linking them. The compound described in this work is a good host for fullerenes. Several common organic reactions, such as free-radical reactions, C-C coupling or click chemistry, are employed demonstrating the versatility of functionalization that this compound can accept. All of these reactions work for planar aromatic molecules. With subtle modifications, it is possible to achieve similar results for nonplanar polyaromatic compounds.

Grazie alla loro particolare geometria, corannulene e helicenes sono molecole che possono adottare una struttura lontano dalla planarità e dar luogo a proprietà interessanti. 1-15 Negli ultimi anni, la ricerca dei recettori molecolari per nanotubi di carbonio e fullereni è una zona molto attiva 16-19 a causa, principalmente, alle loro potenziali applicazioni come materiali per le celle organiche solari, transistor, sensori e altri dispositivi. 20-28 l'ottima complementarietà di forma tra il corannulene e un fullerene hanno attirato l'attenzione di numerosi ricercatori, con l'obiettivo di progettare recettori molecolari in ....

Log in or to access full content. Learn more about your institution’s access to JoVE content here

1. Funzionalizzazione di 2,15-Dimethylhexahelicene

  1. Dibromination di 2,15-dimethylhexahelicene
    1. Pesare 0,356 g (1,0 mmol) di 2,15-dimethylhexahelicene, 0,374 g (2,1 mmoli) di -bromosuccinimide appena ricristallizzato N (NBS) e 24 mg (0,07 mmoli) di perossido di benzoile (BPO) (70% in peso con il 30% di acqua come stabilizzatore). Mettere tutti i solidi in un pallone da 100 ml Schlenk con ancoretta magnetica. Mettere in atmosfera di azoto da tre cicli di evac.......

Log in or to access full content. Learn more about your institution’s access to JoVE content here

Corannulene (3 a) e 2,15-dimethylhexahelicene (3 b) può essere preparato secondo i metodi attuali 46-48 in modo semplice con ottime rese (Figura 5). Entrambi condividono una molecola comune, 2,7-dimetilnaftalene, come materiale di partenza, dando luogo a una divergente alla sintesi convergente della molecola finale.

Log in or to access full content. Learn more about your institution’s access to JoVE content here

Composto finale 7 è stato preparato dopo 6 passi da precursori poliaromatici non planari 3 A e 3 B da moderata a molto buone rese in ogni reazione. La limitazione principale osservata in questo percorso è stata la bromurazione di composti poliaromatici non planari. Tuttavia, nel caso del composto 4 bis, una quantità importante di corannulene libero può essere recuperato per altri usi. La sintesi di .......

Log in or to access full content. Learn more about your institution’s access to JoVE content here

This work was funded by the Spanish Ministerio de Economìa y Competitividad (CTQ 2013-41067-P). H.B. acknowledge with thanks a MEC-FPI grant.

....

Log in or to access full content. Learn more about your institution’s access to JoVE content here

NameCompanyCatalog NumberComments
2,15-DimethylhexaheliceneN/AN/APrepared according to reference 5b,c in the main text.
CorannuleneN/AN/APrepared according to reference 5a in the main text.
N-Bromosuccinimide (NBS)Sigma AldrichB8.125-5ReagentPlus®, 99%. Recrystallized from hot water.
Benzoyl peroxide (BPO)Sigma AldrichB-2030~70% (titration). 30% water as stabilizer.
Sodium azideSigma AldrichS2002ReagentPlus®, ≥99.5%.
Gold (III) chloride HydrateSigma Aldrich50778puriss. p.a., ACS reagent, ≥49% Au basis.
EthynyltrimethylsilaneSigma Aldrich21817098%.
[PdCl2(dppf)]N/AN/APrepared according to reference 6 in the main text.
CuIN/AN/APrepared according to reference 7 in the main text.
KFSigma Aldrich30759999%, spray-dried.
(+)-Sodium L-ascorbateFluka11140BioXtra, ≥99.0% (NT).
Copper(II) Sulphate 5-hydratePanreac131270for analysis.
Carbon tetrachloride (CCl4)Fluka87030for IR spectroscopy, ≥99.9%.
Dichloromethane (DCM)Fisher ScientificD/1852/25Analytical reagent grade. Distilled prior to use.
HexaneFisher ScientificH/0355/25Analytical reagent grade. Distilled prior to use.
Ethyl acetateScharlauAC0145025SReagent grade. Distilled prior to use.
Tetrahydrofuran (THF)Fisher ScientificT/0701/25Analytical reagent grade. Distilled prior to use.
1,2-Dichloroethane (DCE)Sigma AldrichD6,156-3ReagentPlus®, 99%.
Methanol (MeOH)VWR20847.36AnalaR NORMAPUR.
Triethyl amine (NEt3)Sigma AldrichT0886≥99%.
Silica gelAcros360050010Particle size 40-60mm.
Sand - low ironFisher ScientificS/0360/63General purpose grade.
TLC Silica gel 60 F254Merck1.05554.0001
Monowave 300 (Microwave reactor)Anton Para
SonicatorGrupo Selecta30005136 Litres.

  1. Scott, L. T., Hashemi, M. M., Bratcher, M. S. Corannulene bowl-to-bowl inversion is rapid at room temperature. J. Am. Chem. Soc. 114 (5), 1920-1921 (1992).
  2. Sygula, A., et al. Bowl stacking in curved polynuclear aromatic hydrocarbons: crystal and molecular structure of cyclopentacorannulene. J. Chem. Soc., Chem. Commun. (22), 2571-2572 (1994).
  3. Nuckolls, C., et al. Circular Dichroism and UV−Visible Absorption Spectra of the Langmuir−Blodgett Films of an Aggregating Helicene. J. Am. Chem. Soc. 120 (34), 8656-8660 (1998).
  4. Beljonne, D., et al. Electro-optic response of chiral helicenes in isotropic media. J. Chem. Phys. 108 (4), 1301-1304 (1998).
  5. Treboux, G., Lapstun, P., Wu, Z., Silverbrook, K. Electronic conductance of helicenes. Chem. Phys. Lett. 301 (5-6), 493-497 (1999).
  6. Katz, T. J. Syntheses of Functionalized and Aggregating Helical Conjugated Molecules. Angew. Chem., Int. Ed. 39 (11), 1921-1923 (2000).
  7. Furche, F., et al. Circular Dichroism of Helicenes Investigated by Time-Dependent Density Functional Theory. J. Am. Chem. Soc. 122 (8), 1717-1724 (2000).
  8. Urbano, A. Recent Developments in the Synthesis of Helicene-Like Molecules. Angew. Chem., Int. Ed. 42 (34), 3986-3989 (2003).
  9. Botek, E., Champane, B., Turki, M., André, J. M. Theoretical study of the second-order nonlinear optical properties of [N]helicenes and [N]phenylenes. J. Chem. Phys. 120 (4), 2042-2048 (2004).
  10. Lovas, F. J., et al. Interstellar Chemistry: A Strategy for Detecting Polycyclic Aromatic Hydrocarbons in Space. J. Am. Chem. Soc. 127 (12), 4345-4349 (2005).
  11. Wigglesworth, T. J., Sud, D., Norsten, T. B., Lekhi, V. S., Branda, N. R. Chiral Discrimination in Photochromic Helicenes. J. Am. Chem. Soc. 127 (20), 7272-7273 (2005).
  12. Wu, Y. -. T., Siegel, J. S. Aromatic Molecular-Bowl Hydrocarbons: Synthetic Derivatives, Their Structures, and Physical Properties. Chem. Rev. 106 (12), 4843-4867 (2006).
  13. Tsefrikas, V. M., Scott, L. T. Geodesic Polyarenes by Flash Vacuum Pyrolysis. Chem. Rev. 106 (12), 4868-4884 (2006).
  14. Wu, Y. -. T., Hayama, T., Baldrige, K. K., Linden, A., Siegel, J. S. Synthesis of Fluoranthenes and Indenocorannulenes: Elucidation of Chiral Stereoisomers on the Basis of Static Molecular Bowls. J. Am. Chem. Soc. 128 (21), 6870-6884 (2006).
  15. Wu, Y. -. T., Siegel, J. S. Synthesis, structures, and physical properties of aromatic molecular-bowl hydrocarbons. Top. Curr. Chem. 349, 63-120 (2014).
  16. Pérez, E. M., Martìn, N. Curves ahead: molecular receptors for fullerenes based on concave-convex complementarity. Chem. Soc. Rev. 37 (8), 1512-1519 (2008).
  17. Tashiro, K., Aida, T. Metalloporphyrin hosts for supramolecular chemistry of fullerenes. Chem. Soc. Rev. 36 (2), 189-197 (2007).
  18. Kawase, T. Ball- Bowl- and Belt-Shaped Conjugated Systems and Their Complexing Abilities: Exploration of the Concave−Convex π−π Interaction. Chem. Rev. 106 (12), 5250-5273 (2006).
  19. Martin, N., Pérez, E. M. Molecular tweezers for fullerenes. Pure Appl. Chem. 82 (3), 523-533 (2010).
  20. Hoppe, H., Sariciftci, N. S. Morphology of polymer/fullerene bulk heterojunction solar cells. J. Mater. Chem. 16 (1), 45-61 (2006).
  21. Kim, S. N., Rusling, J. F., Papadimitrakopoulos, F. Carbon Nanotubes for Electronic and Electrochemical Detection of Biomolecules. Adv. Mater. 19 (20), 3214-3228 (2007).
  22. Dennler, G., Scharber, M. C., Brabec, C. J. Polymer-Fullerene Bulk-Heterojunction Solar Cells. Adv. Mater. 21 (13), 1323-1338 (2009).
  23. Helgesen, M., Søndergaard, R., Krebs, F. C. Advanced materials and processes for polymer solar cell devices. J. Mater. Chem. 20 (1), 36-60 (2010).
  24. Brabec, C. J., et al. Polymer-Fullerene Bulk-Heterojunction Solar Cells. Adv. Mater. 22 (34), 3839-3856 (2010).
  25. Delgado, J. L., Bouit, P. -. A., Filippone, S., Herranz, M. A., Martìn, N. Organic photovoltaics: a chemical approach. Chem. Commun. 46 (27), 4853-4865 (2010).
  26. Schnorr, J. M., Swager, T. M. Emerging Applications of Carbon Nanotubes. Chem. Mater. 23 (3), 646-657 (2011).
  27. Wang, C., Takei, K., Takahashi, T., Javey, A. Carbon nanotube electronics - moving forward. Chem. Soc. Rev. 42 (7), 2592-2609 (2013).
  28. Park, S., Vosguerichian, M., Bao, Z. A review of fabrication and applications of carbon nanotube film-based flexible electronics. Nanoscale. 5, 1727-1752 (2013).
  29. Mizyed, S., et al. Embracing C60 with Multiarmed Geodesic Partners. J. Am. Chem. Soc. 123 (51), 12770-12774 (2001).
  30. Sygula, A., Sygula, R., Ellern, A., Rabideau, P. W. Novel Twin Corannulene: Synthesis and Crystal Structure Determination of a Dicorannulenobarrelene Dicarboxylate. Org. Lett. 5 (15), 2595-2597 (2003).
  31. Georghiou, P. E., Tran, A. H., Mizyed, S., Bancu, M., Scott, L. T. Concave Polyarenes with Sulfide-Linked Flaps and Tentacles: New Electron-Rich Hosts for Fullerenes. J. Org. Chem. 70 (16), 6158-6163 (2005).
  32. Sygula, A., Fronczek, F. R., Sygula, R., Rabideau, P. W., Olmstead, M. M. A Double Concave Hydrocarbon Buckycatcher. J. Am. Chem. Soc. 129 (13), 3842-3843 (2007).
  33. Yanney, M., Sygula, A. Tridental molecular clip with corannulene pincers: is three better than two?. Tetrahedron Lett. 54 (21), 2604-2607 (2013).
  34. Stuparu, M. C. Rationally Designed Polymer Hosts of Fullerene. Angew. Chem., Int. Ed. 52 (30), 7786-7790 (2013).
  35. Le, V. H., Yanney, M., McGuire, M., Sygula, A., Lewis, E. A. Thermodynamics of Host-Guest Interactions between Fullerenes and a Buckycatcher. J. Phys. Chem. B. 118 (41), 11956-11964 (2014).
  36. Álvarez, C. M. Enhanced association for C70 over C60 with a metal complex with corannulene derivate ligands. Dalton Trans. 43 (42), 15693-15696 (2014).
  37. Álvarez, C. M. Assembling Nonplanar Polyaromatic Units by Click Chemistry. Study of Multicorannulene Systems as Host for Fullerenes. Org. Lett. 17 (11), 2578-2581 (2015).
  38. Yanney, M., Fronczek, F. R., Sygula, A. A 2:1 Receptor/C60 Complex as a Nanosized Universal Joint. Angew. Chem. Int. Ed. 54 (38), 11153-11156 (2015).
  39. Kuragama, P. L. A., Fronczek, F. R., Sygula, A. Bis-corannulene Receptors for Fullerenes Based on Klärner's Tethers: Reaching the Affinity Limits. Org. Lett. 17 (21), (2015).
  40. George, S. R. D., Frith, T. D. H., Thomas, D. S., Harper, J. B. Putting corannulene in its place. Reactivity studies comparing corannulene with other aromatic hydrocarbons. Org. Biomol. Chem. 13 (34), 9035-9041 (2015).
  41. Shen, Y., Chen, C. -. F. Helicenes: Synthesis and Applications. Chem. Rev. 112 (3), 1463-1535 (2012).
  42. Crassous, J., Saleh, N., Shen, C. Helicene-based transition metal complexes: synthesis, properties and applications. Chem. Sci. 5 (10), 3680-3694 (2014).
  43. Nakamura, K., Furumi, S., Takeuchi, M., Shibuya, T., Tanaka, K. Enantioselective Synthesis and Enhanced Circularly Polarized Luminescence of S-Shaped Double Azahelicenes. J. Am. Chem. Soc. 136 (15), 5555-5558 (2014).
  44. Schweinfurth, D., Zalibera, M., Kathan, M., Shen, C., Mazzolini, M., Trapp, N., Crassous, J., Gescheidt, G., Diederich, F. Helicene Quinones: Redox-Triggered Chiroptical Switching and Chiral Recognition of the Semiquinone Radical Anion Lithium Salt by Electron Nuclear Double Resonance Spectroscopy. J. Am. Chem. Soc. 136 (37), 13045-13052 (2014).
  45. Šámal, M., Chercheja, S., Rybáček, J., Vacek Chocholoušová, J., Vacek, J., Bednárová, L., Šaman, D., Stará, I. G., Starý, I. An Ultimate Stereocontrol in Asymmetric Synthesis of Optically Pure Fully Aromatic Helicenes. J. Am. Chem. Soc. 137 (26), 8469-8474 (2015).
  46. Siegel, J. S., Butterfield, A. M., Gilomen, B. Kilogram scale production of corannulene. Organic Process Research & Development. 16 (4), 664-676 (2012).
  47. Mallory, F. B., Mallory, C. W. Photocyclization of stilbenes and related molecules. Organic Reactions. , (1984).
  48. Sato, M., et al. Convenient synthesis and reduction properties of [7] circulene. J. Chem. Soc., Perkin Trans. 2. (9), 1909-1914 (1998).
  49. Anderson, G. K., Lin, M. Bis(Benzonitrile)dichloro complexes of palladium and platinum. Inorg Synth. 28, 60-63 (1990).
  50. Nataro, C., Fosbenner, S. M. Synthesis and Characterization of Transition-Metal Complexes Containing 1,1'-Bis(diphenylphosphino)ferrocene. J. Chem. Ed. 86 (12), 1412-1415 (2009).
  51. Kauffman, G. B., Pinnell, R. P. Copper (I) Iodide. Inorg. Synth. 6, 3-6 (1960).
  52. Sonogashira, K. J. Development of Pd-Cu catalyzed cross-coupling of terminal acetylenes with sp2-carbon halides. Organomet. Chem. 653 (1-2), 46-49 (2002).
  53. Chinchilla, R., Nájera, C. Recent advances in Sonogashira reactions. Chem. Soc. Rev. 40 (10), 5084-5121 (2011).
  54. Kolb, H. C., Finn, M. G., Sharpless, K. B. Click Chemistry: Diverse Chemical Function from a Few Good Reactions. Angew. Chem. Int. Ed. 40 (11), 2004-2021 (2001).
  55. Spiteri, C., Moses, J. E. Copper-Catalyzed Azide-Alkyne Cycloaddition: Regioselective Synthesis of 1,4,5-Trisubstituted 1,2,3-Triazoles. Angew. Chem. Int. Ed. 49 (1), 31-33 (2010).

This article has been published

Video Coming Soon

JoVE Logo

Privacy

Terms of Use

Policies

Contact Us

Recommend to library

JoVE NEWSLETTERS

Research

Education

Authors

Librarians

ABOUT JoVE

Copyright © 2024 MyJoVE Corporation. All rights reserved