Palladium-Catalyzed Naphthylation of Acenaphthylene

Abstract

A bisnaphthyl-substituted acenaphthylene is synthesized via two independent two-step procedures, Pd-catalyzed and classically with Grignard reagents. The subsequent dehydrocyclization stops after the first carbon-carbon bond formation, leading to an octacyclic π-system as the main product.

Key words

palladium - Heck reaction - polycyclic aromatic - hydrocarbons - annulated cyclopentadienes

References and Notes

• 1 Scott LT. Hashemi MM. Meyer DT. Warren HB. J. Am. Chem. Soc.  1991,  113:  7082 
• 2 Stoddart MW. Brownie JH. Baird MC. Schmider HL. J. Organomet. Chem.  2005,  690:  3440 
• 3 Sakurai H. Daiko T. Sakane H. Amaya T. Hirao T. J. Am. Chem. Soc.  2005,  127:  11580 
• 4 Dyker G. J. Org. Chem.  1993,  58:  234 
• 5 Waldvogel SR. Mirk D. In Handbook of C-H Transformations   Wiley-VCH; Weinheim: 2005.  p.251-261  
• 6 Dyker G. Heiermann J. Miura M. Pivsa-Art S. Satoh T. Nomura M. Chem. Eur. J.  2000,  6:  3426 
• 7 Dyker G. Chem. Ber./Recl.  1997,  130:  1567 
• 8 Gundermann KD. Z. Naturforsch., B: Chem. Sci.  1992,  47:  1764 
• 10 Muth E. Ph.D. Thesis   Bochum University; Germany: 2004. 
• 11 Catellani M. Motti E. New J. Chem.  1998,  22:  759 
• 12 Alder RW. Colclough D. Grams F. Orpen AG. Tetrahedron  1990,  46:  7933 
• 13 Olah GA. Husain A. Gupta BGB. Narang SC. Angew. Chem.  1981,  93:  705 
• 14 Simpson CD. Brand JD. Berresheim AJ. Przybilla L. Räder HJ. Müllen K. Chem. Eur. J.  2002,  8:  1424 
• 15 Klumpp DA. Baek DN. Prakash GKS. Olah GA. J. Org. Chem.  1997,  62:  6666 

9

X-ray data for 5 were collected on a Bruker AXS-SMART 1000 (Mo Kα radiation). The structure was solved by direct methods and refined by full matrix least squares using SHELXTL-97 All non-hydrogen atoms were refined using anisotropic thermal parameters.
Crystal Data for 5
T = 213(2) K, C₃₂H₂₀, M = 404.48, monoclinic space group P2₁/n, a = 12.190(5) Å, b = 10.104(4) Å, c = 17.237(7) Å, β = 102.484(9)°, V = 2072.9(15) ų, Z = 4, D _C = 1.296 g/cm³, µ = 0.073 mm^-1, 2.35° < Θ < 25.15°, reflections collected/unique 10788/3646 [R _int = 0.0489], data/restraints/parameters 3646/0/289, GOF 1.021, final R[I > 2σ(I)] R1 = 0.0416, wR2 (all data) = 0.1082, residual density 0.134 and -0.190 e A^-3.
Crystal Data for 6
The crystals were of poor quality, twinned and weakly diffracting. C₃₂H₂₀, M = 404.48, monoclinic space group P2₁/c, a = 11.352(3) Å, b = 24.248(4) Å, c = 7.835(2) Å, β = 96.80(2)°, V = 2141.4(8) ų, Z = 4, T = 293(2) K, µ = 0.071 mm^-1, 32624/3877/2025 reflections collected/unique/observed, R _int = 0.1775, R1 = 0.1268, wR2 (all data) = 0.2319, 290 parameters. All non-hydrogen atoms calculated anisotropic; positions of the H atoms calculated for idealized positions. The structure was solved and refined using SHELXTL-97 (G. M. Sheldrick, Universität Göttingen 1997).
Crystal Data for 11
Again, the crystals were of poor quality and weakly diffracting. C₃₂H₂₀, M = 404.48, tetragonal space group I-4, a = 20.673(2) Å, c = 10.448(1) Å, V = 4465.4(9) ų, Z = 8, T = 293(2) K, µ = 0.068 mm^-1, 2380/1798/934 reflections collected/unique/observed, R _int = 0.0670, R1 = 0.1283, wR2 (all data) = 0.3307, 289 parameters. All non-hydrogen atoms calculated anisotropic; positions of the H atoms calculated for idealized positions. The structure was solved and refined using SHELXTL-97 (G. M. Sheldrick, Universität Göttingen 1997).
X-ray data have been deposited at the Cambridge Crystallographic Data Centre (deposition numbers CCDC-611565 for 5, CCDC-614432 for 6 and CCDC-614433 for 11. Copies of the data can be obtained free of charge at www.ccdc.cam.uk/data_request/cif or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ [fax: [phone]; e-mail: [e-mail]].