A Simple and Versatile Synthesis of 1,2-Diarylacenaphthylenes via Suzuki-Miyaura Coupling, and its Application in the Synthesis of a New ­Acenaphthylene-1,2-bis(p-quinone methide) Derivative

Abstract

1,2-Diaryl-substituted acenaphthylene derivatives were prepared simply via Suzuki-Miyaura coupling in good or excellent yields. By applying this method, acenaphthylene-1,2-bis(p-quinone methide) with two 3,5-di-tert-butyl-4-oxocyclohexadienylidene units, which is a stable deep purple crystalline substance with a very broad absorption in the whole visible region and relatively low ­reduction potential, was prepared and characterized.

Key words

arenes - chromophores - cross-coupling - quinines - ­Suzuki reaction

References and Notes

• 1a Wu Y.-T. Siegel JS. Chem. Rev.  2006,  106:  4843 
• 1b Tsefrikas VM. Scott LT. Chem. Rev.  2006,  106:  4868 
• 1c Echavarren AM. Gomez-Lor B. Gonzalez JJ. de Frutos O. Synlett  2003,  585 
• 2a Neudorff WD. Schulte N. Lentz D. Schlüter AD. Org. Lett.  2001,  3:  3115 
• 2b Gourdon A. Eur. J. Org. Chem.  1998,  2797 
• 3a Bachmann WE. Chu EJ.-H. J. Am. Chem. Soc.  1936,  58:  1118 
• 3b Bartlett PD. Brown RF. J. Am. Chem. Soc.  1940,  62:  2927 
• 3c Lai YH. Chen P. J. Chem. Soc., Perkin Trans. 2  1989,  1665 
• 3d Lai YH. Chen P. Cui YX. J. Chem. Soc., Perkin Trans. 2  1996,  1655 
• 3e Schank K. Beck H. Buschlinger M. Eder J. Heisel T. Pistorius S. Wagner C. Helv. Chim. Acta  2000,  83:  801 
• 4a Kurata H. Tanaka T. Oda M. Chem. Lett.  1999,  749 
• 4b Kurata H. Shimoyama T. Matsumoto K. Kawase T. Oda M. Bull. Chem. Soc. Jpn.  2001,  74:  1327 
• 4c Kurata H. Takehara Y. Kawase T. Oda M. Chem. Lett.  2003,  32:  538 
• 4d Kawase T. Minami Y. Nishigaki N. Okano S. Kurata H. Oda M. Angew. Chem. Int. Ed.  2005,  44:  316 
• 4e Kurata H. Takehara Y. Matsumoto K. Kawase T. Oda M. Chem. Lett.  2005,  34:  1660 
• 4f Kurata H. Kim S. Matsumoto K. Kawase T. Oda M. Chem. Lett.  2007,  36:  386 
• 5a Hassan J. Sevignon M. Gozzi C. Schuz E. Lemaire M. Chem. Rev.  2002,  102:  1359 
• 5b Bellina F. Carpita A. Rossi R. Synthesis  2004,  2419 
• 6 Nickel and platinum complexes of 4 have been reported: Begum RA. Sharp PR. Organometallics  2005,  24:  2670 
• 7 Recently, Dyker et al. reported a Heck-type reaction of a parent acenaphthylene with 1-bromonaphthalene to afford a bisnaphthylated product in 19% yield: Dyker G. Merz K. Oppel IM. Muth E. Synlett  2007,  897 
• 8 Trost BM. Brittelli DR. J. Org. Chem.  1967,  32:  2620 
• 10 Boronic acid 5 was prepared by reaction of 4-bromo-2,6-di-tert-butylphenol with tert-BuLi (3 equiv) and subsequently with tri(isopropoxy)borane (4 equiv). Compound 5 was obtained as a mixture with the corresponding boroxane formed by dehydration.Compound 5: white powder. ¹H NMR (270 MHz, CDCl₃): δ = 7.54 (s, 2 H), 5.48 (s, 1 H), 4.40 (s, 2 H), 1.47 (s 18 H).The boroxane: white powder. ¹H NMR (270 MHz, CDCl₃): δ = 8.10 (s, 6 H), 5.59 (s, 3 H), 1.53 (s, 54 H). The trimethylsilyl-protected derivative of 5 was synthesized by Satoh et al.: Satoh Y. Shi C. Synthesis  1994,  1146 
• 11 Kurata H. Tanaka T. Sauchi T. Kawase T. Oda M. Chem. Lett.  1997,  947 
• 15 Richter F. J. Org. Chem.  1960,  25:  356 

9

In agreement with literature reports, [3c] [7] ¹H NMR spectra of 1e and 1f show the presence of 1:1 mixtures of rotational isomers.

12

Crystallographic data of 3: C₄₀H₄₆O₂, M = 558.80, monoclinic, P2₁/c, a = 21.040 (9), b = 13.717 (6), c = 24.053 (10) Å, β = 103.24 (4)°, V = 6757 (17) ų, Z = 8, D _c = 1.098 g cm^-3, 64264 reflections measured, 15373 unique (R _int = 0.145) used in refinement. R1 = 0.058 [I > 2σ(I)], wR = 0.155 (all data). T = 200 K. X-ray data have been deposited at the Cambridge Crystallographic Data Centre (CCDC-649872). 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]].

13

Variable-temperature NMR measurement of 3 was performed in a bromobenzene-d ₅ solution. The coalescence temperature of the tert-butyl signals was 78 ± 3 °C.

14

Measurements were carried out in DMF solution at r.t. using a glassy carbon electrode with tetrabutylammonium perchlorate as the supporting electrolyte.