Synthesis 2019; 51(13): 2648-2659
DOI: 10.1055/s-0037-1611562
feature
© Georg Thieme Verlag Stuttgart · New York

Vicinal Dichlorination of o-Vinylbiphenyls and the Synthesis of 9-(Arylmethyl)fluorenes via Tandem Friedel–Crafts Alkylations

Zhensheng Zhao
,
Islam Jameel
,
This work was supported by a Discovery Grant from the Natural Sciences and Engineering Research Council (NSERC) of Canada (Grant No. 418602-2013).
Further Information

Publication History

Received: 25 March 2019

Accepted after revision: 02 May 2019

Publication Date:
28 May 2019 (online)

Abstract

Reacting ortho-vinylbiphenyls with (dichloroiodo)benzene (PhICl2) gives vicinal dichlorides, rapidly, and in excellent yield at room temperature. Treating the vic-dichlorides with 50 mol% AlCl3 in the presence of arene nucleophiles results in sequential intramolecular and intermolecular Friedel–Crafts alkylations to generate 9-(arylmethyl)fluorene derivatives. The dichlorination and alkylation reactions are operationally simple and tolerant of a variety of functional groups and substitution patterns, and give the products in moderate to excellent yield.

Supporting Information

 
  • References

  • 1 Willgerodt C. J. Prakt. Chem. 1886; 33: 154
  • 3 Lucas HJ, Kennedy ER. Org. Synth. 1942; 22: 69
  • 4 Zhao XF, Zhang C. Synthesis 2007; 551
    • 5a Montanari V, Resnati G. Tetrahedron Lett. 1994; 35: 8015
    • 5b Bravo P, Montanari V, Resnati G, Desmarteau DD. J. Org. Chem. 1994; 59: 6093
    • 5c Yusubov MS, Drygunova LA, Zhdankin VV. Synthesis 2004; 2289
    • 5d Podgorsek A, Jurisch M, Stavber S, Zupan M, Iskra J, Gladysz JA. J. Org. Chem. 2009; 74: 3133
    • 6a Yusubov MS, Zhdankin VV. Mendeleev Commun. 2010; 20: 185
    • 6b Chen JM, Zeng XM, Middleton K, Zhdankin VV. Tetrahedron Lett. 2011; 52: 1952
    • 7a Varvoglis A. Synthesis 1984; 709
    • 7b Merkushev EB. Russ. Chem. Rev. 1987; 56: 826
  • 8 Romero RM, Wöste TH, Muñiz K. Chem. Asian J. 2014; 9: 972
    • 9a Zhao Z, Racicot L, Murphy GK. Angew. Chem. Int. Ed. 2017; 56: 11620
    • 9b Zhao Z, Britt LH, Murphy GK. Chem. Eur. J. 2018; 24: 17002
    • 9c Zhao Z, Murphy GK. Beilstein J. Org. Chem. 2018; 14: 796
  • 10 Depken C, Krätzschmar F, Breder A. Org. Chem. Front. 2016; 3: 314

    • HVI-mediated reactions of styryl derivatives are prone to 1,2-phenyl shifts, which is also possible here; for further information see:
    • 11a Singh FV, Wirth T. Synthesis 2013; 45: 2499
    • 11b Brown M, Kumar R, Rehbein J, Wirth T. Chem. Eur. J. 2016; 22: 4030
    • 12a Ishibashi Y, Miyata K, Kitamura M. Eur. J. Org. Chem. 2010; 2010: 4201
    • 12b Sakai N, Nakajima T, Yoneda S, Konakahara T, Ogiwara Y. J. Org. Chem. 2014; 79: 10619
    • 12c Boo BH, Lee M, Jeon K.-S, Kim S.-J. J. Phys. Chem. A 2014; 118: 2269
    • 13a Greenhow EJ, McNeil D, White EN. J. Chem. Soc. 1952; 986
    • 13b Gualtieri F, Teodori E, Bellucci C, Pesce E, Piacenza G. J. Med. Chem. 1985; 28: 1621
    • 14a Claxton GP, Grisar JM, Roberts EM, Fleming RW. J. Med. Chem. 1972; 15: 500
    • 14b Dow RL. WO9221660A1, 1992
    • 14c Hamilton GS, Mewshaw RE, Bryant CM, Feng Y, Endemann G, Madden KS, Janczak JE, Perumattam J, Stanton LW, Yang XJ, Yin ZW, Venkataramen B, Liu DY. J. Med. Chem. 1995; 38: 1650
    • 14d Mahboobi S, Sellmer A, Pongratz H, Leonhardt M, Kraemer O, Boehmer F.-D, Kelter G. WO2016020369A1, 2016
    • 15a Fleckenstein CA, Plenio H. Organometallics 2008; 27: 3924
    • 15b Fleckenstein CA, Kadyrov R, Plenio H. Org. Process Res. Dev. 2008; 12: 475
    • 16a de Frutos Ó, Granier T, Gómez-Lor B, Jiménez-Barbero J, Monge Á, Gutiérrez-Puebla E, Echavarren AM. Chem. Eur. J. 2002; 8: 2879
    • 16b Kwag G, Park E, Lee SN. J. Appl. Polym. Sci. 2005; 96: 1335
  • 17 Formation of 9-tolyl-9,10-dihydrophenanthrene was also considered. Given the symmetry elements found in the 13C NMR spectrum of 5a, and that the spectra matched previous reports (see ref. 20), we deemed its structure to be correct. For reference, the spectra of 9-tolyl-9,10-dihydrophenanthrene can be found here: Goerner RN, Cote PN, Vittimberga BM. J. Org. Chem. 1977; 42: 19
    • 18a Yamato T, Komine M, Matsuo K. J. Chem. Res., Synop. 1997; 82
    • 18b Yamato T, Komine M, Nagano Y. Org. Prep. Proced. Int. 1997; 29: 300
    • 18c Comprehensive Organic Synthesis, 1st ed. Trost BM, Fleming I. Pergamon; Oxford: 1991
    • 18d Yamato T, Sakaue N, Shinoda N, Matsuo K. J. Chem. Soc., Perkin Trans. 1 1997; 1193
  • 19 Ohwada T. J. Am. Chem. Soc. 1992; 114: 8818
  • 20 Chen J, Li Y, Li S, Liu J, Zheng F, Zhang Z, Xu Q. Green Chem. 2017; 19: 623