Lithium(1+)-Catalyzed Nazarov-Type Cyclization of 1-Arylbuta-2,3-dien-1-ols: Synthesis of Benzofulvene Derivatives

Abstract

Lithium hexafluorophosphate proved to be an effective catalyst for a Nazarov-type cyclization of 1-arylbuta-2,3-dien-1-ols to afford benzofulvenes, valuable as building blocks for functional materials and bioactive compounds.

Key words

catalysis - cyclizations - benzofulvenes - dienols - lithium

• References and Notes


For applications of benzofulvenes in material chemistry, see:
• 1a Rogers JS, Lachicotte RJ, Bazan GC. Organometallics 1999; 18: 3976
• 1b Escarpa Gaede P. J. Organomet. Chem. 2000; 616: 29
• 1c Nakano T, Takewaki K, Yade T, Okamoto Y. J. Am. Chem. Soc. 2001; 123: 9182
• 1d Cappelli A, Mohr GP, Anzini M, Vomero S, Donati A, Casolaro M, Mendichi R, Giorgi G, Makovec F. J. Org. Chem. 2003; 68: 9473
• 1e Basurto S, García S, Neo AG, Torroba T, Marcos CF, Miguel D, Barberá J, Ros MB, de la Fuente MR. Chem. Eur. J. 2005; 11: 5362
• 1f Görl C, Alt HG. J. Organomet. Chem. 2007; 692: 5727
• 1g Kosaka Y, Kitazawa K, Inomata S, Ishizone T. ACS Macro Lett. 2013; 2: 164
• 1h Zhang Y, Ma H, Huang J. J. Mol. Catal. A: Chem. 2013; 373: 85
• 1i Cappelli A, Grisci G, Paolino M, Castriconi F, Giuliani G, Donati A, Lamponi S, Mendichi R, Boccia AC, Samperi F, Battiato S, Paccagnini E, Gentile M, Licciardi M, Giammona G, Vomero S. Chem. Eur. J. 2013; 19: 9710

For applications of benzofulvenes in medicinal chemistry, see:
• 2a Alcalde E, Mesquida N, Frigola J, López-Pérez S, Mercè R. Org. Biomol. Chem. 2008; 6: 3795
• 2b Felts AS, Siegel BS, Young SM, Moth CW, Lybrand TP, Dannenberg AJ, Marnett LJ, Subbaramaiah K. J. Med. Chem. 2008; 51: 4911
• 2c Walters MJ, Blobaum AL, Kingsley PJ, Felts AS, Sulikowski GA, Marnett LJ. Bioorg. Med. Chem. Lett. 2009; 19: 3271
• 2d Jeffrey JL, Sarpong R. Tetrahedron Lett. 2009; 50: 1969

For Pd-catalyzed Heck-type reactions, see:
• 3a Dyker G, Borowski S, Henkel G, Kellner A, Dix I, Jones PG. Tetrahedron Lett. 2000; 41: 8259
• 3b Rahman SM. A, Sonoda M, Itahashi K, Tobe Y. Org. Lett. 2003; 5: 3411
• 3c Furuta T, Asakawa T, Iinuma M, Fujii S, Tanaka K, Kan T. Chem. Commun. 2006; 3648
• 3d Lee C.-Y, Wu M.-J. Eur. J. Org. Chem. 2007; 3463
• 3e Ye S, Gao K, Zhou H, Yang X, Wu J. Chem. Commun. 2009; 5406
• 3f Kim KH, Kim SH, Park BR, Kim JN. Tetrahedron Lett. 2010; 51: 3368
• 3g Ye S, Yang X, Wu J. Chem. Commun. 2010; 2950
• 3h Ye S, Wu J. Org. Lett. 2011; 13: 5980
• 3i Wang W.-Y, Sun L.-L, Deng C.-L, Tang R.-Y. Zhang X.-G. 2013; 45: 118
• 3j Lim CH, Kim KH, Lim JW, Kim JN. Tetrahedron Lett. 2013; 54: 5808

For Au-catalyzed transformations, see:
• 3k Li C, Zeng Y, Wang J. Tetrahedron Lett. 2009; 50: 2956
• 3l Álvarez E, Miguel D, García-García P, Fernández-Rodríguez MA, Rodríguez F, Sanz R. Synthesis 2012; 44: 1874
• 3m Hashmi AS. K, Braun I, Nösel P, Schädlich J, Wieteck M, Rudolph M, Rominger F. Angew. Chem. Int. Ed. 2012; 51: 4456

For radical cyclizations, see:
• 3n Kovalenko SV, Peabody S, Manoharan M, Clark RJ, Alabugin IV. Org. Lett. 2004; 6: 2457
• 3o Peabody SW, Breiner B, Kovalenko SV, Patil S, Alabugin IV. Org. Biomol. Chem. 2005; 3: 218
• 3p Schmittel M, Vavilala C. J. Org. Chem. 2005; 70: 4865
• 3q Vavilala C, Byrne N, Kraml CM, Ho DM, Pascal RA. Jr. J. Am. Chem. Soc. 2008; 130: 13549
• 3r Bucher G, Mahajan AA, Schmittel M. J. Org. Chem. 2008; 73: 8815

For C–H bond activations, see:
• 3s Tsuchikama K, Kasagawa M, Endo K, Shibata T. Synlett 2010; 97
• 3t Lee P.-S, Fujita T, Yoshikai N. J. Am. Chem. Soc. 2011; 133: 17283
• 3u Chinnagolla RK, Jeganmohan M. Eur. J. Org. Chem. 2012; 417

For other methods, see:
• 3v Schreiner PR, Prall M, Lutz V. Angew. Chem. Int. Ed. 2003; 42: 5757
• 3w Watanabe M, Shiine K, Ideta K, Matsumoto T, Thiemann T. J. Chem. Res. 2008; 669
• 3x Lu J.-M, Zhu Z.-B, Shi M. Chem. Eur. J. 2009; 15: 963

For recent reviews on the Nazarov cyclization, see:
• 4a Grant TN, Rieder CJ, West FG. Chem. Commun. 2009; 5676
• 4b Nakanishi W, West FG. Curr. Opin. Drug Discovery Dev. 2009; 12: 732
• 4c Shimada N, Stewart C, Tius MA. Tetrahedron 2011; 67: 5851
• 4d Vaidya T, Eisenberg R, Frontier AJ. ChemCatChem 2011; 3: 1531
• 4e Spencer WT. III, Vaidya T, Frontier AJ. Eur. J. Org. Chem. 2013; 3621
• 4f Tius MA. Chem. Soc. Rev. 2014; 43: 2979
• 4g West FG, Scadeng O, Wu Y.-K, Fradette RJ, Joy S. In Comprehensive Organic Synthesis II, Vol. 5 . Molander GA, Knochel P. Elsevier; Amsterdam: 2014. 2nd ed., Chap. 5.18, 827
• 5 Toda F, Ooi N, Akagi K. Bull. Chem. Soc. Jpn. 1971; 44: 1050
• 6a Langer P. Chem. Commun. 1999; 1217
• 6b Langer P, Döring M, Seyferth D, Görls H. Chem. Eur. J. 2001; 7: 573
• 7 Cordier P, Aubert C, Malacria M, Lacôte E, Gandon V. Angew. Chem. Int. Ed. 2009; 48: 8757
• 8 Poonoth M, Krause N. Adv. Synth. Catal. 2009; 351: 117 ; and references cited therein
• 9 Activation of the alcohol functionality by a combination of LiNTf₂ and Bu₄NPF₆ has been reported, see: Niggemann M, Meel MJ. Angew. Chem. Int. Ed. 2010; 49: 3684
• 10 α-Allenols can be readily prepared by titanium-mediated selective allenylation of ketones and aldehydes, see: Nakagawa T, Kasatkin A, Sato F. Tetrahedron Lett. 1995; 36: 3207
• 11 Benzofulvenes 2 readily undergo polymerization even at low temperature (–20 °C) when they are stored as neat oils.
• 12 LiPF₆ (H₂O: 20 ppm max; 99.9+%-Li) was purchased from Strem Chemicals, Inc., Newburyport, MA, USA.
• 13 A combination of LiPF₆ with hexane has been reported to be an efficient system for the tetrahydropyranylation of tertiary alcohols, see: Hamada N, Sato T. Synlett 2004; 1802
• 14 The spectroscopic data for E-3 were in full agreement with those reported in the literature.

For recent reviews on the Meyer–Schuster rearrangement, see:
• 15a Engel DA, Dudley GB. Org. Biomol. Chem. 2009; 7: 4149
• 15b Cadierno V, Crochet P, García-Garrido SE, Gimeno J. Dalton Trans. 2010; 39: 4015
• 16 2,3-Dimethyl-1-methylene-1H-indene (2a); Typical Procedure In a glove box, an oven-dried test tube equipped with a magnetic stirrer bar was charged with LiPF₆ (3.8 mg, 0.025 mmol). The tube was removed from the glove box and a solution of α-allenol 1a (87.1 mg, 0.50 mmol) in hexane (3.0 mL) was added. The mixture was heated at 65 °C for 1 h, cooled to r.t., and passed through a short column of activated alumina, eluting with Et₂O. The eluent was concentrated and the residue was purified by column chromatography (silica gel, hexane) to give a yellow oil; yield: 67.7 mg (87%). IR (neat): 3047, 2971, 1611, 1441, 1412 cm^–1; ¹H NMR (500 MHz, CDCl₃): δ = 2.05–2.07 (m, 3 H), 2.08–2.10 (m, 3 H), 5.57 (s, 1 H), 5.89 (s, 1 H), 7.10–7.14 (m, 2 H), 7.23 (ddd, J = 7.5, 7.5, 1.0 Hz, 1 H), 7.48–7.52 (m, 1 H); ¹³C NMR (125 MHz, CDCl₃) δ = 9.8, 10.7, 108.4, 117.7, 119.0, 124.8, 128.1, 132.0, 136.2, 137.3, 144.7, 148.7; HRMS (EI): m/z [M⁺] calcd for C₁₂H₁₂: 156.0939; found: 156.0933.