Synthesis of Trifluoromethyl-Substituted Ethyl Picolinate Derivatives by the Cobalt-Catalyzed Regioselective Intermolecular [2+2+2] Cycloaddition

Abstract

We demonstrated the intermolecular [2+2+2] cycloaddition of aryl- and trifluoromethyl-substituted internal alkyne and ethyl cyano­formate, and succeeded in constructing the pyridine derivatives using the CoI₂/dcype/Zn catalyst system. The reaction proceeded with a high regioselectivity, and two trifluoromethyl-substituted ethyl picolinate derivatives were obtained as a single regioisomer.

Key words

cobalt - cycloaddition - fluorine - pyridines - nitriles - alkynes

• References and Notes

• 1a Bönnemann H. Angew. Chem., Int. Ed. Engl. 1985; 24: 248
• 1b Varela JA, Saá C. Chem. Rev. 2003; 103: 3787
• 1c Henry GD. Tetrahedron 2004; 60: 6043
• 1d Chopade PR, Louie J. Adv. Synth. Catal. 2006; 348: 2307
• 1e Heller B, Hapke M. Chem. Soc. Rev. 2007; 36: 1085
• 1f Varela JA, Saá C. Synlett 2008; 2571
• 1g Galan BR, Rovis T. Angew. Chem. Int. Ed. 2009; 48: 2830
• 1h Domínguez G, Pérez-Castells J. Chem. Soc. Rev. 2011; 40: 3430
• 1i Weding N, Hapke M. Chem. Soc. Rev. 2011; 40: 4525
• 1j Broere DL. J, Ruijter E. Synthesis 2012; 44: 2639
• 1k Tanaka K. Heterocycles 2012; 85: 1017
• 1l Okamoto S, Sugiyama Y. Synlett 2013; 24: 1044
• 2a Varela JA, Castedo L, Saá S. J. Am. Chem. Soc. 1998; 120: 12147
• 2b Naiman A, Vollhardt KP. C. Angew. Chem., Int. Ed. Engl. 1977; 16: 708
• 2c Brien DJ, Naiman A, Vollhardt KP. C. J. Chem. Soc., Chem. Commun. 1982; 133
• 2d Parnell C, Vollhardt KP. C. Tetrahedron 1985; 24: 5791
• 2e Varela JA, Castedo L, Saá C. J. Am. Chem. Soc. 1998; 120: 12147
• 2f Moretto AF, Zhang H.-C, Maryanoff BE. J. Am. Chem. Soc. 2001; 123: 3157
• 2g Boñaga LV. R, Zhang H.-C, Moretto AF, Ye H, Gauthier DA, Li J, Leo GC, Maryanoff BE. J. Am. Chem. Soc. 2005; 127: 3473
• 2h Young DD, Deiters A. Angew. Chem. Int. Ed. 2007; 46: 5187
• 2i Chang H.-T, Jeganmohan M, Cheng C.-H. Org. Lett. 2007; 9: 505
• 2j Kase K, Goswami A, Ohtaki K, Tanabe E, Saino N, Okamoto S. Org. Lett. 2007; 9: 931
• 2k Geny A, Agenet N, Iannazzo L, Malacria M, Aubert C, Gandon V. Angew. Chem. Int. Ed. 2009; 48: 1810
• 2l Garcia P, Moulin S, Miclo Y, Leboeuf D, Gandon V, Aubert C, Malacria M. Chem. Eur. J. 2009; 15: 2129
• 2m Mclver AL, Deiters A. Org. Lett. 2010; 12: 1288
• 2n Hapke M, Kral K, Fischer C, Spannenberg A, Gutnov A, Redkin D, Heller B. J. Org. Chem. 2010; 75: 3993
• 2o Hapke M, Weding N, Spannenberg A. Organometallics 2010; 29: 4298
• 2p Garcia P, Evanno Y, George P, Sevrin M, Ricci G, Malacria M, Aubert C, Gandon V. Org. Lett. 2011; 13: 2030
• 2q Zou Y, Liu Q, Deiters A. Org. Lett. 2011; 13: 4352
• 2r Swami A, Ramana CV. Synlett 2015; 26: 604
• 3a Nishida G, Suzuki N, Noguchi K, Tanaka K. Org. Lett. 2006; 8: 3489
• 3b Tanaka K, Hara H, Nishida G, Hirano M. Org. Lett. 2007; 9: 1907
• 3c Komine Y, Kamisawa A, Tanaka K. Org. Lett. 2009; 11: 2361
• 3d Shibata T, Uchiyama T, Endo K. Org. Lett. 2009; 11: 3906
• 3e Konno T, Moriyasu K, Kinugawa R, Ishihara T. Org. Biomol. Chem. 2010; 8: 1718
• 3f Neely JM, Rovis T. J. Am. Chem. Soc. 2013; 135: 66
• 3g Haraburda E, Lledó A, Roglans A, Pla-Quintana A. Org. Lett. 2015; 17: 2882
• 3h Xu F, Wang C, Wang H, Li X, Wan B. Green Chem. 2015; 17: 799
• 3i Kashima K, Ishii M, Tanaka K. Eur. J. Org. Chem. 2015; 1092
• 4a D’Souza BR, Lane TK, Louie J. Org. Lett. 2011; 13: 2936
• 4b Richard V, Ipouck M, Mérel DS, Gaillard S, Whitby RJ, Witulski B, Renaud J.-L. Chem. Commun. 2014; 50: 593
• 5a Yamamoto Y, Ogawa R, Itoh K. J. Am. Chem. Soc. 2001; 123: 6189
• 5b Yamamoto Y, Okuda S, Itoh K. Chem. Commun. 2001; 1102
• 5c Yamamoto Y, Kinpara K, Ogawa R, Nishiyama H, Itoh K. Chem. Eur. J. 2006; 12: 5618
• 5d Medina S, Domínguez G, Pérez-Castells J. Org. Lett. 2012; 14: 4982
• 6 Onodera G, Shimizu Y, Kimura J, Kobayashi J, Ebihara Y, Kondo K, Sakata K, Takeuchi R. J. Am. Chem. Soc. 2012; 134: 10515
• 7a Tekavec TN, Zuo G, Simon K, Louie J. J. Org. Chem. 2006; 71: 5834
• 7b Kumar P, Prescher S, Louie J. Angew. Chem. Int. Ed. 2011; 50: 10694
• 7c Stolley RM, Duong HA, Louie J. Organometallics 2013; 32: 4952
• 8a Varela JA, Castedo L, Saá C. J. Org. Chem. 2003; 68: 8595
• 8b Yamamoto Y, Kinpara K, Saigoku T, Takagishi H, Okuda S, Nishiyama H, Itoh K. J. Am. Chem. Soc. 2005; 127: 605
• 9a McCormick MM, Duong HA, Zuo G, Louie J. J. Am. Chem. Soc. 2005; 127: 5030
• 9b Hoshimoto Y, Ohata T, Ohashi M, Ogoshi S. Chem. Eur. J. 2014; 20: 4105
• 9c Zhong Y, Spahn NA, Stolley RM, Nguyen MH, Louie J. Synlett 2015; 26: 307
• 10a Wakatsuki Y, Yamazaki H. Tetrahedron Lett. 1973; 36: 3383
• 10b Bönnemann H, Brinkmann R, Schenkluhn H. Synthesis 1974; 575
• 10c Bönnemann H, Brinkmann R. Synthesis 1975; 600
• 10d Wakatsuki Y, Yamazaki H. J. Chem. Soc., Dalton Trans. 1978; 1278
• 10e Jeller B, Sundermann B, Fischer C, You J, Chen W, Drexler H.-J, Knochel P, Bonrath W, Gutnov A. J. Org. Chem. 2003; 68: 9221
• 10f Senaiar RS, Young DD, Deiters A. Chem. Commun. 2006; 1313
• 10g Young DD, Teske JA, Deiters A. Synthesis 2009; 3785
• 11a Cioni P, Diversi P, Ingrosso G, Lucherini A, Ronca P. J. Mol. Catal. 1987; 40: 337
• 11b Diversi P, Ingrosso G, Lucherini A, Minutillo A. J. Mol. Catal. 1987; 40: 359
• 11c Pietro D, Ermini L, Ingrosso G, Lucherini A. J. Organomet. Chem. 1993; 447: 291
• 11d Costa M, Dias FS, Chiusoli GP, Gazzola GL. J. Organomet. Chem. 1995; 488: 47
• 11e Costa M, Dalcanale E, Dias FS, Graiff C, Tiripicchio A, Bigliardi L. J. Organomet. Chem. 2001; 619: 179
• 11f Tanaka K, Suzuki N, Nishida G. Eur. J. Org. Chem. 2006; 3917
• 11g Komine Y, Tanaka K. Org. Lett. 2010; 12: 1312
• 12a Wang C, Li X, Wu F, Wan B. Angew. Chem. Int. Ed. 2011; 50: 7162
• 12b Lane TK, D’Souza BR, Louie J. J. Org. Chem. 2012; 77: 7555
• 12c Wang C, Wang D, Xu F, Pan B, Wan B. J. Org. Chem. 2013; 78: 3065
• 13 Satoh Y, Obora Y. J. Org. Chem. 2013; 78: 7771
• 14a Isanbor C, O’Hagan D. J. Fluorine Chem. 2006; 127: 303
• 14b Bégué J.-P, Bonnet-Delpon D. J. Fluorine Chem. 2006; 127: 992
• 14c Lirk KL. J. Fluorine Chem. 2006; 127: 1013
• 14d Müller K, Faeh C, Diederich F. Science 2007; 317: 1881
• 14e Purser S, Moore PR, Swallow S, Gouverneur V. Chem. Soc. Rev. 2008; 37: 320
• 14f Wang J, Sánchez-Roselló M, Aceña JL, del Pozo C, Sorochinsky AE, Fustero S, Soloshonok VA, Liu H. Chem. Rev. 2014; 114: 2432
• 14g Campbell MG, Ritter T. Chem. Rev. 2015; 115: 612
• 15a Kawatsura M, Wada S, Hayase S, Itoh T. Synlett 2006; 2483
• 15b Kawatsura M, Hirakawa T, Tanaka T, Ikeda D, Hayase S, Itoh T. Tetrahedron Lett. 2008; 49: 2450
• 15c Hirakawa T, Ikeda K, Ogasa H, Kawatsura M, Itoh T. Synlett 2010; 2887
• 15d Kawatsura M, Namioka J, Kajita K, Yamamoto M, Tsuji H, Ioth T. Org. Lett. 2011; 13: 3285
• 15e Hirakawa T, Ikeda K, Ikeda D, Tanaka T, Ogasa H, Kawatsura M, Itoh T. Tetrahedron 2011; 67: 8238
• 15f Kawatsura M, Terasaki S, Minakawa M, Hirakawa T, Ikeda K, Itoh T. Org. Lett. 2014; 16: 2442
• 15g Isa K, Minakawa M, Kawatsura M. Chem. Commun. 2015; 51: 6761
• 15h Ishikawa T, Sonehara T, Minakawa M, Kawatsura M. Org. Lett. 2016; 18: 1422
• 15i Ikeda K, Futamura T, Hanakawa T, Minakawa M, Kawatsura M. Org. Biomol. Chem. 2016; 14: 3501
• 16a Kawatsura M, Yamamoto M, Namioka J, Kajita K, Hirakawa T, Itoh T. Org. Lett. 2011; 13: 1001
• 16b Minakawa M, Ishikawa T, Namioka J, Hirooka S, Zhou B, Kawatsura M. RSC Adv. 2014; 4: 41353
• 17a Konno T, Chae J, Kanda M, Nagai G, Tamura K, Ishihara T, Yamanaka H. Tetrahedron 2003; 59: 7571
• 17b Konno T. Synlett 2014; 25: 1350
• 17c Sakaguchi Y, Nakazaki Y, Moriyasu K, Konno T. J. Fluorine Chem. 2015; 179: 64
• 17d Müller C, Lachicotte RJ, Jones WD. Organometallics 2002; 21: 1975
• 18 The reaction provided detectable amount of benzene derivative, which was formed by the trimerization of 1a, as a side product.
• 19 General Procedure for the Cobalt-Catalyzed [2+2+2] Cycloaddition of Aryl- and Trifluoromethyl-Substituted Internal Alkynes 1 and Ethyl Cyanoformate (2) A typical procedure is given for the reaction of 1-(4-methoxyphenyl)-3,3,3-trifluoropropyne (1a) with ethyl cyanoformate (2, Table 1, entry 14). CoI₂ (19 mg, 0.061 mmol) and dcype (51 mg, 0.121 mmol) were suspended in 0.6 mL of THF, and the mixture was stirred at room temperature for 5 min. Alkyne 1a (121 mg, 0.605 mmol), ethyl cyanoformate (2, 30 mg, 0.303 mmol), and Zn powder (24 mg, 0.367 mmol) were added to the reaction mixture, then stirred at 60 °C for 16 h. The reaction mixture was diluted with EtOAc, and the mixture was passed through a pad of silica gel and Florisil, then the filtrate was concentrated in vacuo. The NMR yield (C₆H₅CF₃ as an internal standard) was determined to be 94% yield. The residue was chromatographed on silica gel (hexane–Et₂O, 7:3) to give 139 mg (92%) of 3a as a white solid; mp 151–153 °C. ¹H NMR (500 MHz, CDCl₃): δ = 1.44 (t, J = 6.3 Hz, 3 H), 2.26 (s, 6 H), 4.52 (q, J = 6.3 Hz, 2 H), 6.81 (d, J = 6.3 Hz, 4 H), 6.97 (d, J = 6.3 Hz, 4 H). ¹³C NMR (125 Hz, CDCl₃): δ = 13.9, 55.1, 63.0, 113.0, 120.2 (q, J _CF = 277.1 Hz), 122.3 (q, J _CF = 275.9 Hz), 124.7, 124.8 (q, J _CF = 29.6 Hz), 126.2, 130.1, 130.9, 139.1, 148.0 (q, J _CF = 33.4 Hz), 148.7, 154.0, 159.2, 159.3, 165.3. ¹⁹F NMR (470 MHz, CDCl₃): δ = 99.8 (s, 3 F), 107.7 (s, 3 F). IR (KBr): 2969, 2941, 2841, 1757, 1611, 1519, 1031, 626, 552 cm^–1. ESI-HRMS: m/z calcd for C₂₄H₂₀F₆NO₄ [M + H]⁺: 500.1291; found: 500.1320
• 20 We recovered unreacted 1k and 1l in 75% NMR yield and 86% NMR yield, respectively. These results suggest that the coordination of alkynes to cobalt or formation of the cobaltcyclopentadiene (complex I in Scheme 1) is very slow.