Regio- and Stereoselectivity in the 1,3-Dipolar Cycloaddition Reactions of Isoquinolinium Ylides with Cyclopenta[a]acenaphthylen-8-ones

Abstract

A convenient regio- and diastereoselective synthesis of functionalized 5a,5b-dihydro-5H,13H-naphtho[1′′,8′′:4′,5′,6′]pentaleno[1′:3,4]pyrrolo[2,1-a]isoquinolin-5-ones via 1,3-dipolar cycloaddition reaction of 8H-cyclopenta[a]acenaphthylen-8-ones with carbonyl-stabilized isoquinolinium N-ylides, is described. Based on DFT calculations at b3lyp/6-311+g(d,p) level of theory, a nonconcerted mechanism is proposed to explain the regioselectivity of this reaction. The structure of a typical product was confirmed by X-ray crystallographic analysis.

Key words

regioselective synthesis - 1,3-dipolar cycloaddition - isoquinolinium ylide - cyclopentadienones - DFT calculations

Publication History

Received: 02 April 2020

Accepted after revision: 20 July 2020

Article published online:
11 August 2020

• References and Notes

• 1 Chapman OL, McIntosh CL. J. Chem. Soc., Chem. Commun. 1971; 770
• 2 Pal R, Mukherjee S, Chandrasekhar S, Guru RT. N. J. Phys. Chem. A 2014; 118: 3479
• 3 Ogliaruso MA, Romanelli MG, Becker EI. Chem. Rev. 1965; 65: 261
• 4 Potter RG, Hughes TS. J. Org. Chem. 2008; 73: 2995
• 5 White DM. J. Org. Chem. 1974; 39: 1951
• 6 Quintard A, Rodriguez J. Angew. Chem. Int. Ed. 2014; 53: 4044
• 7a Argyropoulos NG, Alexandrou NE. J. Heterocycl. Chem. 1979; 16: 731
• 7b Tsatsaroni EG, Argyropoulos NG, Alexandrou NE, Houndas A, Terzis A. J. Heterocycl. Chem. 1984; 21: 701
• 7c Tsatsaroni EG, Argyropoulos NG, Alexandrou NE, Houndas A, Terzis A. J. Heterocycl. Chem. 1984; 21: 1405
• 8a Shi R.-G, Sun J, Yan C.-G. ACS Omega 2017; 2: 7820
• 8b An J, Yang QQ, Wang Q, Xiao WJ. Tetrahedron Lett. 2013; 54: 3834
• 8c Fernández N, Carrillo L, Vicario JL, Badia D, Reyes E. Chem. Commun. 2011; 47: 12313
• 8d Ruano JL. G, Fraile A, Martin MR, Gonzalez G, Fajardo C, Martin-Castro AM. J. Org. Chem. 2011; 76: 3296
• 8e Peng W, Zhu S. J. Chem. Soc., Perkin Trans. 1 2001; 3204
• 9a Allen CF. H, Van Allan JA. J. Org. Chem. 1952; 17: 845
• 9b Craig JT, Robins MD. W. Aust. J. Chem. 1968; 21: 2237
• 10 Typical Procedure for the Preparation of 8To a stirred mixture of N-substituted isoquinolinium salts 7 (1.0 mmol) and Et₃N (1.1 mmol) in MeCN (6.0 mL) was added cyclopentadienone 4 (1 mmol),^9a and the resulting mixture was stirred at 80 °C for 3 h. After completion of the reaction (TLC monitoring), the mixture was filtered, and the precipitate was washed with cold MeCN and n-hexane to afford the products 8a–j.Dimethyl 4-Benzoyl-5-oxo-4H,12cH-naphtho-[1′′,8′′:4′,5′,6′]-pentaleno[1′:3,4]pyrrolo[2,1-a]isoquinoline-4a,6(5H)-dicarboxylate (8a)Orange crystals; yield 0.487 g (86%); mp 224–225 °C. IR (KBr): 3061, 2976, 1742, 1730, 1680, 1608, 1020 cm^–1. ¹H NMR: δ = 3.51 (s, 3 H), 3.86 (s, 3 H), 4.82 (d, J = 7.3 Hz, 1 H), 4.93 (s, 1 H), 5.26 (d, J = 7.3 Hz, 1 H), 6.07 (t, J = 7.3 Hz, 1 H), 6.13 (s, 1 H), 6.37 (d, J = 7.5 Hz, 1 H), 6.75 (d, J = 7.3 Hz, 1 H), 6.83 (t, J = 7.3 Hz, 1 H), 7.50 (t, J = 7.0 Hz, 1 H), 7.56 (t, J = 7.0 Hz, 1 H), 7.62 (d, J = 7.0 Hz, 2 H), 7.78 (d, J = 7.0 Hz, 1 H), 7.84 (t, J = 8.0 Hz, 1 H), 8.00 (t, J = 8.0 Hz, 2 H), 8.15 (d, J = 8.0 Hz, 2 H), 8.27 (d, J = 7.0 Hz, 1 H). ¹³C NMR: δ = 52.0 (MeO), 52.6 (MeO), 71.7 (CH), 73.1 (C), 73.7 (CH), 75.0 (C), 103.0 (CH), 121.7 (CH), 123.4 (C) 124.3 (CH), 124.5 (2 CH), 124.8 (C), 125.7 (CH), 126.1 (CH), 127.9 (CH), 128.2 (CH), 128.8 (2 CH), 129.0 (CH), 129.1 (CH), 129.2 (CH), 130.6 (C), 130.7 (C), 131.0 (CH), 132.2 (C), 133.8 (CH), 135.3 (C), 135.4 (CH), 139.1 (C), 141.9 (C), 161.5 (C = O), 165.7 (C = O), 190.0 (C), 193.7 (C = O), 198.2 (C = O). MS (EI, 70 eV): m/z (%) = 567 (4) [M⁺], 437 (50), 338 (31), 301 (54), 279 (36), 244 (45), 203 (18), 187 (27), 105 (100). Anal. Calcd for C₃₆H₂₅NO₆ (567.60): C, 76.18; H, 4.44; N, 2.47. Found: C, 75.88; H, 4.46; N, 2.46.
• 11 X-ray Crystal-Structure Determination of 8eCCDC 1969492 contains the supplementary crystallographic data for this paper (structure 8e). The data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/getstructures.
• 12a CalculationsAll calculations in this paper were carried out with Gaussian 09 package^12a by using the DFT method. Through the comparison of theoretical and experimental data, obtained from X-ray crystallography, we found that b3lyp/6-311+g(d,p)^12b,^c results were in best agreement with the experimental data. These comparisons were based on bond lengths, bond angles, and dihedral angles. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Petersson GA, Nakatsuji H, Li X, Caricato M, Marenich A, Bloino J, Janesko BG, Gomperts R, Mennucci B, Hratchian HP, Ortiz JV, Izmaylov AF, Sonnenberg JL, Williams-Young D, Ding F, Lipparini F, Egidi F, Goings J, Peng B, Petrone A, Henderson T, Ranasinghe D, Zakrzewski VG, Gao J, Rega N, Zheng G, Liang W, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Throssell K, Montgomery JA. Jr, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Keith T, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Millam J, Klene MM, Adamo C, Cammi R, Ochterski JW, Martin RL, Morokuma K, Farkas O, Foresman JB, Fox DJ. Gaussian 09, Revision A.02. 2016
• 12b Johnson BG, Fisch MJ. J. Chem. Phys. 1994; 100: 7429
• 12c Gauss J. J. Chem. Phys. 1993; 99: 3629
• 13a Sustmann R. Pure Appl. Chem. 1974; 40: 569
• 13b Meyer AG, Ryan JH. Molecules 2016; 21: 935
• 14a Beyramabadi A, Morsali A. Int. J. Phys. Sci. 2011; 6: 1780
• 14b Babu NS, Sagar GY. J. Chem. Pharm. Res. 2015; 7: 4063
• 14c Alshamaileh E. Comput. Chem. 2014; 2: 43
• 15 Vektariene A, Vektaris G, Svoboda J. ARKIVOC 2009; (vii): 311
• 16 Parr RG, Pearson RG. J. Am. Chem. Soc. 1983; 105: 7512
• 17 Parr RG, Szentpaly L, Liu SB. J. Am. Chem. Soc. 1999; 121: 1922