Synlett 2024; 35(13): 1565-1568
DOI: 10.1055/a-2219-5767
letter

Update of the Imine-Anion-Mediated Smiles Rearrangement: Application to Migration of Electron-Neutral/Rich Aromatic Groups

Shunki Jinno
,
Tomoko Kawasaki-Takasuka
,
Keiji Mori
This work was partially supported by a Grant-in-Aid for Scientific Research from the Japan Society for the Promotion of Science


Abstract

We have revisited the imine-anion-mediated Smiles rearrangement for the synthesis of ortho-hydroxyphenyl arylketimines. Detailed examinations revealed that migration of various aromatic groups, previously considered to be unsuited to SNAr-type reactions, such as electron-rich or sterically hindered aromatic groups, can be accomplished by introducing bulky 9-anthryllithium as a nucleophile. Among the aromatic groups examined, naphthyl groups (1- and 2-naphthyl groups) exhibited an excellent performance, and their migration ability was well illustrated by the reaction with less bulky nucleophiles.

Supporting Information



Publication History

Received: 09 November 2023

Accepted after revision: 29 November 2023

Accepted Manuscript online:
29 November 2023

Article published online:
04 January 2024

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  • References and Notes


    • For selected examples, see:
    • 1a Krunic A, Vallat A, Mo S, Lantvit DD, Swanson SM, Orjala J. J. Nat. Prod. 2010; 73: 1927
    • 1b Jokela J, Herfindal L, Wahlsten M, Permi P, Selheim F, Vasconcelos V, Doskeland SO, Sivonen K. ChemBioChem 2010; 11: 1594
    • 1c Evans BS, Ntai I, Chen Y, Robinson SJ, Kelleher NL. J. Am. Chem. Soc. 2011; 133: 7316
    • 1d Willson TA, Tokarski RJ. II, Sullivan P, Demoret RM, Orjala J, Rokotondraibe LH, Fuchs JR. J. Nat. Prod. 2018; 81: 534

    • For selected reviews, see:
    • 1e Adrover-Castellano ML, Schmidt JJ, Sherman DH. ChemCatChem 2021; 13: 2095
    • 1f Maglangit F, Yu Y, Deng L. Nat. Prod. Rep. 2021; 38: 782
    • 3a Esteban F, Cieślik W, Arpa EM, Guerrero-Corella A, Díaz-Tendero S, Perles J, Fernández-Salas JA, Fraile A, Alemán J. ACS Catal. 2018; 8: 1884
    • 3b Guerrero-Corella A, Esteban F, Iniesta M, Martín-Somer A, Parra M, Díaz-Tendero S, Fraile A, Alemán J. Angew. Chem. Int. Ed. 2018; 57: 5350
    • 4a Dalla Cort A, Mandolini L, Palmieri G, Pasquini C, Schiaffino L. Chem. Commun. 2003; 2178
    • 4b Frischmann P, Jiang J, Hui JK.-H, Grzybowski JJ, MacLachlan MJ. Org. Lett. 2008; 10: 1255
    • 4c Nguyen TB, Wang Q, Guéritte F. Synth. Commun. 2012; 42: 2648
    • 4d Liao Z.-Q, Dong C, Carlson KE, Srinivasan SS, Nwachukwu JC, Chesnut RW, Sharma A, Nettles KW, Katzenellenbogen JA, Zhou H.-B. J. Med. Chem. 2014; 57: 3532
    • 4e Seo M.-S, Jang S, Jung H, Kim H. J. Org. Chem. 2018; 83: 14300
  • 5 Jinno S, Senoo T, Mori K. Org. Lett. 2022; 24: 4140

    • A related approach (nucleophilic addition to CN group/SNAr reaction sequence) has been used for the formation of phenanthridines, see:
    • 6a Lysén M, Kristensen JL, Vedsø P, Begtrup M. Org. Lett. 2002; 4: 257
    • 6b Kristensen JL, Vedsø P, Begtrup M. J. Org. Chem. 2003; 68: 4091

      For some examples of reactions between imine anions and electrophiles, see:
    • 7a Chan L.-H, Rochow EG. J. Organomet. Chem. 1967; 9: 231
    • 7b Padwa A, Koehn WP. J. Org. Chem. 1975; 40: 1896
    • 7c Hose DR. J, Mahon MF, Molloy KC, Raynham T, Wills M. J. Chem. Soc., Perkin Trans. 1 1996; 691
    • 7d Ortiz-Marciales M, Tirado LM, Colón R, Ufret ML, Figueroa R, Lebrón M, DeJesús M, Martínez J, Malavé T. Synth. Commun. 1998; 28: 4067
    • 8a Van der Plas HC. Acc. Chem. Res. 1978; 11: 462
    • 8b Makosza M, Winiarski J. Acc. Chem. Res. 1987; 20: 282
    • 8c El Kaim L, Grimaud L. Eur. J. Org. Chem. 2014; 7749
    • 8d Chen Z.-M, Zhang X.-M, Tu Y.-Q. Chem. Soc. Rev. 2015; 44: 5220
    • 8e Holden CM, Greaney MF. Chem. Eur. J. 2017; 23: 8992
    • 8f Wu X, Zhu C. Acc. Chem. Res. 2020; 53: 1620
    • 8g Wu X, Ma Z, Feng T, Zhu C. Chem. Soc. Rev. 2021; 50: 11577
    • 8h Allen AR, Noten EA, Stephenson CR. Chem. Rev. 2022; 122: 2695
    • 9a Levy AA, Rains HC, Smiles S. J. Chem. Soc. 1931; 3264
    • 9b Evans WJ, Smiles S. J. Chem. Soc. 1935; 181
    • 9c Bunnett JF, Zahler RE. Chem. Rev. 1951; 49: 273
    • 9d Truce WE, Ray WJ. Jr, Norman OL, Eickemeyer DB. J. Am. Chem. Soc. 1958; 80: 3625
    • 9e Crowther GP, Hauser CR. J. Org. Chem. 1968; 33: 2228
    • 9f Truce WE, Kreider EM, Brand WW. Org. React. (Hoboken, NJ U. S.) 1970; 18: 99
  • 10 Yasui K, Kamitani M, Fujimoto H, Tobisu M. Org. Lett. 2021; 23: 1572
    • 11a Clayden J, Dufour J, Grainger DM, Helliwell M. J. Am. Chem. Soc. 2007; 129: 7488
    • 11b Costil R, Dale HJ. A, Fey N, Whitcombe G, Matlock JV, Clayden J. Angew. Chem. Int. Ed. 2017; 56: 12533
    • 11c Leonard DJ, Ward JW, Clayden J. Nature 2018; 562: 104
  • 12 To the best of our knowledge, this is the first example showing the reactivity difference between a 1-naphthyl group and a 2-naphthyl group. No clear difference in the migration abilities of 1-naphthyl and 2-naphthyl groups is found in the report by the Clayden group.11a
  • 13 Synthesis of Ketimines by the Imine-Anion-Mediated Smiles Rearrangement: General Procedure A 1.60 M solution of BuLi in hexane (0.28 mmol, 1.40 equiv) was added to a solution of the appropriate aryl bromide (0.30 mmol, 1.50 equiv.) in THF (1.0 mL) at –78 °C, and the mixture was stirred for 15 min at –78 °C. A solution of the appropriate benzonitrile (0.20 mmol) in THF (2.0 mL) was then added and then the solution was gradually allowed to warm to r.t. When the reaction was complete, it was stopped by adding H2O. The crude products were extracted with EtOAc (×3), and the combined organic extracts were washed with brine, dried (Na2SO4), and concentrated in vacuo. The residue was purified by column chromatography. 2-[(E)-9-Anthryl(phenylimino)methyl]phenol (4a) Purified by column chromatography [silica gel, hexane–EtOAc (30:1)] to give a yellow solid; yield: 73.5 mg (quant); mp 261–263 °C. IR (neat): 3049, 1604, 1567, 1482, 1449, 1355, 1298, 1264, 1247, 1224, 1197, 1168, 930 cm–1. 1H NMR (300 MHz, CDCl3): δ = 14.85 (s, 1 H), 8.43 (s, 1 H), 8.02–7.91 (m, 2 H), 7.88–7.74 (m, 2 H), 7.51–7.26 (m, 5 H), 7.16 (d, J = 7.8 Hz, 1 H), 6.88–6.60 (m, 5 H), 6.57–6.40 (m, 2 H). 13C NMR (75 MHz, CDCl3): δ = 172.6, 162.1, 146.6, 133.4, 132.0, 130.6, 129.1, 128.7, 128.6, 128.5, 128.0, 126.8, 125.7, 125.5, 124.8, 120.7, 120.5, 118.5, 117.9. Anal. Calcd for C27H19NO: C, 86.84; H, 5.13; N, 3.75. Found: C, 86.70; H, 5.41; N, 3.58. 2-[(E)-1-Naphthyl(phenylimino)methyl]phenol (4b) Purified by column chromatography [silica gel, hexane–EtOAc (20:1)] to give a yellow solid; yield: 40.7 mg (60%); mp 129–131 °C. IR (neat): 3059, 2927, 2854, 1602, 1593, 1593, 1566, 1484, 1451, 1399, 1306, 1248, 1195, 1148, 1119, 1072, 1036 cm–1. 1H NMR (300 MHz, CDCl3): δ = 14.70 (s, 1 H), 7.80 (d, J = 7.8 Hz, 2 H), 7.68 (d, J = 7.8 Hz, 1 H), 7.47–7.27 (m, 4 H), 7.23 (d, J = 7.2 Hz, 1 H), 7.11 (d, J = 8.1 Hz, 1 H), 7.01–6.92 (m, 2 H), 6.87–6.71 (m, 4 H), 6.57 (ddd, J = 8.1, 8.1, 0.9 Hz, 1 H). 13C NMR (75 MHz, CDCl3): δ = 173.0, 162.1, 146.8, 133.2, 132.9, 132.2, 132.2, 130.9, 129.2, 128.4, 128.2, 126.9, 126.7, 126.3, 125.7, 124.8, 124.7, 121.4, 120.3, 118.2, 117.9. Anal. Calcd for C23H17NO: C, 85.42; H, 5.30; N, 4.33. Found: C, 85.15; H, 5.07; N, 4.59. 2-[(E)-9-Anthryl(1-naphthylimino)methyl]phenol (11a) Purified by column chromatography [silica gel, hexane–EtOAc (30:1)] to give a yellow solid; yield: 87.4 mg (92%); mp 268–269 °C. IR (KBr): 3054, 2925, 2851, 1599, 1569, 1520, 1496, 1447, 1391, 1354, 1293, 1262, 1226, 1152, 1122, 1081 cm–1. 1H NMR (300 MHz, CDCl3): δ = 15.17 (s, 1 H), 8.50 (d, J = 8.1 Hz, 1 H), 8.41 (s, 1 H), 7.93 (d, J = 8.4 Hz, 2 H), 7.86 (d, J = 8.7 Hz, 2 H), 7.62 (d, J = 8.4 Hz, 1 H), 7.55 (dd, J = 7.2, 7.2 Hz, 1 H), 7.44 (d, J = 7.2 Hz, 1 H), 7.42–7.20 (m, 7 H), 6.67 (dd, J = 8.1, 8.1 Hz, 1 H), 6.62–6.49 (m, 2 H), 6.42 (d, J = 7.2 Hz, 1 H). 13C NMR (100 MHz, CDCl3): δ = 173.0, 162.3, 142.5, 133.5, 133.5, 132.1, 130.6, 129.5, 128.7, 128.5, 128.4, 127.8, 127.6, 126.8, 126.1, 125.6, 125.4, 124.8, 123.3, 121.0, 118.6, 118.1, 115.1. Anal. Calcd for C31H21NO: C, 87.92; H, 5.00; N, 3.31. Found: C, 87.70; H, 5.14; N, 3.52. 2-[(E)-9-Anthryl(2-naphthylimino)methyl]phenol (12a) Purified by column chromatography [silica gel, hexane–EtOAc (30:1)] to give a yellow solid; yield: 77.3 mg (86%); mp 227–229 °C. IR (neat): 3054, 2968, 1743, 1596, 1562, 1491, 1445, 1356, 1294, 1262, 1226, 1205, 1163, 1150, 1123 cm–1. 1H NMR (300 MHz, CDCl3): δ = 14.91 (s, 1 H), 8.39 (s, 1 H), 7.96–7.85 (m, 4 H), 7.49–7.11 (m, 12 H), 6.88 (dd, J = 8.7, 2.1 Hz, 1 H), 6.59–6.46 (m, 2 H). 13C NMR (75 MHz, CDCl3): δ = 172.8, 162.2, 144.2, 133.5, 133.0, 132.0, 130.9, 130.6, 129.2, 128.8, 128.6, 127.9, 127.5, 127.3, 126.9, 125.9, 125.6, 125.5, 125.0, 120.9, 120.6, 118.6, 118.2, 118.0. Anal. Calcd for C31H21NO: C, 87.92; H, 5.00; N, 3.31. Found: C, 88.11; H, 5.28; N, 3.19. For characterization data for the other new compounds, see the Supporting Information.