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DOI: 10.1055/a-2219-5767
Update of the Imine-Anion-Mediated Smiles Rearrangement: Application to Migration of Electron-Neutral/Rich Aromatic Groups
This work was partially supported by a Grant-in-Aid for Scientific Research from the Japan Society for the Promotion of Science
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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
- Supporting information for this article is available online at https://doi.org/10.1055/a-2219-5767.
- Supporting Information
Publikationsverlauf
Eingereicht: 09. November 2023
Angenommen nach Revision: 29. November 2023
Accepted Manuscript online:
29. November 2023
Artikel online veröffentlicht:
04. Januar 2024
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- 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.
For selected examples, see:
For selected reviews, see:
For selected reviews on salen (Schiff base) complexes, see:
A related approach (nucleophilic addition to CN group/SNAr reaction sequence) has been used for the formation of phenanthridines, see:
For some examples of reactions between imine anions and electrophiles, see: