Regioselective Mercury(I)/Palladium(II)-Catalyzed Single-Step Approach for the Synthesis of Imines and 2-Substituted Indoles
Abstract
:1. Introduction
2. Results and Discussion
2.1. Synthesis of Imines 5a–n by Hg(I)-catalyzed Hydroamination of Alkynes 2a–d with Anilines 1a–k
2.2. One-Pot Synthesis of Indoles 6a–p by Subsequent Hg(I)- and Pd(II)-Catalyzed Conversion of Anilines 1a–g and 1i–k with Alkynes 2a–g
2.3. Mechanism of the Formation of Indoles 6a–p
3. Materials and Methods
3.1. General
3.2. General Method A for the Preparation of Imines 5a–n
3.3. General Method B for the Preparation of Indoles 6a–p
3.4. General Method C for the Preparation of Indoles 6a and 6h–i Starting from Imines 5a and 5i–j
3.5. Preparation and Characterization of Imines 5a–n
3.5.1. (E)-N-(1-Phenylethylidene)aniline (5a)
3.5.2. (E)-2-Methyl-N-(1-phenylethylidene)aniline (5b)
3.5.3. (E)-2-Methoxy-N-(1-phenylethylidene)aniline (5c)
3.5.4. (E)-3-Methyl-N-(1-phenylethylidene)aniline (5d)
3.5.5. (E)-3-Methoxy-N-(1-phenylethylidene)aniline (5e)
3.5.6. (E)-3-Chloro-N-(1-phenylethylidene)aniline (5f)
3.5.7. (E)-4-Methyl-N-(1-phenylethylidene)aniline (5g)
3.5.8. (E)-4-(N,N-dimethylamino)-N-(1-phenylethylidene)aniline (5h)
3.5.9. (E)-4-Methoxy-N-(1-phenylethylidene)aniline (5i)
3.5.10. (E)-4-Chloro-N-(1-phenylethylidene)aniline (5j)
3.5.11. (E)-2-Bromo-4-methoxy-N-(1-phenylethylidene)aniline (5k)
3.5.12. (E)-4-Methoxy-N-(1-(p-tolyl)ethylidene)aniline (5l)
3.5.13. (E)-4-(1-((4-methoxyphenyl)imino)ethyl)benzonitrile (5m)
3.5.14. (E)-4-Methoxy-N-(1-(4-methoxyphenyl)ethylidene)aniline (5n)
3.6. Preparation and Characterization of Indoles 6a–p
3.6.1. 2-Phenyl-1H-indole (6a)
3.6.2. 7-Methyl-2-phenyl-1H-indole (6b)
3.6.3. 7-Methoxy-2-phenyl-1H-indole (6c)
3.6.4. 6-Methyl-2-phenyl-1H-indole (6d). 4-Methyl-2-phenyl-1H-indole (6d’)
3.6.5. 6-Methoxy-2-phenyl-1H-indole (6e). 4-Methoxy-2-phenyl-1H-indole (6e’)
3.6.6. 6-Chloro-2-phenyl-1H-indole (6f). 4-Chloro-2-phenyl-1H-indole (6f’)
3.6.7. 5-Methyl-2-phenyl-1H-indole (6g)
3.6.8. 5-Methoxy-2-phenyl-1H-indole (6h)
3.6.9. 5-Chloro-2-phenyl-1H-indole (6i)
3.6.10. 7-Bromo-5-methyl-2-phenyl-1H-indole (6j)
3.6.11. 5-Methoxy-2-(p-tolyl)-1H-indole (6k)
3.6.12. 2-(4-Cyanophenyl)-5-methoxy-1H-indole (6l)
3.6.13. 5-Methoxy-2-(4-methoxyphenyl)-1H-indole (6m)
3.6.14. 5-Methoxy-2-propyl-1H-indole (6n)
3.6.15. 2-Cyclopropyl-5-methoxy-1H-indole (6o)
3.6.16. 2-(Cyclohex-1-en-1-yl)-5-methoxy-1H-indole (6p)
3.7. Single-Crystal X-ray Crystallography
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
Sample Availability
References
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Entry | 1 (Ar) | Catalyst | Additive (mol equiv.) | T (°C) | T (h) | 5 (Yield, %) b |
---|---|---|---|---|---|---|
1 | 1e (C6H4-3-OMe) | Hg2Cl2 | –– | 20 | 24 | 5e (99) c |
2 | 1i (C6H4-4-OMe) | Hg2Cl2 | –– | 20 | 24 | 5i (61) d |
3 | 1i (C6H4-4-OMe) | Hg2Cl2 | –– | 20 | 48 | 5i (82) d |
4 | 1i (C6H4-4-OMe) | Hg2Cl2 | –– | 45 | 4 | 5i (87) d |
5 | 1e (C6H4-3-OMe) | Ag2CO3 | –– | 20 | 72 | 5e (0) d |
6 | 1i (C6H4-4-OMe) | Hg2Cl2 | –– | 60 | 2 | 5i (72) |
7 e | 1i (C6H4-4-OMe) | Hg2Cl2 | Li2CO3 (0.2) | 60 | 2 | 5i (91) |
8 e | 1i (C6H4-4-OMe) | Hg2Cl2 | (f) | 60 | 2 | 5i (70) |
9 e | 1i (C6H4-4-OMe) | HgCl2 | Li2CO3 (0.2) | 60 | 2 | 5i (78) |
10 e | 1i (C6H4-4-OMe) | Hg0 | Li2CO3 (0.2) | 60 | 2 | 5i (0) |
Entry | 1 | 2 (R’) | R | T (h) | 5 (Yield, %) b |
---|---|---|---|---|---|
1 | 1a | 2a (H) | H | 4 | 5a (88) |
2 | 1b | 2a (H) | 2-Me | 4 | 5b (85) |
3 | 1c | 2a (H) | 2-OMe | 4 | 5c (87) |
4 | 1d | 2a (H) | 3-Me | 4 | 5d (83) |
5 | 1e | 2a (H) | 3-OMe | 4 | 5e (84) |
6 | 1f | 2a (H) | 3-Cl | 4 | 5f (53) |
7 | 1g | 2a (H) | 4-Me | 2 | 5g (91) |
8 | 1h | 2a (H) | 4-NMe2 | 2 | 5h (68) |
9 | 1i | 2a (H) | 4-OMe | 2 | 5i (91) |
10 | 1j | 2a (H) | 4-Cl | 2 | 5j (78) |
11 | 1k | 2a (H) | 2-Br-4-Me | 8 | 5k (42) |
12 | 1i | 2b (Me) | 4-OMe | 2 | 5l (91) |
13 | 1i | 2c (CN) | 4-OMe | 2 | 5m (90) c |
14 | 1i | 2d (OMe) | 4-OMe | 2 | 5n (83) |
Entry | Oxidant (mol equiv.) b | Additive (mol equiv.) | 5i/6h (Ratio) c (Yield, %) d |
---|---|---|---|
1 | Cu(OAc)2 (3.0) | Li2CO3 (0.2) | 78:22 |
2 | O2 | Li2CO3 (0.2) | 85:15 |
3 | Cu(OAc)2/O2 (3.0) | Li2CO3 (0.2) | 46:54 |
4 | KMnO4/O2 (3.0) | Li2CO3 (0.2) | 56:44 |
5 | NMMO/O2 (3.0) | Li2CO3 (0.2) | 67:33 |
6 | DTBP/O2 (3.0) | Li2CO3 (0.2) | 65:35 |
7 | Cu(OTf)2/O2 (3.0) | Li2CO3 (0.2) | 100:0 |
8 | Cu(OAc)2/O2 (1.0) | Li2CO3 (0.2) | 53:47 |
9 e | Cu(OAc)2/O2 (3.0) | Li2CO3 (0.2) | 13:87 |
10 e | Cu(OAc)2/O2 (3.0) | Li2CO3 (0.2) | 6h (45) |
11 e | Cu(OAc)2/O2 (3.0) | –– | 6h (50) |
12 e,f | Cu(OAc)2/O2 (3.0) | EtCO2H (0.2) | 6h (46) |
13 e,f | Cu(OAc)2 (3.0) | Li2CO3 (0.2) | 6h (52) |
14 e | Cu(OAc)2 (3.0) | –– | 6h (80) |
Structure | 5i | 6e | 6l |
---|---|---|---|
CCDC number | 2082632 | 2082633 | 2082634 |
Empirical formula | C15H15NO | C15H13NO | C16H12N2O |
Molecular weight | 225.28 | 223.26 | 248.28 |
Temperature | 292(2) K | 292(2) K | 292(2) K |
Crystal size | 0.79 × 0.47 × 0.27 mm3 | 0.50 × 0.30 × 0.21 mm3 | 0.52 × 0.30 × 0.27 mm3 |
Crystal system | monoclinic | orthorhombic | monoclinic |
Space group | P21/n | P212121 | P21/c |
Unit cell parameters | a = 10.0110(6) Å, α = 90º b = 8.7430(5) Å, β = 104.172(7) ºc = 14.6687(11) Å, γ = 90º | a = 5.6782(3) Å, α = 90º b = 8.0462(3) Å, β = 90º c = 25.5690(16) Å, γ = 90º | a = 7.0104(3) Å, α = 90º b = 14.5242(8) Å, β = 98.202(4)º c = 12.5032(7) Å, γ = 90º |
Volume | 1244.82(14) Å3 | 1168.19(11) Å3 | 1260.06(11) Å3 |
Z | 4 | 4 | 4 |
Density | 1.202 mg/m3 | 1.269 mg/m3 | 1.309 mg/m3 |
Absorption coefficient | 0.075 mm−1 | 0.080 mm–1 | 0.084 mm−1 |
Theta range | 3.655–29.183º | 3.187–29.557º | 2.936–29.453º |
Reflections collected | 5094 | 3635 | 5405 |
Independent reflections | 2839 | 2352 | 2909 |
Observed reflections | 1999 | 2017 | 2171 |
Final R indices | R1 = 0.0505; wR2 = 0.1110 | R1 = 0.0387; wR2 = 0.0841 | R1 = 0.0450; wR2 = 0.1001 |
Goodness-of-fit on F2 | 1.042 | 1.056 | 1.022 |
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Gutiérrez, R.U.; Hernández-Montes, M.; Mendieta-Moctezuma, A.; Delgado, F.; Tamariz, J. Regioselective Mercury(I)/Palladium(II)-Catalyzed Single-Step Approach for the Synthesis of Imines and 2-Substituted Indoles. Molecules 2021, 26, 4092. https://doi.org/10.3390/molecules26134092
Gutiérrez RU, Hernández-Montes M, Mendieta-Moctezuma A, Delgado F, Tamariz J. Regioselective Mercury(I)/Palladium(II)-Catalyzed Single-Step Approach for the Synthesis of Imines and 2-Substituted Indoles. Molecules. 2021; 26(13):4092. https://doi.org/10.3390/molecules26134092
Chicago/Turabian StyleGutiérrez, Rsuini U., Mayra Hernández-Montes, Aarón Mendieta-Moctezuma, Francisco Delgado, and Joaquín Tamariz. 2021. "Regioselective Mercury(I)/Palladium(II)-Catalyzed Single-Step Approach for the Synthesis of Imines and 2-Substituted Indoles" Molecules 26, no. 13: 4092. https://doi.org/10.3390/molecules26134092