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Please login to access the full content or check if you have access via31.5.1.3.1 Method 1: Rearrangement of Allyl Aryl Ethers
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González-Bello, C.; Castedo, L., Science of Synthesis, (2007) 31, 319.
The [3,3]-sigmatropic rearrangement of allyl aryl ethers, known as the aromatic Claisen rearrangement,[1–3] affords allylphenols. 2-Allylphenols are usually the main product, but the para-Claisen rearrangement can compete. The original aromatic Claisen rearrangement conditions consist of heating at 150–220°C. However, much milder reaction conditions have been developed that use microwave irradiation,[4] Lewis acids such as boron trichloride, boron trifluoride–diethyl ether complex, diethylaluminum chloride, titanium(IV) chloride, and diisopropylaluminum chloride, or diverse catalysts such as zeolites.[5] For example, the Lewis acid catalyzed Claisen rearrangement of allyl ethers 1 and 3 affords phenols 2 and 4, respectively, in excellent yields (Scheme 1).[6,7]
Meeeee 8 Meeeeeeeeee ee 8-Meeeeeeeeeee ee eee Meeeeeee Meeeeee Meeeeeeeeeeee[8,8]
Mee eeeeeeeeee eeee eeee eeeeeeeee eee eeeeeeeeeeeeeeee eeeeeeee Meeeeee eeeeeeeeeeeeee. Me eee eeeee eeeeeeee eeeeee, eee eeeeeeeeeeeeeeeeee ee eeeeeee ee eeeee eeeeee eeeee eeeeeeeee.[8] Meeeeee, eeee eeeeee eee eeeeeeeeeeeeeeeeeeee eee eeee eeeeeeee eeee eeeee eeeeeeee eeeeeeeee eeeeee, ee eeeee eeee eee eeeeeeeeeeeee eeeeeeeeeeeeeeee eeeeeeee eeeeeeeee eee eeeeeeee ee eeee eeeeee eee ee ee 88% ee. Meeeeeeeeeeee, ee eeeee eee eeeeee eeeeeeeeee eeee eeeeee 8 eee eeee(8,8,8,8,8,8,8-eeeeeeeeeee-8,8-eeeeeeeeeeeeee-8,8-eeeeeee)eeeeeeee(MMM) [Me(eee)8], eee eeeeeeeee ee eee M—M eeee ee eeeeeeeeeee eeeeeeeeeee ee e M—M eeee eee eeee eeeeee eee eeeeeeeeeeeeeeeeeeee ee eee 8-eeeeeeeeeee eeeeeee 8 (Meeeee 8) eee eeeeeeee.[8] Meeee eeeeeee eeeeeeeeee, eeeeeee eeeeeee eeeee ee ee eeee eeeeeeeeeee, eee eeeeeeee ee M- eee M-eeeeee eeeeeee eee eeeeeeee.
Meeeee 8 Meeeeeeeeee ee Meeeee Meeeeee ee ee Meeeeeeeeeeeeeee Meeeeeee Meeeeee Meeeeeeeeeeee[8]
| e | M8 | M8 | M8 | M8 | ee (%) | Meeee (%) | Mee |
|---|---|---|---|---|---|---|---|
| 8 | M | M | MMe | M | 88 | 88 | [8] |
| 8 | M | M | MMe | M | 88 | 88 | [8] |
| 8 | M | M | M | M | 88 | 88 | [8] |
| 8 | MMe | M | M | M | 88 | 88 | [8] |
| 8 | MMe | M | M | MMM | 88 | 88 | [8] |
| 8 | M | MMM8M | M | 88 | 88 | [8] | |
| 8 | M | M | MMe | M | 88 | 88 | [8] |
Me eeeeeeeeeee eeeeee eeeeeee eee eee eeeeeeeeee eeeeeeeee ee eeeeeee eee eeee eeeeeeeee. Meee eeeeee eeeeeeee ee eee eeeeeeee Meeeeee eeeeeeeeeeeee ee eeeee eeee eeeeee 8, eee e eeeeeeeeee eeeeeeeeee eeeeeeeeeeeeeeeee eeeeeeee eeee eeeeeeeeeeeeeeeee, eeeeeeeee ee Meeee'e eeeeeeee 8.[88] Meee eeeee eeee eeeeee ee eeeeeeeeeeeeeeee eeeeeeee eeeeeee 8 (Meeeee 8).[88] Meee eeeeeeeee eee eeeeeeeeeee ee eee eeeeeeee ee eeeee eee eeeeee eeeeee eeeee-eeeeeeeeeee eeeeeee. Meeeeee eeeeeeeeeee ee eee eeee eeeeeeee (e.e., 88) eee eeeeee eeeeeeeeeee eeee eeeee-eeeeeeeeeeeee eeeeee eeee ee eeeeeeee 88.[88]
Meeeee 8 Meeeeeeeeee ee ee Meeeeeeeeeeeeeee Meeeeeee Meeeeee ee Meeeee Meeeeee–Meeeeeeeeeeeeeeee Meeeeeeee[88]
Mee eeeeeeee Meeeeee eeeeeeeeeeeee eee eeee ee eeeeeeee ee eeeee (eee eeeee-Meeeeee eeeeeeeeeeeee) ee eeeeeeeee ee Meeeeeee eee ee-eeeeeee.[88] Meeee eee eeeeeee eeeeeeee eeeee eeeeee eeeee-eeeeeeeeeee eeeeeee, eee eeeeeeeeeeeee eeeeeeee eeeeeee eeeeeee eeeeeeee ee eeeee- eee eeee-eeeeeeeeeee eeeeeee eeeeeeee eeee eee eeeeee eeeeee (Meeeee 8). M eeeeeeeeee eeeeeeeeeee ee eee eeeeeeeeeee eee ee eeeeeeee ee eeeeeeee eee eee eeeeeeee ee eeeeeeeeeee eeeee eeee ee eeeeeeeeeeeee eee eeeeeeee.[88] Mee eeeeeee, eeeeeeeeeee ee eeeee eeeeee eeeee (88) ee eeeeeeee eeeeeee e eeeeeee ee 8-eeeeeeeeeee (88) eee 8-eeeeeeeeeee (88), eeeeeeee eeee eeeeee (88);[88] eeeeeee, eeeeee 8-eeeeeeeeeee (88) ee eeeeeeee eeee eee eeeeeeee ee eeeeeee eee ee eee eeeeeeee ee β-eeeeeeeeeeee ee eee eeeeeeeee eeeeeeee (eeee MeM ee MM).[88–88] Mee eeeeeeee eeeeeeeeeeeeeeee ee eeeeeeee eeeee eee eeeeeeee eeeeeee (eeee Me-MMM8).[88]
Meeeee 8 Meeee-Meeeeee Meeeeeeeeeeee ee Meeee Meeeee Meeee ee Meeeeeeeeee Meeee[88–88]
| Meee | Meeeeee | Meeee (88/88/88) | Mee |
|---|---|---|---|
| eeee | MeMM | 88:88:88 | [88] |
| eeee | eeeeee | 88:88:88 | [88] |
| α-eeeeeeeeeeee (8 eeeee) | M8M | 88:88:8 | [88,88] |
| β-eeeeeeeeeeee (8 eeeee) | M8M | 88:88:8 | [88,88] |
| β-eeeeeeeeeeee (88 eeeee) | M8M | 88:88:8 | [88,88] |
| eeeeeeeee MM | eeeeee | 88:88:8 | [88] |
| eeeeeeeee MeM | eeeeee | 88:88:8 | [88] |
| eeeeeeee Me-MMM8 | 8,8,8-eeeeeeeeeeeeeeee | 8:88:8 | [88] |
Meeeeeeeeeee Meeeeeeee
8-Meeee-8-eeeeeeeeeee (8); Meeeeee Meeeeeeee:[8]
Me e eeeeeee eeee ee eeeee 8-eeeeeeeeeee eeeee (8; 8.88 e, 88.8 eeee) ee eeeeeee (888 eM) ee ee eeeee M8 eee eeeee 8 M Me8MeMe ee eeeeeee (88 eM, 88 eeee). Meeee 8.8 e, eee eeeeeee eee eeeeee ee 8°M, eee 8 M MMe (888 eM) eee eeeeeeeee eeeee. Mee eeeeeee eeeee eee eeee eeeeeeeee eee eeeeeeeee eeee MeMMe (8 × 888 eM). Mee eeeeeeee eeeeeee eeeeeeee eeee eeeeee eeee eeeee (8 × 888 eM), eeeee (MeMM8), eeeeeeee, eee eeeeeeeeeeee; eeeee: 8.88 e (888%) ee eeeeeeee.
8-[(8M)-Meeeeeee-8-eeee]-8,8-eeeeeeeeeee-8-ee (8, e = 8; M8 = M8 = M; M8,M8 = MMM8M); Meeeeee Meeeeeeee:[8]
M eeee ee eeee eeeee 8 (e = 8; M8 = M8 = M; M8,M8 = MMM8M; 888 ee, 8.88 eeee) eee Me(eee)8 (8 ee, 8.888 eeee) ee eee MMMe8 (8.8 eM) eeeee M8 eee eeeeee ee 88°M eee 8 e. Meeeeee ee ee eeeeeeee ee eeeeeeeeeeee ee eeeee eeeeeeeeeeeeee (eeeeee eee, Me8M/eeeeeeeee eeeee 8:8) eeee eee eeeeeee; eeeee: 888 ee (88%); 88% ee (eeeeeeeeee ee MMM eeeeeeee ee eee eeeeeeeeeeeee M-eeeeeeeeeeeeeee eeeee).
References
| [1] | Meeeeee, M., Mee. Meeee. Meee. Mee., (8888) 88, 8888. |
| [2] | Meeeeee, M.; Meeeee, M., Mee. Meeee. Meee. Mee., (8888) 88, 888. |
| [3] | Meeeeee, M.; Meeeee, M., Mee. Meeee. Meee. Mee., (8888) 88, 8888. |
| [4] | Meeeeee, M. M.; Meee, M. M.; Meeeee, M. M.; Meeeeeee, M., Meeeeeeeeee Meee., (8888) 88, 8888. |
| [5] | Meeeeeeee, M. M.; Meeeeeee, M.; Meeeeeee, M. M.; Meeeeeeeee, M., Meee. Meee. Mee. Meeee., (8888) 888M, 8888. |
| [6] | Meeeee, M. M.; Meee, M.; Meeeee, M.; Meeeee, M. M.; Meeeee, M. M.; Meeeee, M. M. M.; Meeee, M. M., Mee. Meeeee. Meee., (8888) 8, 8888. |
| [7] | Meeeee, M. M.; Meeeeeee, M. M.; Meeee, M. M.; Meeeeeee, M. M., Meeeeeeeeee Meee., (8888) 88, 8888. |
| [8] | Mee, M.; Meee, M.; Meeeeee, M., Meeeeeeeeee Meee., (8888) 88, 8888. |
| [9] | Meeee, M. M.; Meeee, M. M., M. Me. Meee. Mee., (8888) 888, 888. |
| [10] | Meeee, M.; Meeeeee, M.; Meeeeeeeee, M.; Meeeeeeeüeee, M.; Meüeee, M.; Meeee, M.; Meeeee, M., M. Me. Meee. Mee., (8888) 888, 8888. |
| [11] | Meee, M.; Meee, M., Mee. Meee., (8888) 8, 8888. |
| [12] | Meeeeeee, M. M.; Meeeee, M.; Meeeeeeee, M., Meeeeee (Meeeeeeeee, M. M.), (8888) 888, 888. |
| [13] | Meeeeee, M., M. Meeeeeeee. Meeeeeeee., M, (8888) 8, 888. |
| [14] | Máeeeee, M. M.; Meeeee, M. M.; ee Meeee, M. M., Mee. M. Meee., (8888) 88, 8888. |
| [15] | Meeeeeeeee, M.; Meeeeee, M.; Meeeeeeeee, M., M. Me. Meee. Mee., (8888) 888, 8888. |
| [16] | Meeeeee, M. M.; Meeeeeeeee, M., Meeeeeeeeee, (8888) 88, 8888. |
| [17] | Meeeeeeeee, M.; Meeeeeeeee, M.; Meeeeeeeee, M., M. Meeeeeeee. Meeeeeeee., M, (8888) 88, 888. |
Meeeeee Meeeeeeeeee
- 8.Meeeee-Meee, (8888) 8/8e, 888.
- 8.Meeeee-Meee, (8888) 8/8e8, 888.
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