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DOI: 10.1055/s-2006-951546
Synthesis of Functionalized Diaryl Ethers by [3+3] Cyclization of 1,3-Bis(Silyl Enol Ethers) with 2-Aryloxy-3-(silyloxy)alk-2-en-1-ones
Publication History
Publication Date:
23 November 2006 (online)
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Abstract
Functionalized and sterically encumbered diaryl ethers were prepared by [3+3] cyclization of 1,3-bis(silyl enol ethers) with 2-aryloxy-3-(silyloxy)alk-2-en-1-ones.
Key words
arenes - cyclizations - diaryl ethers - silyl enol ethers
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References and Notes
General Procedure for the Synthesis of Diaryl Ethers 6a-n.
To a CH2Cl2 solution (2 mL/mmol) of 4 (1.0 mmol) and 5 (1.0 mmol) was added TiCl4 (1.0 mmol) at -78 °C. The solution was allowed to warm to ambient temperature within 20 h. To the solution was added a sat. solution of NaHCO3 (10 mL). The organic and the aqueous layer were separated and the latter was extracted with Et2O (3 × 30 mL). The filtrate was concentrated in vacuo and the residue was puri-fied by chromatography (silica gel, EtOAc-n-heptane, 1:4).
Synthesis of Methyl 4,6-Dimethyl-5-(4-chloro-phenoxy)salicylate (
6h).
Starting with 1,3-bis(silyl enol ether) 5d (500 mg, 1.9 mmol), 3-(siloxy)alk-2-en-1-one 4d (574 mg, 1.9 mmol) and TiCl4 (0.21 mL, 1.9 mmol), 6h was isolated as a colorless solid (315 mg, 54%); mp 83 °C. 1H NMR (300 MHz, CDCl3): δ = 2.09 (s, 3 H, CH3), 2.30 (s, 3 H, CH3), 3.95 (s, 3 H, OCH3), 6.67 (d, 2 H, J = 9.0 Hz, ArH), 6.76 (s, 1 H, ArH), 7.20 (d, 2 H, J = 9.0 Hz, ArH), 11.10 (s, 1 H, OH). 13C NMR (75 MHz, CDCl3): δ = 15.2, 17.1, 52.2 (CH3), 111.1 (C), 115.7 (2 C), 117.6 (CH), 126.3 (C), 129.6 (2 C, CH), 133.5, 139.7, 143.6, 156.5, 159.7, 171.7 (C). IR (KBr): 3431 (m), 2959 (w), 1661 (s), 1486 (s), 1442 (m), 1361 (m), 1326 (s), 1318 (s), 1074 (m), 825 (m), 803 (m) cm-1. GC-MS (EI, 70 eV): m/z (%) = 306 (33) [M+], 274 (100), 246 (10), 163.1 (8). Anal. Calcd (%) for C16H15ClO4 (306.74): C, 62.65; H, 4.93. Found: C, 62.42; H, 4.68.