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DOI: 10.1055/s-2007-968010
N,N-Dimethylglycine-Promoted Ullmann-Type Coupling Reactions of Aryl Iodides with Aliphatic Alcohols
Publikationsverlauf
Publikationsdatum:
24. Januar 2007 (online)
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Abstract
The Ullmann-type coupling reactions of aryl iodides and aliphatic alcohols occur at 110 °C with N,N-dimethylglycine as the ligand, giving aryl alkyl ethers in good to excellent yields.
Key words
cross-coupling - aliphatic alcohols - catalysis - ligands - aryl iodides
-
1a
Yamazaki N.Washio I.Shibasaki Y.Mitsuru Ueda M. Org. Lett. 2006, 8: 2321 -
1b
Asano M.Inoue M.Katoh T. Synlett 2005, 2599 -
1c
Jiang H.Leger J.-M.Huc I. J. Am. Chem. Soc. 2003, 125: 3448 -
1d
Bolm C.Hildebrand JP.Muñiz K.Hermanns N. Angew. Chem. Int. Ed. 2001, 40: 3284 -
1e
Gu WX.Jing XB.Pan XF.Chan ASC.Yang TK. Tetrahedron 2000, 41: 6079 -
1f
Matsumoto Y.Uchida W.Nakahara H.Yanagisawa I.Shibanuma T.Nohira H. Chem. Pharm. Bull. 2000, 48: 428 -
1g
Cao B.Haengsoon Park H.Joullie MM. J. Am. Chem. Soc. 2002, 124: 520 -
1h
Temal-Laïb T.Chastanet J.Zhu J. J. Am. Chem. Soc. 2002, 124: 583 -
1i
Kawata S.Hirama M. Tetrahedron Lett. 1998, 39: 8707 -
1j
Thompson A.Delaney A.James M.Hamby J.Schroeder M.Spoon T.Crean S.Showalter HDH.Denny W. J. Med. Chem. 2005, 48: 4628 - 2
Lindley J. Tetrahedron 1984, 40: 1433 - For some recent reports on palladium-catalyzed aryl ether synthesis, see:
-
3a
Vorogushin AV.Huang X.Buchwald SL. J. Am. Chem. Soc. 2005, 127: 8146 -
3b
Kataoka N.Shelby Q.Stambuli J.Hartwig J. J. Org. Chem. 2002, 67: 5553 -
3c
Kuwabe S.Torraca KE.Buchwald SL. J. Am. Chem. Soc. 2001, 123: 12202 -
3d
Prim D.Campagna J.-M.Joseph D.Andrioletti B. Tetrahedron 2002, 58: 2041 -
3e
Hartwig JF. Angew. Chem. Int. Ed. 1998, 37: 2046 -
3f
Palucki M.Wolfe J.Buchwald SL. J. Am. Chem. Soc. 1997, 119: 3395 -
3g
Torraca K.Huang X.Parrish C.Buchwald S. J. Am. Chem. Soc. 2001, 123: 10770 - 4
an der Heiden MR.Frey GD.Plenio H. Organometallics 2004, 23: 3548 - For some recent reviews on copper-catalyzed Ullmann-type reaction, see:
-
5a
Kunz K.Scholz U.Ganzer D. Synlett 2003, 2428 -
5b
Frlan R.Kikelj D. Synthesis 2006, 2271 -
5c
Beletskaya I.Cheprakov A. Coord. Chem. Rev. 2004, 248: 2337 -
5d
Ley S.Thomas A. Angew. Chem. Int. Ed. 2003, 42: 5400 -
6a
Wolter M.Nordmann GE.Buchwald SL. Org. Lett. 2002, 4: 973 -
6b
Job G.Buchwald SL. Org. Lett. 2002, 4: 3703 -
6c
Hosseinzadeh R.Tajbakhsh M.Mohadjerani M.Alikarami M. Synlett 2005, 1101 -
6d
Manbeck GF.Lipman A.Stockland RA.Freidl A.Hasler A.Stone J.Guzei I. J. Org. Chem. 2005, 70: 244 -
7a
Ma D.Zhang Y.Yao J.Wu S.Tao F. J. Am. Chem. Soc. 1998, 120: 12459 -
7b
Ma D.Xia C. Org. Lett. 2001, 3: 2583 -
7c
Ma D.Cai Q.Zhang H. Org. Lett. 2003, 5: 2453 -
7d
Ma D.Cai Q. Org. Lett. 2003, 5: 3799 -
7e
Zhang H.Cai Q.Ma D. J. Org. Chem. 2005, 70: 5164
References and Notes
N , N -Dimethylglycine-Promoted Coupling Reactions of Aryl Halides with Alcohols; General Procedure: A re-sealable tube or test tube with a removable cap was charged with CuI (10 mol%), N,N-dimethylglycine·HCl (20 mol%), Cs2CO3 (2 equiv), and aryl halide (if solid, 2 mmol). The tube was evacuated and backfilled with N2 (3 cycles). Alcohol (2 mL) and aryl halide (if liquid, 2 mmol) were added by syringe at r.t. under nitrogen. The sealed or capped tube was put into the oil bath that was preheated to 110 °C and the reaction mixture was stirred for the time specified. The cooled mixture was partitioned between H2O (10 mL) and EtOAc or Et2O (20 mL). The organic layer was separated, and the aqueous layer was extracted with EtOAc or Et2O (10 mL) each time until TLC showed no trace of product left in the aqueous layer. The combined organic layers were washed with brine, dried over Na2SO4 and concentrated. Purification of the residue by flash chromatography on silica gel [2 × 20 cm, PE (30-60 °C)-EtOAc or Et2O] gave the desired product.
94-Benzoxyanisole (Table 2, Entry 3): white solid; mp 60-62 °C (Lit. [6a] mp 63 °C). 1H NMR (400 MHz, CDCl3): δ = 7.25-7.43 (m, 5 H), 6.91 (d, J = 8.9 Hz, 2 H), 6.83 (d, J = 8.9 Hz, 2 H), 5.02 (s, 2 H), 3.77 (s, 3 H). MS (EI): m/z = 214 [M+], 123, 95, 92, 91, 65, 63, 41.
103-(3-Methylbut-2-enyloxy)pyridine (Table 2, Entry 20): yellow oil. 1H NMR (500 MHz, CDCl3): δ = 8.32 (s, 1 H), 8.21 (s, 1 H), 7.20 (s, 2 H), 5.46-5.49 (m, 1 H), 4.56 (d, J = 7.0 Hz, 2 H), 1.80 (s, 3 H), 1.75 (s, 3 H). 13C NMR (125 MHz, CDCl3): δ = 155.0, 141.9, 139.0, 138.1, 123.8, 121.4, 119.0, 65.1, 25.8, 18.3. MS (EI): m/z = 163 [M+], 162, 95, 69, 68, 67, 41. HRMS (EI): m/z [M+] calcd for C10H13NO: 163.0997; found: 163.1002.