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DOI: 10.1055/s-2005-868495
A Convenient Protocol for the α-Iodination of α,β-Unsaturated Carbonyl Compounds with I2 in an Aqueous Medium
Publication History
Publication Date:
25 April 2005 (online)
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Abstract
A variety of cyclic and acyclic α,β-unsaturated carbonyl compounds undergo α-iodination exclusively, in high yields, with I2 in aqueous THF catalyzed by DMAP and quinuclidine.
Key words
α,β-unsaturated carbonyl compounds - α-iodination - aqueous medium - regioselective
- 1 For review of α-iodo carbonyl compounds in synthesis, see:
Negishi E. J. Organomet. Chem. 1999, 179 - 2
Bovonsombat P.Angara GJ.McNelis E. Tetrahedron Lett. 1994, 35: 6787 - 3
Whang JP.Yang SG.Kim YH. Chem. Commun. 1997, 1355 - 4
Alimardanov A.Negishi E. Tetrahedron Lett. 1999, 40: 3839 - 5
Johnson CJ.Adam JP.Braun MP.Senanayake CBW.Wovkulich PM.Uskokovic MR. Tetrahedron Lett. 1992, 33: 917 - 6
Djuardi E.Bovonsombat P.McNelis E. Synth. Commun. 1997, 24: 2497 - 7
Spivey AC.Arseniyadis S. Angew. Chem. Int. Ed. 2004, 43: 5436 - 8 For review of Baylis-Hillman chemistry, see:
Basavaiah D.Rao AJ.Satyanarayana T. Chem. Rev. 2003, 103: 811 - 9
Aggarwal VK.Emme I.Fulford SY. J. Org. Chem. 2003, 68: 692 - 10
Lee KY.GowriSankar S.Kim JN. Tetrahedron Lett. 2004, 45: 5485 - 11
Aggarwal VK.Mereu A. Chem. Commun. 1999, 2311 - 12
Burger JD.Liebhafsky HA. Anal. Chem. 1973, 45: 600 - 13
Bergstrom D.Lin X.Wang G.Rotstein D.Beal P.Norrix P.Ruth J. Synlett 1992, 179 - 14
Goodwin JT.Glick GD. Tetrahedron Lett. 1993, 34: 5549 - 17
Dodero VI.Koll LC.Faraoni MB.Mitchell TN.Podestá JC. J. Org. Chem. 2003, 68: 10087 - 18
Banwell MG.Kelly BD.Kokas OJ.Lupton DW. Org. Lett. 2003, 5: 2497
References
Compound 2l was extracted with acetonitrile.
16Selected data:
Compound 2f: 1H NMR (300 MHz, CDCl3): δ = 6.83 (d, J = 2.1 Hz, 1 H, CHH=C), 6.86 (d, J = 2.1, 1 H, CHH=C), 7.46 (t, J = 6.8 Hz, 2 H, Ar), 7.59 (t, J = 7.5 Hz, 1 H, Ar), 7.81 (d, J = 7.2 Hz, 2 H, Ar). 13C NMR (75 MHz CDCl3): δ = 107.9, 128.5 (2 C), 129.9 (2 C), 133.1, 133.8, 191.7.
Compound 2j: 1H NMR (300 MHz, CDCl3): δ = 2.00 (s, 3 H, CH
3), 2.04 (s, 3 H, CH
3), 2.50 (s, 3 H, CH
3). 13C NMR (75 MHz, CDCl3): δ = 22.1, 28.9, 30.9, 95.9, 145.7, 199.4.
Compound 2m: 1H NMR (300 MHz, CDCl3): δ = 3.92 (s, 3 H, OCH
3), 6.67 (s, 1 H, CHH=C), 7.55 (CHH=C). 13C NMR (75 MHz CDCl3): δ = 53.7, 95.8, 139.9, 163.0.
Compound 2n: 1H NMR (300 MHz, CDCl3): δ = 1.16 (t, J = 7.2 Hz, 3 H, CH2CH
3), 1.81 (d, J = 6.6 Hz, 3 H, CH
3CHC), 4.11 (q, J = 7.2 Hz, 2 H, CH
2CH3), 7.15 (q, J = 6.6 Hz, 1 H, CH3CHC). 13C NMR (75 MHz CDCl3): δ = 14.2, 22.9, 62.5, 96.9, 148.3, 162.8.