PAPER
a-Iodination of Ketones
2-Iodo-1-(4-methoxyphenyl)pentan-1-one (4a)
1541
IR (neat): 1657, 1593, 1258, 856 cm–1.
Yellow oil.
IR (neat): 1667, 1598, 1253, 842 cm–1.
1H NMR (CDCl3, 200 MHz): d = 7.98 (d, 2 H, J = 8.5 Hz), 6.94 (d,
2 H, J = 8.5 Hz), 5.29 (t, 1 H, J = 7.4 Hz), 3.87 (s, 3 H), 2.13 (m, 2
H), 1.50–1.26 (m, 4 H), 0.88 (t, 3 H, J = 14.6 Hz).
1H NMR (CDCl3, 200 MHz): d = 8.02 (d, 1 H, J = 8.8 Hz), 6.86 (dd,
1 H, J = 8.8, 2.1 Hz), 6.70 (d, 1 H, J = 2.1 Hz), 4.95 (t, 1 H, J = 3.6
Hz), 3.84 (s, 3 H), 3.18–3.01 (m, 2 H), 2.31–2.00 (m, 2 H).
13C NMR (CDCl3, 50 MHz): d = 190.7, 164.0, 145.3, 131.1, 122.7,
113.7, 112.4, 55.4, 32.8, 30.9, 28.2.
Anal. Calcd for C11H11IO2: C, 43.73; H, 3.67. Found: C, 43.91; H,
3.77.
13C NMR (CDCl3, 50 MHz): d = 193.2, 163.8, 130.9 (2), 126.9,
114.0 (2), 55.5, 34.9, 31.7, 25.9, 22.1, 13.8.
Anal. Calcd for C13H17IO2: C, 47.00; H, 5.16. Found: C, 46.99; H,
5.17.
5-Bromo-2-iodo-3,4-dihydro-2H-naphthalen-1-one (2e)
Beige crystals; mp 78–81 °C.
IR (neat): 1672, 1439, 610 cm–1.
(4-Methoxyphenyl)phenylacetic Acid Ethyl Ester (5)
Spectral properties were similar to previously reported values.19
1H NMR (CDCl3, 200 MHz): d = 8.14 (d, 1 H, J = 7.8 Hz), 7.84 (d,
1 H, J = 7.8 Hz), 7.32 (t, 1 H, J = 7.8 Hz), 5.04 (t, 1 H, J = 3.8 Hz),
3.25–2.92 (m, 2 H), 2.45–2.11 (m, 2 H).
13C NMR (CDCl3, 50 MHz): d = 191.0, 141.6, 137.7, 131.2, 128.0,
127.9, 124.5, 31.3, 28.6, 28.3.
Acknowledgment
The CNRS is gratefully thanked for support of this research. We
also thank the Servier Group for a doctoral fellowship to G. L.B.
P.-B. Le Calvez is thanked for carrying out some experiments.
Anal. Calcd for C10H8BrIO: C, 34.22; H, 2.30. Found: C, 34.31; H,
2.38.
6-Allyl-2-iodo-3,4-dihydro-2H-naphthalen-1-one (2f)
Yellow crystals; mp 67–71 °C.
References
(1) For a recent review, see: Takami, K.; Usugi, S. I.; Yorimitsu,
H.; Oshima, K. Synthesis 2005, 824.
(2) Ringold, H. J.; Stork, G. J. Am. Chem. Soc. 1958, 80, 250.
(3) Takeda, A.; Tsuboi, S.; Sakai, T. J. Org. Chem. 1974, 39,
2601.
(4) Motohashi, S.; Satomi, M. Synthesis 1982, 1021.
(5) Jullian, P. L.; Karpel, W. J. J. Am. Chem. Soc. 1950, 72, 362;
and references cited therein.
(6) Bergman, J.; Bäckvall, J. E. Tetrahedron 1975, 31, 2063.
(7) (a) Wolff, L.; Greulich, R. Justus Liebigs Ann. Chem. 1912,
394, 36. (b) McKillop, A.; Fowler, J. S.; Zelesko, M. J.;
Hunt, J. D.; Taylor, E. C.; McGillivray, G. Tetrahedron Lett.
1969, 2427.
IR (neat): 1659, 1590, 1493, 1431, 1245, 1163, 1082 cm–1.
1H NMR (CDCl3, 200 MHz): d = 8.10 (d, 1 H, J = 8.8 Hz), 6.87 (dd,
1 H, J = 8.8, 2.2 Hz), 6.73 (d, 1 H, J = 2.2 Hz), 6.13–5.94 (m, 1 H),
5.46–5.29 (m, 2 H), 4.97 (t, 1 H, J = 3.6 Hz), 4.59 (d, 2 H, J = 5.0
Hz), 3.19–3.03 (m, 1 H), 2.86–2.74 (dt, 1 H, J = 17.0, 3.6 Hz), 2.33–
2.01 (m, 2 H).
13C NMR (CDCl3, 50 MHz): d = 190.7, 163.1, 145.2, 132.3, 131.2,
122.8, 188.2, 114.3, 113.3, 68.6, 32.9, 30.8, 28.3.
Anal. Calcd for C13H13IO2: C, 47.58; H, 3.99. Found: C, 47.66; H,
3.89.
2,2-Dimethylpropionic Acid 6-Iodo-5-oxo-5,6,7,8-tetrahydro-
naphthalen-2-yl Ester (2g)
Beige crystals; mp 124–125 °C.
(8) Cambie, R. C.; Hayward, R. C.; Jurlina, J. L.; Ruthledge, P.
S.; Woodgate, P. D. J. Chem. Soc., Perkin Trans. 1 1978,
126.
IR (neat): 1752, 1672, 1600, 1246, 1104 cm–1.
(9) (a) Rubottom, G. M.; Mott, R. C.; Juve, H. D. Jr. J. Org.
Chem. 1981, 46, 2717. (b) Rubottom, G. M.; Mott, R. C. J.
Org. Chem. 1979, 44, 1731.
(10) D’Auria, M.; D’Onofrio, F.; Piancatelli, G.; Scettri, A.
Synth. Commun. 1982, 12, 1127.
(11) Horiuchi, C. A.; Kiji, S. Bull. Chem. Soc. Jpn. 1997, 70, 421.
(12) (a) Bekaert, A.; Barberan, O.; Gervais, M.; Brion, J.-D.
Tetrahedron Lett. 2000, 41, 2903. (b) Bekaert, A.; Provot,
O.; Rasolojaona, O.; Alami, M.; Brion, J.-D. Tetrahedron
Lett. 2005, 46, 4187.
1H NMR (CDCl3, 200 MHz): d = 8.13 (d, 1 H, J = 8.4 Hz), 7.07–
7.00 (m, 2 H), 5.01 (t, 1 H, J = 3.6 Hz), 3.24–3.05 (m, 1 H), 2.95–
2.75 (dt, 1 H, J = 17.0, 3.6 Hz), 2.34–2.06 (m, 2 H), 1.37 (s, 9 H).
13C NMR (CDCl3, 50 MHz): d = 190.6, 176.3, 155.5, 144.5, 130.5,
126.8, 121.2, 120.5, 39.1, 32.5, 30.1, 27.8, 26.9 (3).
Anal. Calcd for C15H17IO3: C, 48.40; H, 4.60. Found: C, 48.43; H,
4.72.
(13) For a recent review on Selenium chemistry, see: Nogueira,
C. W.; Zeni, G.; Rocha, J. B. T. Chem. Rev. 2004, 104, 6255.
(14) Cahiez, G.; Alami, M. Manganese Dioxide, In Encyclopedia
of Reagents for Organic Synthesis, Vol. 5; Paquette, L., Ed.;
Wiley: Chichester, 1995, 3229.
(15) We have observed that shorter reaction times (e.g., 1 h 30, 3
h 30 and 12 h) led to partial a-iodination of tetralones and
after optimization, refluxing for 18 h led to better yields of
iodo compounds.
6-(tert-Butyldimethylsilyloxy)-2-iodo-3,4-dihydro-2H-naphtha-
len-1-one (2h)
Beige crystals; mp 58–60 °C.
IR (neat): 1676, 1597, 1254, 966 cm–1.
1H NMR (CDCl3, 200 MHz): d = 8.00 (d, 1 H, J = 8.6 Hz), 6.78 (dd,
1 H, J = 8.6, 2 Hz), 6.68 (d, 1 H, J = 2 Hz), 4.97 (t, 1 H, J = 3.4 Hz),
3.17–3.01 (m, 1 H), 2.83–2.71 (m, 1 H), 2.32–2.02 (m, 2 H), 0.99
(s, 9 H), 0.24 (s, 6 H).
13C NMR (CDCl3, 50 MHz): d = 190.8, 160.8, 145.2, 131.1, 123.2,
119.2, 118.9, 32.9, 30.8, 28.0, 25.5 (3), 18.1, –4.4 (2).
(16) Starting materials (ketones) and a-iodo ketones were easily
separated by chromatography on silica gel.
(17) Lee, J. C.; Bae, Y. H. Synlett 2003, 507.
(18) Olivi, N.; Thomas, E.; Peyrat, J. F.; Alami, M.; Brion, J. D.
Synlett 2004, 2175.
Anal. Calcd for C16H23IO2Si: C, 47.76; H, 5.76. Found: C, 47.62; H,
5.69.
(19) Moradi, W. A.; Buchwald, S. L. J. Am. Chem. Soc. 2001,
123, 7996.
Synthesis 2006, No. 9, 1537–1541 © Thieme Stuttgart · New York