PAPER
Reaction of Enol Ethers with the I2–H2O2 System
4165
1H NMR (200 MHz, CDCl3): d = 0.73–2.13 [m, 18 H, CH3,
(CH3)2CHCH2, CH2], 3.42 (s, 0.45 H, CH3O), 3.45 (s, 2.55 H,
CH3O), 4.37 (d, J = 2.4 Hz, 0.85 H, CHI), 4.51 (d, J = 2.9 Hz, 0.15
H, CHI), 7.91 (br s, 0.15 H, OOH), 8.04 (br s, 0.85 H, OOH).
13C NMR (50 MHz, CDCl3): d = 22.4, 22.6, 23.8, 23.9, 24.1, 24.6,
24.7, 29.1 [CH(CH3)2, CH3, CHI], 40.8, 41.9 (CH2), 49.5, 51.1
(CH3O), 107.0 (COOH).
1H NMR (200 MHz, CDCl3): d = 0.78–0.99 (m, 6 H, CH3), 1.13–
1.98 (m, 8 H, CH2CH2CH3), 2.47–2.88 (m, 2 H, CH2CO), 4.42 (t,
J = 14.7, 7.3 Hz, 1 H, CHI).
13C NMR (50 MHz, CDCl3) d: 13.2, 13.8, 22.1, 22.6, 26.4, 32.6,
36.3, 38.5, 204.8.
3-Iodo-2,6-dimethylheptan-4-one (6b)
Yellow oil.
IR (CCl4): 1706 (C=O) cm–1.
Anal. Calcd for C10H21IO3: C, 37.99; H, 6.69; I, 40.14. Found: C,
37.84; H, 6.47; I, 40.32.
1H NMR (200 MHz, CDCl3): d = 0.76–1.24 (m, 12 H, CH3), 1.89–
2.28 [m, 2 H, CH(CH3)2], 2.49–2.61 (m, 2 H, CH2), 4.20 (d, J = 8.79
Hz, 1 H, CHI).
13C NMR (50 MHz, CDCl3): d = 20.1, 22.1, 22.4, 23.5, 24.3, 30.8,
44.7, 48.4, 204.0.
2-Iodocyclohexanone (5a)18
Yellow oil.
1H NMR (200 MHz, CDCl3): d = 0.95–2.46 (m, 7 H, CH2, HCH-
CO), 3.02–3.33 (m, 1 H, HCHCO), 4.55–4.81 (m, 1 H, CHI).
13C NMR (75 MHz, CDCl3): d = 22.4, 26.6, 32.4, 36.3, 37.2, 204.6.
Anal. Calcd for C9H17IO: C, 40.31; H, 6.39; I 47.33. Found: C,
40.54; H, 6.15; I, 47.80.
2-Iodo-4-methylcyclohexanone (5b)19
Yellow oil.
1H NMR (300 MHz, CDCl3): d = 0.92–2.39 (m, 9 H, CH3, CH2,
HCHCO, CH3CH), 3.26–3.40 (m, 1 H, HCHCO), 4.54–4.59 (m, 1
H, CHI).
13C NMR (50 MHz, CDCl3): d = 20.5, 27.4, 29.9, 34.5, 34.6, 43.6,
205.5.
Acknowledgment
This work was supported by the Program for Support of Leading
Scientific Schools of the Russian Federation (Grant NSh
2942.2008.3) and an RFBR grant (project No. 10-03-91220-CT).
4-tert-Butyl-2-iodocyclohexanone (5c)20
Yellow oil.
References
(1) (a) Jefford, C. W. Drug Discovery Today 2007, 12, 487.
(b) Borstnik, K.; Paik, I.-H.; Shapiro, T. A.; Posner, G. H.
Int. J. Parasitol. 2002, 32, 1661. (c) Dussault, P. H.; Lee, I.
Q.; Lee, H. J.; Lee, R. J.; Niu, Q. J.; Schultz, J. A.; Zope, U.
R. J. Org. Chem. 2000, 65, 8407. (d) Jin, H.-X.; Liu, H.-H.;
Zhang, Q.; Wu, Y. Tetrahedron Lett. 2005, 46, 5767.
(e) McCullough, K. J.; Wood, J. K.; Bhattacharjee, A. K.;
Dong, Y.; Kyle, D. E.; Milhous, W. K.; Vennerstrom, J. L.
J. Med. Chem. 2000, 43, 1246. (f) Wu, Y.-L.; Li, Y. Med.
Chem. Res. 1995, 5, 569. (g) Jin, H.-X.; Zhang, Q.; Kim,
H.-S.; Wataya, Y.; Liu, H.-H.; Wu, Y. Tetrahedron 2006,
62, 7699. (h) Bernat, V.; André-Barrès, C.; Baltas, M.;
Saffon, N.; Vial, H. Tetrahedron 2008, 64, 9216. (i) Šolaja,
B. A.; Terzić, N.; Pocsfalvi, G.; Gerena, L.; Tinant, B.;
Opsenica, D.; Milhous, W. K. J. Med. Chem. 2002, 45,
3331. (j) Atheaya, H.; Khan, S. I.; Mamgain, R.; Rawat, D.
S. Bioorg. Med. Chem. Lett. 2008, 18, 1446. (k) Sabbani,
S.; Stocks, P. A.; Ellis, G. L.; Davies, J.; Hedenstrom, E.;
Ward, S. A.; O’Neill, P. M. Bioorg. Med. Chem. Lett. 2008,
18, 5804.
(2) (a) Amewu, R.; Stachulski, A. V.; Ward, S. A.; Berry, N.
G.; Bray, P. G.; Davies, J.; Labat, G.; Vivas, L.; O’Neill, P.
M. Org. Biomol. Chem. 2006, 4, 4431. (b) Dong, Y.; Tang,
Y.; Chollet, J.; Matile, H.; Wittlin, S.; Charman, S. A.;
Charman, W. N.; Tomas, J. S.; Scheurer, C.; Snyder, C.;
Scorneaux, B.; Bajpai, S.; Alexander, S. A.; Wang, X.;
Padmanilayam, M.; Cheruku, S. R.; Brun, R.; Vennerstrom,
J. L. Bioorg. Med. Chem. 2006, 14, 6368. (c) Singh, C.;
Malik, H.; Puri, S. K. Bioorg. Med. Chem. Lett. 2004, 14,
459.
1H NMR (200 MHz, CDCl3): d = 0.89 (s, 9 H, CH3C), 1.16–2.36
(m, 6 H, CH2, CHC, HCHCO), 3.10–3.40 (m, 1 H, HCHCO), 4.61–
4.67 (m, 1 H, CHI).
13C NMR (50 MHz, CDCl3): d = 27.3, 27.5, 29.6, 31.1, 34.8, 36.8,
42.1, 205.7.
2-Iodocycloheptanone (5d)10b
Yellow oil.
1H NMR (300 MHz, CDCl3): d = 1.05–2.48 (m, 9 H, CH2, HCH-
CO), 2.84–2.98 (m, 1 H, HCHCO), 4.54 (dd, J = 16.1, 5.9 Hz, 1 H,
CHI).
13C NMR (75 MHz, CDCl3): d = 25.3, 28.3, 29.3, 32.21, 35.5, 38.2,
207.4.
2-Iodocyclooctanone (5e)10b
Yellow oil.
IR (CCl4): 1692 cm–1.
1H NMR (300 MHz, CDCl3): d = 0.95–2.02 (m, 9 H, CH2, HCH-
CO), 2.22–2.59 (m, 2 H, CH2CH2CO), 2.89–3.04 (m, 1 H, HCH-
CO), 4.68 (dd, J = 16.1, 3.7 Hz, 1 H, CHI).
13C NMR (75 MHz, CDCl3): d = 23.6, 25.3, 29.4, 29.7, 33.9, 34.1,
35.0, 209.7.
2-Iodocyclododecanone (5f)18
White or pale-yellow crystals; mp 48–50 °C (Lit.18 mp 52–
52.5 °C).
IR (CCl4): 1702 cm–1.
(3) (a) Dembitsky, V. M.; Gloriozova, T. A.; Poroikov, V. V.
Mini-Rev. Med. Chem. 2007, 7, 571. (b) Jung, M.; Kim, H.;
Lee, K.; Park, M. Mini-Rev. Med. Chem. 2003, 3, 159.
(c) Kim, J.; Park, E. J. Curr. Med. Chem. Anticancer Agents
2002, 2, 485. (d) Dembitsky, V. M. Eur. J. Med. Chem.
2008, 43, 223. (e) Terzić, N.; Opsenica, D.; Milić, D.;
Tinant, B.; Smith, K. S.; Milhous, W. K.; Šolaja, B. A.
J. Med. Chem. 2007, 50, 5118.
1H NMR (300 MHz, CDCl3): d = 1.11–2.03 (m, 17 H, CH2, HCH-
CO), 2.37–2.58 (m, 2 H, CH2CH2CO), 2.90–3.02 (m, 1 H, HCH-
CO), 4.68 (dd, J = 16.1, 3.7 Hz, 1 H, CHI).
13C NMR (75 MHz, CDCl3): d = 22.1, 23.3, 24.20, 24.24, 24.4,
25.05, 25.12, 25.7, 28.1, 35.0, 36.4, 205.9.
4-Iodononan-5-one (6a)21
Yellow oil.
Synthesis 2009, No. 24, 4159–4166 © Thieme Stuttgart · New York