T. Mutsumi et al. / Tetrahedron 67 (2011) 1158e1165
1165
Sajiki, H. Heterocycles 2005, 66, 361; (g) Ito, N.; Watahiki, T.; Maesawa, T.;
Maegawa, T.; Sajiki, H. Adv. Synth. Catal. 2006, 348, 1025; (h) Esaki, H.; Ito, N.;
Sakai, S.; Maegawa, T.; Monguchi, Y.; Sajiki, H. Tetrahedron 2006, 62, 10954; (i)
Esaki, H.; Ohtaki, R.; Maegawa, T.; Monguchi, Y.; Sajiki, H. J. Org. Chem. 2007, 72,
2143; (j) Esaki, H.; Aoki, F.; Umemura, M.; Kato, M.; Maegawa, T.; Monguchi, Y.;
Sajiki, H. Chem.dEur. J. 2007, 13, 4052; (k) Kurita, T.; Hattori, K.; Seki, S.; Miz-
umoto, T.; Aoki, F.; Yamada, Y.; Ikawa, K.; Maegawa, T.; Monguchi, Y.; Sajiki, H.
Chem.dEur. J. 2008, 14, 664; (l) Ito, N.; Watahiki, T.; Maesawa, T.; Maegawa, T.;
Sajiki, H. Synthesis 2008, 1467; (m) Kurita, T.; Aoki, F.; Mizumoto, T.; Maejima,
T.; Esaki, H.; Maegawa, T.; Monguchi, Y.; Sajiki, H. Chem.dEur. J. 2008, 14, 3371;
(n) Maegawa, T.; Fujiwara, Y.; Inagaki, Y.; Esaki, H.; Monguchi, Y.; Sajiki, H.
Angew. Chem., Int. Ed. 2008, 47, 5394; (o) Ito, N.; Esaki, H.; Imamiya, E.; Mae-
sawa, T.; Maegawa, T.; Sajiki, H. Bull. Chem. Soc. Jpn. 2008, 81, 278; (p) Maegawa,
T.; Fujiwara, Y.; Inagaki, Y.; Monguchi, Y.; Sajiki, H. Adv. Synth. Catal. 2008, 350,
2215; (q) Maegawa, T.; Ito, N.; Oono, K.; Monguchi, Y.; Sajiki, H. Synthesis 2009,
16, 2674.
4. (a) Brown, W. G.; Garnett, J. L. J. Am. Chem. Soc. 1958, 80, 5272; (b) Fraser, R. R.;
Renaud, R. N. J. Am. Chem. Soc. 1966, 88, 4365; (c) Garnett, J. L.; Hodges, R. J. J. Am.
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B. J. Chem. Soc., Chem. Commun. 1973, 749; (e) Blake, M. R.; Garnett, J. L.; Gregor, I.
K.; Hannan, W.; Hoa, K.; Long, M. A. J. Chem. Soc., Chem. Commun. 1975, 930; (f)
Hesk, D.; Jones, J. R.; Lockley, W. J. S. J. Labelled Compd. Radiopharm.1990, 28,1427;
(g) Hesk, D.; Jones, J. R.; Lockley, W. J. S. J. Pharm. Sci. 1991, 80, 887; (h) Heys, J. R.;
Shu, A. Y. L.; Senderoff, S. G.; Phillips, N. M. J. Labelled Compd. Radiopharm.1993, 33,
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E.; Clement, O. J. Chem. Soc., PerkinTrans. 2 1995,1333; (k) Van Genderen, M. H. P.;
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3661; (l) Hardacre, C.; Holbrey, J. D.; McMth, S. E. J. Chem. Commun. 2001, 367; (m)
Klei, S. R.; Golden, J. T.; Tilley, T. D.; Bergman, R. G. J. Am. Chem. Soc. 2002, 124,
2092; (n) Hickey, M. J.; Jones, J. R.; Kingston, L. P.; Lockley, W. J. S.; Mather, A. N.;
McAuley, B. M.; Wilkinson, D. J. TetrahedronLett. 2003, 44, 3959; (o) Matsubara, S.;
Yokota, K.; Oshima, K.; Matsubara, S. Chem. Commun. 2004, 1714; (p) Yamamoto,
M.; Oshima, K.; Matsubara, S. Chem. Commun. 2004, 1714; (q) Yamamoto, M.;
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Oshima, K.; Matsubara, S. Chem. Lett. 2005, 34, 664; (t)Derdau,V.;Atzrodt,J. Synlett
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J¼7.1 Hz, 2H, CH2), 7.50e7.56 (m, 2H, 3-H, 5-H), 7.66 (t, J¼7.3 Hz,
0.22H, 4-H), 7.97 (d, J¼7.9 Hz, 2H, 2-H, 6-H); 2H NMR: 7.67 (br); MS
(EIþ): m/z 151 [M]þ; HRMS (EIþ): calcd for C9H92HO2 [M]þ:
151.07436, found: 151.07344.
4.1.20. 1-Deuteronaphthalene (36, Table 5, entry 11). A mixture of 1-
bromonaphthalene (60.0 mg, 290
348 mol), and V-65 (14.4 mg, 58.0
stirred at reflux for 3 h. Bu3SnH (93.6
(14.4 mg, 58.0 mol) were added, and the mixture was stirred at
m
m
mol), Bu3SnH (93.6
mol) in THF-d8 (6 mL) was
L, 348 mol) and V-65
mL,
m
m
m
m
reflux for 2 h. The mixture was concentrated in vacuo, and the res-
idue was purified by column chromatography on silica gel (hexane)
to give 1-deuteronaphthalene (25.6 mg, 68%). IR (ATR) cmꢁ1; 3054,
1
1593, 1504, 1381, 1346, 1265, 1214, 1127, 1011; H NMR (270 MHz,):
7.49e7.55 (m, 4H, 2-H, 3-H, 6-H, 7-H), 7.89e7.95 (m, 3.43H, 1-H, 4-H,
5-H, 8-H); 2H NMR: 7.93 (br); MS (EIþ): m/z 129 [M]þ; HRMS (EIþ):
calcd for C10H27H [M]þ: 129.06888, found: 129.06915.
4.1.21. 1-Deutero-2,3-dimethoxynaphthalene (38, Table 5, entry
12). A mixture of 1-bromo-2,3-dimethoxynaphthalene (60.1 mg,
225
45.1
(72.6
m
m
mol), Bu3SnH (72.6
mol) in THF-d8 (6 mL) was stirred at reflux for 3 h. Bu3SnH
L, 270 mol) and V-65 (11.2 mg, 45.1 mol) were added three
mL, 270 mmol), and V-65 (11.2 mg,
m
m
m
times every 3 h. The mixture was concentrated in vacuo, and the
residue was purified by column chromatography on silica gel twice
(hexane/hexane/ethyl acetate¼20:1/hexane/ethyl acetate¼4:1,
and hexane/ethyl acetate¼4:1) to give 1-deutero-2,3-dimethox-
ynaphthalene (38.3 mg, 90%). IR (ATR) cmꢁ1; 3057, 3015, 2999,
2970, 2937, 2833, 1619, 1598, 1503, 1486, 1465, 1431, 1326, 1260,
1219, 1197, 1165, 1114, 1052, 1003; 1H NMR (270 MHz): 3.88 (s, 6H,
OeCH3), 7.29e7.34 (m, 3.25H,1-H, 4-H, 6-H, 7-H), 7.72e7.77 (m, 2H,
5-H, 8-H); 2H NMR: 7.32 (br); MS (EIþ): m/z 189 [M]þ; HRMS (EIþ):
calcd for C12H112HO2 [M]þ: 189.09001, found: 189.09094.
5. (a) Junk, T.; Catallo, W. J. Tetrahedron Lett. 1996, 37, 3445; (b) Junk, T.; Catallo,
W. J.; Civils, L. D. J. Labelled Compd. Radiopharm. 1997, 36, 625; (c) Junk, T.;
Catallo, W. J.; Elguero, J. Tetrahedron Lett. 1997, 38, 6309.
6. (a) Vaidyanathan, S.; Surber, B. W. Tetrahedron Lett. 2005, 46, 5195; (b) Hakala,
U.; Wahala, K. J. Org. Chem. 2007, 72, 5817.
7. (a) Garnett, J. L.; Hodges, R. J. J. Am. Chem. Soc. 1967, 89, 4645; (b) Garnett, J. L.;
Iiodges, R. J. J. Chem. Soc., Chem. Commun. 1967, 1001; (c) Bean, G. P.; Johnson, A.
R.; Katrizky, A. R.; Ridgewell, B. J.; White, A. M. J. Chem. Soc. B 1967, 1219; (d)
Long, M. A.; Garnett, J. L.; Vining, R. F. W.; Mole, T. J. Am. Chem. Soc. 1972, 94,
8632; (e) Werstiuk, N. H.; Kadai, T. Can. J. Chem. 1974, 52, 2169; (f) Tashiro, M.;
Nakayama, K. J. Chem. Soc., Perkin Trans. 1 1983, 2315; (g) Iranzo, G. Y.; Elguero, J.
J. Labelled Compd. Radiopharm. 1990, 28, 967; (h) Okazaki, M.; Uchino, N.; No-
zaki, N.; Kubo, K. Bull. Chem. Soc. Jpn. 1995, 68, 1024.
4.1.22. 2-Deuteronaphthalene (40, Table 5, entry 13). A mixture of
2-bromonaphthalene (40.0 mg, 193
mmol), Bu3SnH (62.4 mL,
232 mol), and V-65 (9.6 mg, 38.7 mol) in THF-d8 (4 mL) was
m
m
stirred at reflux for 3 h. The mixture was concentrated in vacuo, and
the residue was purified by column chromatography on silica gel
(pentane) to give 2-deuteronaphthalene (22.1 mg, 88%). 1H NMR
(400 MHz,): 7.49e7.52 (m, 3.28H, 2-H, 3-H, 6-H, 7-H), 7.89e7.91 (m,
4H, 1-H, 4-H, 5-H, 8-H); 2H NMR: 7.53 (br); MS (EIþ): m/z 129 [M]þ;
HRMS (EIþ): calcd for C10H27H [M]þ: 129.06888, found: 129.06937.
8. (a) Neumann, W. P. Synthesis 1987, 665; (b) Oba, M.; Nishiyama, K. Synthesis
1994, 624; (c) Albert, H. J.; Neumann, W. P. Synthesis 1980, 942.
9. We reported preliminary results regarding the iodineedeuterium exchange
reaction on pyrimidine and purine nuclei as a communication, see Mutsumi, T.;
Maruhashi, K.; Monguchi, Y.; Sajiki, H. Synlett 2008, 18, 2811.
References and notes
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12. Bu3SnH was selected over (Bu3Sn)2 because of the most efficient consumption
of the substrate with almost equivalent D content and yield.
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proceeded with moderate
D efficiencies (50e80%) by the competitive
abstraction of deuterium atom of THF-d8 versus hydrogen atom of excess
amount of Bu3SnH.
17. Harrowven, D. C.; Guy, I. L. Chem. Commun. 2004, 1968.