T. Suzuki et al. / Bioorg. Med. Chem. Lett. 15 (2005) 2583–2585
2585
(2a)3b 1H NMR (270 MHz, CDCl3): d = 2.29 (s, 3H),
6.28 (s, 1H), 7.34–8.25 (m, 4H). 3-Phenylisocoumarin
(2b)3b 1H NMR (270 MHz, CDCl3): d = 6.97 (s, 1H),
7.42–7.54 (m, 5H), 7.70–7.76 (m, 1H), 7.86–7.92 (m, 2H),
8.30–8.34 (m, 1H). 1-(2-Hydroxymethylphenyl)-2-propa-
References and notes
1. (a) Barry, R. D. Chem. Rev. 1964, 64, 229; (b) Hepworth,
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Prep. Proced. Int. 1997, 29, 631.
2. (a) Lewis, C. N.; Spargo, P. L.; Staunton, J. Synthesis
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68, 5936, and references therein.
3. (a) Larock, R. C.; Varaprath, S.; Lau, H. H.; Fellows, C.
A. J. Am. Chem. Soc. 1984, 106, 5274; (b) Hauser, F. M.;
Baghdanov, V. M. J. Org. Chem. 1988, 53, 4676; (c)
Shimoyama, I.; Zhang, Y.; Wu, G.; Negishi, E. Tetrahe-
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Nandi, B. J. Chem. Soc., Perkin Trans. 1 1998, 561; (e)
Miura, M.; Tsuda, T.; Satoh, T.; Pivsa-Art, S.; Nomura,
M. J. Org. Chem. 1998, 63, 5211; (f) Wang, L.; Shen, W.
Tetrahedron Lett. 1998, 39, 7625; (g) Sashida, H.; Kaw-
amukai, A. Synthesis 1999, 1145; (h) Larock, R. C.; Doty,
M. J.; Han, X. J. Org. Chem. 1999, 64, 8770.
4. (a) Ogawa, Y.; Maruno, M.; Wakamatsu, T. Heterocycles
1995, 41, 2587; (b) Bellina, F.; Ciucci, D.; Vergamini, P.;
Rossi, R. Tetrahedron 2000, 56, 2533.
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6. Negishi, E.; Makabe, H.; Shimoyama, I.; Wu, G.; Zhang,
Y. Tetrahedron 1998, 54, 1095.
7. (a) Suzuki, T.; Morita, K.; Tsuchida, M.; Hiroi, K. Org.
Lett. 2002, 4, 2361; (b) Suzuki, T.; Morita, K.; Matsuo,
Y.; Hiroi, K. Tetrahedron Lett. 2003, 44, 2003; (c) Suzuki,
T.; Morita, K.; Tsuchida, M.; Hiroi, K. J. Org. Chem.
2003, 68, 1601.
1
none (3a) H NMR (270 MHz, CDCl3): d = 1.49 (s, 3H),
2.56 (br s, 1H), 2.89 and 3.02 (ABq, J = 16.2 Hz, 2H),
4.75 and 5.00 (ABq, J = 15.0 Hz, 2H), 6.92–7.18 (m, 4H).
IR (NaCl) mmax (cmÀ1): 3399 (OH), 1705 (C@O). MS m/z:
164 (M+), 145, 115, 104, 91, 78, 65, 51, 43, 39. HRMS
m/z: (M+) Calcd for C10H12O2: 164.0837. Found:
164.0862.
11. For recent examples of Tishchenko and related reactions,
see: (a) Ooi, T.; Ohmatsu, K.; Sasaki, K.; Miura, T.;
Maruoka, K. Tetrahedron Lett. 2003, 44, 3191; (b)
Gnanadesikan, V.; Horiuchi, Y.; Ohshima, T.; Shibasaki,
M. J. Am. Chem. Soc. 2004, 126, 7782; for a recent review:
(c) To¨rma¨kangas, O. P.; Koskinen, A. M. P. Recent Res.
Devel. Org. Chem. 2001, 5, 225.
12. (a) Uenishi, J.; Masuda, S.; Wakabayashi, S. Tetrahedron
Lett. 1991, 32, 5097; (b) Hsu, J.-L.; Chen, C.-T.; Fang,
J.-M. Org. Lett. 1999, 1, 1989; (c) Adinolfi, M.; Barone,
G.; De Lorenzo, F.; Iadonisi, A. Synlett 1999, 336.
13. Lange, G. L.; Organ, M. G. Synlett 1991, 665.
14. For the intramolecular Tishchenko reaction of dialdehyde,
see: (a) Bergens, S. H.; Fairlie, D. P.; Bosnich, B.
Organometallics 1990, 9, 566; (b) Onozawa, S.-y.; Sakak-
ura, T.; Tanaka, M.; Shiro, M. Tetrahedron 1996, 52,
4291.
15. The reaction using other solvents such as THF, dichloro-
ethane, CH3CN, toluene, and 2-butanone gave unsatis-
factory results.
16. General procedure for the intramolecular Tishchenko
reaction of 1. To a 10 mL test tube containing [Cp*IrCl2]2
(7.2 mg, 0.009 mmol), 2,2-diphenylglycinol17 (3.8 mg,
0.018 mmol), and KOH (5.0 mg, 0.09 mmol) was added
CH2Cl2 (1.8 mL). The mixture was stirred for 2 h at room
temperature, and the insoluble materials were removed by
filtration. 2-Propanol (0.3 mL, 3.92 mmol) was added to
this catalyst solution, and stirred at room temperature for
30 min, then volatile materials were removed under
vacuum, and a solution of 1 (0.36 mmol) in t-BuOH was
added. The mixture was refluxed for 16 h. After cooling to
room temperature, the mixture was passed through a short
silica gel column (12 g, ethyl acetate) to remove the
catalyst and the eluate was concentrated under reduced
pressure. The products were purified by preparative TLC
(hexane–ethyl acetate). In the case of the reaction of 1b,
the product was obtained as an inseparable mixture and
the yield was determined by 270 MHz 1H NMR. 3,4-
8. Recent examples of transfer hydrogenation using Cp*Ir
complexes, see; (a) Mashima, K.; Abe, T.; Tani, K. Chem.
Lett. 1998, 1199; (b) Murata, K.; Ikariya, T.; Noyori, R. J.
Org. Chem. 1999, 64, 2186; (c) Ogo, S.; Makihara, N.;
Watanabe, Y. Organometallics 1999, 18, 5470; (d) Ogo, S.;
Makihara, N.; Kaneko, Y.; Watanabe, Y. Organometallics
2001, 20, 4903; (e) Fujita, K.; Furukawa, S.; Yamaguchi,
R. J. Organomet. Chem. 2002, 649, 289; (f) Fujita, K.;
Yamamoto, K.; Yamaguchi, R. Org. Lett. 2002, 4, 2691;
(g) Abura, T.; Ogo, S.; Watanabe, Y.; Fukuzumi, S. J.
Am. Chem. Soc. 2003, 125, 4149; (h) Fujita, K.; Li, Z.;
Ozeki, N.; Yamaguchi, R. Tetrahedron Lett. 2003, 44,
2687; (i) Fujita, K.; Kitatsuji, C.; Furukawa, S.; Yama-
guchi, R. Tetrahedron Lett. 2004, 45, 3215; (j) Fujita, K.;
Fujii, T.; Yamaguchi, R. Org. Lett. 2004, 6, 3525; (k)
Hanasaka, F.; Fujita, K.; Yamaguchi, R. Organometallics
2004, 23, 1490; (l) Cami-Kobeci, G.; Slatford, P. A.;
Whittlesey, M. K.; Williams, J. M. J. Bioorg. Med. Chem.
Lett. 2005, 15, 535.
Dihydro-3-methylisocoumarin
(5a)18a
1H
NMR
(270 MHz, CDCl3): d = 1.52 (d, J = 6.3 Hz, 3H), 2.87–
3.04 (m, 2H), 4.62–4.75 (m, 1H), 7.24–8.10 (m, 4H).
3,4-Dihydro-3-phenylisocoumarin (5b)18b 1H NMR
(270 MHz, CDCl3): d = 3.14 (dd, J = 16.4, 3.2 Hz, 1H),
3.36 (dd, J = 16.4, 11.9 Hz, 1H), 5.57 (dd, J = 11.9, 3.2 Hz,
1H), 7.2–7.9 (m, 8H), 8.16 (d, J = 7.6 Hz, 1H).
9. Richard, J. P.; Nagorsi, R. W. J. Am. Chem. Soc. 1999,
121, 4763.
10. General procedure for the oxidative lactonization of 1. A
10 mL test tube equipped with a magnetic stirring bar
was charged with 97.7 mg (0.3 mmol) of Cs2CO3 and
9.7 mg (0.02 mmol, 5 mol%) of Ir complex 3. A solution
of 1 (0.36 mmol) in toluene (3.6 mL) and pivalaldehyde
(117 lL, 1.08 mmol) was added to the above mixture and
the whole was stirred at room temperature for 16 h. The
reaction mixture was passed through a short silica gel
column (12 g, ethyl acetate) to remove the catalyst and
then concentrated under reduced pressure. The products
of 2a,b were purified by silica gel column chromatogra-
phy (hexane–ethyl acetate, 4:1). 3-Methylisocoumarin
17. Newman, M. S.; Edwards, W. M. J. Am. Chem. Soc. 1954,
76, 1840.
18. (a) Anttus, S.; Snatzke, G.; Steinke, I. Liebigs Ann. Chem.
1983, 2247; (b) Bobicelli, P.; Lupattelli, P.; Crescenzi, B.;
Sanetti, A.; Bernini, R. Tetrahedron 1999, 55, 14719.
19. Although the details of the mechanism are unclear at
present, one possibility would be a dehydrogenation
mechanism; see Ref. 8f.