1410
N. Hayashi et al.
LETTER
(8) We and other groups have developed the generation and
References and Notes
synthetic use of dihaloindium hydrides (HInX2). See:
(a) Baba, A.; Shibata, I. Chem. Rec. 2005, 5, 323. (b)Inoue,
K.; Sawada, A.; Shibata, I.; Baba, A. Tetrahedron Lett.
2001, 42, 4661. (c) Inoue, K.; Sawada, A.; Shibata, I.; Baba,
A. J. Am. Chem. Soc. 2002, 124, 906. (d) Hayashi, N.;
Shibata, I.; Baba, A. Org. Lett. 2004, 6, 4981. (e) Hayashi,
N.; Shibata, I.; Baba, A. Org. Lett. 2005, 7, 3093.
(f) Takami, K.; Yorimitsu, H.; Oshima, K. Org. Lett. 2002,
4, 2993. (g) Miura, K.; Tomita, M.; Yamada, Y.; Hosomi, A.
J. Org. Chem. 2007, 72, 787.
(1) (a) Yamamoto, Y.; Asao, N. Chem. Rev. 1993, 93, 2207.
(b) Roush, W. R. In Comprehensive Organic Synthesis, Vol.
2; Trost, B. M.; Fleming, I., Eds.; Pergamon Press: Oxford,
1991, Chap. 1.1, 1.
(2) (a) Thomas, E. J. Chem. Commun. 1997, 411. (b) Marshall,
J. A. Chem. Rev. 1996, 96, 31. (c) Nishigaichi, Y.; Takuwa,
A. Tetrahedron 1993, 49, 7395.
(3) (a) Brown, H. C.; Liotta, R.; Kramer, G. W. J. Org. Chem.
1978, 43, 1058. (b) Collins, S.; Dean, W. P.; Ward, D. G.
Organometallics 1988, 7, 2289. (c) Kira, M.; Hino, T.;
Sakurai, H. Tetrahedron Lett. 1989, 30, 1099. (d) Satoh,
M.; Nomoto, Y.; Miyaura, N.; Suzuki, A. Tetrahedron Lett.
1989, 30, 3789. (e) Kobayashi, S.; Nishio, K. Synthesis
1994, 457. (f) Masuyama, Y.; Tsunoda, M.; Kurusu, Y.
J. Chem. Soc., Chem. Commun. 1994, 1451. (g) Gao, Y.;
Urabe, H.; Sato, F. J. Org. Chem. 1994, 59, 5521.
(h) Kobayashi, S.; Nishio, K. J. Org. Chem. 1994, 59, 6620.
(i) Sell, M. S.; Klein, W. R.; Rieke, R. D. J. Org. Chem.
1995, 60, 1077. (j) Takai, K.; Matsukawa, N.; Takahashi,
A.; Fujii, T. Angew. Chem. Int. Ed. 1998, 37, 152.
(k) Takai, K.; Toratsu, C. J. Org. Chem. 1998, 63, 6450.
(l) Bareille, L.; Gendre, P. L.; Moise, C. Chem. Commun.
2005, 775. (m) The generation of allylic indium from diene
by Ni catalyst was reported, see: Hirashita, T.; Kambe, S.;
Tsuji, H.; Araki, S. Chem. Commun. 2006, 2595.
(4) Hayashi, N.; Honda, H.; Yasuda, M.; Shibata, I.; Baba, A.
Org. Lett. 2006, 8, 4553.
(9) Typical Procedure
A 10 mL round-bottom flask charged with InCl3 (2.0 mmol)
was dried by heating to 110 °C under reduced pressure (1
mmHg) for 1 h. After the nitrogen was filled, THF (2 mL)
was added to dissolve InCl3. To the mixture was added
Bu3SnH (2.0 mmol) at –78 °C. The mixture was then stirred
for 10 min to prepare dichloroindium hydride (HInCl2).
After the solution was warmed up to r.t., 2,3-dimethyl-1,3-
butadiene (1a, 4.0 mmol) was added and the resulting
mixture was stirred for 5 h. Then benzil (2b, 1.0 mmol) was
added and stirred for 14 h. The resulting mixture was
quenched by aq 1 N HCl (5 mL) and extracted with Et2O
(3 × 10 mL). The combined organic layer was treated with
aq NH4F and then the precipitate was filtered to remove the
tin compound. The filtrate was extracted with Et2O and dried
over MgSO4. Concentration followed by silica gel column
chromatography eluting with hexane–EtOAc (90:10)
afforded 4ab as a solid.
(5) (a) Cintas, P. Synlett 1995, 1087. (b) Marshall, J. A.
Chemtracts: Org. Chem. 1997, 10, 481. (c) Li, C.-J.; Chan,
T.-H. Tetrahedron 1999, 55, 11149. (d)Araki, S.;Hirashita,
T. In Main Group Metals in Organic Synthesis, Vol. 1;
Yamamoto, H.; Oshima, K., Eds.; Wiley-VCH: Weinheim,
2004, 323–386.
(6) a-Selective allylations: (a) Yanagisawa, A.; Habaue, S.;
Yamamoto, H. J. Am. Chem. Soc. 1991, 113, 8955.
(b) Yanagisawa, A.; Ogasawara, K.; Yasue, K.; Yamamoto,
H. Chem. Commun. 1996, 367. (c) Yanagisawa, A.;
Habaue, S.; Yasue, K.; Yamamoto, H. J. Am. Chem. Soc.
1994, 116, 6130. (d) Ito, A.; Kishida, M.; Kurusu, Y.;
Masuyama, Y. J. Org. Chem. 2000, 65, 494.
(10) Analytical and Spectroscopic Data of Selected
Compounds
Compound 3ab: mp 65–66 °C. IR (KBr): 3494 (OH), 1685
(C=O) cm–1. 1H NMR (400 MHz, CDCl3): d = 7.67–7.59 (m,
4 H), 7.37–7.23 (m, 6 H), 5.12 (s, 1 H), 5.02 (s, 1 H), 3.52 (s,
1 H), 1.56 (s, 3 H), 1.46 (s, 3 H), 1.23 (s, 3 H). 13C NMR (100
MHz, CDCl3): d = 203.43, 151.81, 138.62, 138.42, 131.38,
129.46, 127.79, 127.62, 127.56, 127.15, 115.61, 83.54,
49.37, 24.49, 24.15, 22.85. MS (CI): m/z = 295 (70) [M+ +
1], 278 (22), 277 (100), 212 (20), 211 (86), 105(34). HRMS
(CI, +0.9 mmu): m/z calcd for C20H23O2: 295.1698; found:
295.1707 [M+ + 1].
Compound 4ab: mp 88–89 °C. IR (KBr): 3498 (OH), 1670
(C=O) cm–1; 1H NMR (400 MHz, CDCl3): d = 7.89–7.79 (m,
2 H), 7.63–7.53 (m, 2 H), 7.43–7.25 (m, 6 H), 3.63 (s, 1 H),
3.40 (d, J = 13.8 Hz, 1 H), 2.96 (d, J = 13.8 Hz, 1 H), 1.66
(s, 3 H), 1.61 (s, 3 H), 1.39 (s, 3 H). 13C NMR (100 MHz,
CDCl3): d = 201.39, 143.14, 135.29, 132.61, 132.35, 130.32,
128.69, 127.89, 127.54, 125.11, 122.84, 81.80, 44.66, 21.22,
21.02, 19.74. MS (CI): m/z = 295 (67) [M+ + 1], 278 (22),
277 (100). HRMS (CI, +0.5 mmu): m/z calcd for C20H23O2:
295.1698; found: 295.1703 [M+ + 1].
(e) Yamamoto, Y.; Maruyama, K. J. Org. Chem. 1983, 48,
1565. (f) Yamamoto, Y.; Saito, Y.; Maruyama, K. J. Org.
Chem. 1983, 48, 5408. (g) Kanagawa, Y.; Nishiyama, Y.;
Ishii, Y. J. Org. Chem. 1992, 57, 6988. (h) Keck, G. E.;
Abbott, D. E.; Boden, E. P.; Enholm, E. J. Tetrahedron Lett.
1984, 25, 3927. (i) Ganis, P.; Marton, D.; Peruzzo, V.;
Tagliavini, G. J. Organomet. Chem. 1982, 231, 307.
(j) Benkeser, R. A.; Siklosi, M. P.; Mozdzen, E. C. J. Am.
Chem. Soc. 1978, 100, 2134.
Compound 4ac: IR (neat): 3514 (OH), 1732 (C=O) cm–1. 1H
NMR (400 MHz, CDCl3): d = 7.65 (d, J = 8.0 Hz, 2 H), 7.35
(dd, J = 8.0, 7.5 Hz, 2 H), 7.29 (d, J = 7.5 Hz, 1 H), 3.74 (s,
3 H), 3.50 (s, 1 H), 3.10 (d, J = 13.8 Hz, 1 H), 2.87 (d,
J = 13.8 Hz, 1 H), 1.68 (s, 6 H), 1.60 (s, 3 H). 13C NMR (100
MHz, CDCl3): d = 175.59, 142.20, 131.19, 128.08, 127.58,
125.64, 122.15, 78.00, 52.91, 44.71, 21.11, 21.00, 19.48. MS
(EI, 70 eV): m/z = 248 (1) [M+], 105 (100), 84 (39), 77 (23).
HRMS (EI, +0.2 mmu): m/z calcd for C15H20O3: 248.1412;
found: 248.1414 [M+].
(7) a-Selective allylations by allylic indiums: (a) Miyabe, H.;
Yamaoka, Y.; Naito, T.; Takemoto, Y. J. Org. Chem. 2003,
68, 6745. (b) Isaac, M. B.; Chan, T. H. Tetrahedron Lett.
1995, 36, 8957. (c) Hirashita, T.; Hayashi, Y.; Mitsui, K.;
Araki, S. J. Org. Chem. 2003, 68, 1309. (d) Tan, K. T.;
Chng, S. S.; Cheng, H. S.; Loh, T. P. J. Am. Chem. Soc.
2003, 125, 2958. (e) Loh, T. P.; Tan, K. T.; Yang, J. Y.;
Xiang, C. L. Tetrahedron Lett. 2001, 42, 8701. (f) Loh, T.
P.; Tan, K. T.; Hu, Q. Y. Tetrahedron Lett. 2001, 42, 8705.
(g) Araki, S.; Ito, H.; Katsumura, N.; Butsugan, Y.
J. Organomet. Chem. 1989, 369, 291.
Compound 4ad: IR (neat): 3564 (OH) cm–1. 1H NMR (400
MHz, CDCl3): d = 7.44 (d, J = 8.0 Hz, 2 H), 7.31 (dd,
J = 8.0, 7.2 Hz, 2 H), 7.23 (t, J = 7.2 Hz, 1 H), 3.67 (d,
J = 9.3 Hz, 1 H), 3.57 (d, J = 9.3 Hz, 1 H), 3.37 (s, 3 H), 2.78
(s, 1 H), 2.75 (d, J = 13.8 Hz, 1 H), 2.47 (d, J = 13.8 Hz, 1
Synlett 2008, No. 9, 1407–1411 © Thieme Stuttgart · New York