Table 3 The Ni-catalyzed InI-mediated reaction of piperylene with
benzaldehyde
of the v-formyl diene and benzaldehyde through intramolecular
cyclization. Further applications of this procedure are currently
under study.
a
Entry
Conditions
DMI, H O (200 mol%),
THF, 18 h
Yield (%)
This work was partially supported by a Grant-in-Aid for
Scientific Research (No. 14340195) from the Ministry of
Education, Science, Sport and Culture, Japan.
1
2
a
2
7: 5 (71 : 29), 8: 44
(77 : 11 : 6 : 6) , 9: 47
7: trace, 8: trace, 9: 79
d
e
4
h
d
(
28 : 2 : 26 : 12 : 28 : 4)
All reactions were carried out with piperylene (0.50 mmol),
benzaldehyde (0.50 mmol), InI (0.50 mmol), Ni(acac) (10 mol%)
and PPh (40 mol%) in solvent (1 mL) at room temperature.
Notes and references
2
3
1 (a) P. Cintas, Synlett, 1995, 1087; (b) J. A. Marshall, Chemtracts: Org.
Chem., 1997, 10, 481; (c) C.-J. Li and T.-H. Chan, Tetrahedron, 1999, 55,
11149; (d) S. Araki and T. Hirashita, in Main Group Metals in Organic
Synthesis, ed. H. Yamamoto and K. Oshima, Wiley-VCH, Weinheim,
b
1
c
Determined by H NMR. A small amount (1%) of 1-phenylhex-
-en-1-ol was also obtained. Determined by GC analysis of the
d
3
corresponding diacetates. Diastereomeric ratio was not determined.
e
2004, vol. 1, pp. 323–386.
2
3
S. Araki, H. Ito and Y. Butsugan, J. Org. Chem., 1988, 53, 1831.
S. Araki, T. Kamei, T. Hirashita, H. Yamamura and M. Kawai, Org.
Lett., 2000, 2, 847 and references therein.
4
5
T. Hirashita, S. Kambe, H. Tsuji, H. Omori and S. Araki, J. Org. Chem.,
2004, 69, 5054.
Reviews: (a) Y. Tamaru, J. Organomet. Chem., 1999, 576, 215; (b)
S. Ikeda, Angew. Chem., Int. Ed., 2003, 42, 5120; (c) Ni-catalyzed reaction
of dienes with carbonyl compounds: Y. Sato, M. Takimoto, K. Hayashi,
T. Katsuhara, K. Takagi and M. Mori, J. Am. Chem. Soc., 1994, 116,
9771; (d) J. Montgomery, E. Oblinger and A. V. Savchenko, J. Am.
Chem. Soc., 1997, 119, 4911; (e) M. Kimura, A. Ezoe, K. Shibata and
Y. Tamaru, J. Am. Chem. Soc., 1998, 120, 4033; (f) M. Takimoto,
Y. Hiraga, Y. Sato and M. Mori, Tetrahedron Lett., 1998, 39, 4543; (g)
Y. Sato, T. Takanashi, M. Hoshiba and M. Mori, Tetrahedron Lett.,
Scheme 6
1
998, 39, 5579; (h) Y. Sato, N. Saito and M. Mori, Tetrahedron, 1998, 54,
Table 4 The intramolecular cyclization of diene 10
1153; (i) M. Kimura, H. Fujimatsu, A. Ezoe, K. Shibata, M. Shimizu,
1
0 : PhCHO
Yield of 11 (%)
(diastereomeric ratio)
S. Matsumoto and Y. Tamaru, Angew. Chem., Int. Ed., 1999, 38, 397; (j)
M. Kimura, S. Matsuo, K. Shibata and Y. Tamaru, Angew. Chem., Int.
Ed., 1999, 38, 3386; (k) M. Kimura, K. Shibata, Y. Koudahashi and
Y. Tamaru, Tetrahedron Lett., 2000, 41, 6789; (l) Y. Sato, N. Saito and
M. Mori, J. Am. Chem. Soc., 2000, 122, 2371; (m) Y. Sato, M. Takimoto
and M. Mori, J. Am. Chem. Soc., 2000, 122, 1624; (n) K. Shibata,
M. Kimura, K. Kojima, S. Tanaka and Y. Tamaru, J. Organomet.
Chem., 2001, 624, 348; (o) Y. Sato, R. Sawaki and M. Mori,
Organometallics, 2001, 20, 5510; (p) Y. Kimura, A. Ezoe, S. Tanaka
and Y. Tamaru, Angew. Chem., Int. Ed., 2001, 40, 3600; (q) A. Ezoe,
M. Kimura, T. Inoue, M. Mori and Y. Tamaru, Angew. Chem., Int. Ed.,
a
Entry (mmol)
Conditions
1
2
3
a
0.25/0.50
0.25/0.50
0.50/0.50
DMI, 4 h
THF, 24 h
55 (7 : 42 : 6 : 21 : 24)
55 (7 : 7 : 22 : 28 : 36)
O (1 mmol), 24 h 56 (6 : 57 : 3 : 10 : 24)
DMI, H
2
Determined by GC analysis.
2
002, 41, 2784; (r) Y. Sato, N. Saito and M. Mori, J. Org. Chem., 2002,
7, 9310; (s) Y. Sato, N. Saito and M. Mori, Chem. Lett., 2002, 18; (t)
Y. Sato, R. Sawaki, N. Saito and M. Mori, J. Org. Chem., 2002, 67, 656;
u) R. Sawaki, Y. Sato and M. Mori, Org. Lett., 2004, 6, 1131; (v)
M. Kimura, A. Ezoe, M. Mori and Y. Tamaru, J. Am. Chem. Soc., 2005,
27, 201.
2-(4-Acetyloxy-4-phenylbut-1-enyl)-4,4-dimethylcyclopentyl acetate (11):
Anhydrous Ni(acac) was prepared from Ni(acac) ?2H O (15 mg,
.050 mmol, 20 mol%) by heating with a heat gun before use. To a
mixture of the Ni(acac) , InI (121 mg, 0.50 mmol) and PPh (52 mg,
.20 mmol, 80 mol%) in DMI (1.0 mL), 3,3-dimethylocta-5,7-dienal
38 mg, 0.25 mmol) and benzaldehyde (52 mL, 0.50 mmol) were added
6
(
1
6
2
2
2
0
2
3
0
(
and the reaction mixture was stirred at room temperature for 4 h. After
the reaction mixture was treated with DMAP (10 mg), pyridine (1 mL)
and acetic anhydride (1 mL) at room temperature for 1 h, the reaction
Scheme 7
2
was quenched with H O (3 mL) and the products were extracted with
(
entry 2) and even in moist DMI (entry 3), 11 was solely obtained.
diethyl ether. The combined ether layer was successively washed with 1 M
HCl, saturated aq. NaHCO and brine. The ether solution was dried over
These facts indicate that the intramolecular chelation depicted as C
in Scheme 7 is much tighter than that in the cases of the 1,3-dienes
in Table 1, Table 2 and Table 3 and/or the bulkiness arising from
the cyclopentyl substituent of D is crucial for preventing the
reaction at the c-position.
3
2 4
Na SO and the solvent was removed under reduced pressure to give
the crude product (158 mg). Chromatographic separation on silica gel,
using hexane–EtOAc (15 : 1 to 4 : 1) as eluent, gave 11 (47 mg, 55%, dr =
7
: 42 : 6 : 21 : 24) (Found: C, 72.92; H, 8.51. Calc. for C21
73.23; H, 8.19%); The diastereomeric ratio was determined by GC; dH
200 MHz; CDCl ; Me Si): (major) 2.06, 2.07 (s, total 6 H, Ac 6 2),
.99–1.02, 1.06–1.19 (m, total 6 H, Me ), 1.25–1.84 (m, 4 H, CH CCH ),
.50–2.75 (m, 2 H, LCHCH ), 2.62–2.80, 2.82–2.99 (m, total 1 H, CH),
.04–5.17 (m, 1 H, CHCHOAc), 5.23–5.50 (m, 2 H, CHLCH), 5.66–5.76
(m, 1 H, CHPh), 7.23–7.34 (m, 5 H, Ph).
28 4
H O : C,
(
0
2
5
3
4
In conclusion, the double addition of aldehydes toward 1,3-
dienes has been achieved by the Ni-catalyzed InI-mediated
reaction. The regioselectivity has successfully been controlled by
water in the solvent. The reaction has been applied to the coupling
2
2
2
2
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Chem. Commun., 2006, 2595–2597 | 2597