1
04
Y. Terao et al. / Tetrahedron Letters 43 (2002) 101–104
Hz, 1H), 7.07 (d, J=8.1 Hz, 2H), 7.17 (d, J=8.1 Hz,
References
+
2H), 9.63 (d, J=2.2 Hz, 1H); HRMS m/z (M ) calcd for
1
2
3
. Tsuji, J. Palladium Reagents and Catalysts; Wiley:
Chichester, 1995.
C H O 218.1670, found 218.1673.
Compound 7: Oil; H NMR (400 MHz, CDCl ) l=0.86
(t, J=7.0 Hz, 3H), 1.20–1.34 (m, 8H), 1.64–1.75 (m, 1H),
15
22
1
3
. Metal-Catalyzed Cross-Coupling Reactions; Diederich,
F.; Stang, P. J., Eds.; Wiley-VCH: Weinheim, 1997.
. (a) Satoh, T.; Kawamura, Y.; Miura, M.; Nomura, M.
Angew. Chem., Int. Ed. Engl. 1997, 36, 1740; (b) Satoh,
T.; Inoh, J.-I.; Kawamura, Y.; Kawamura, Y.; Miura,
M.; Nomura, M. Bull. Chem. Soc. Jpn. 1998, 71, 2239; (c)
Satoh, T.; Kametani, Y.; Terao, Y.; Miura, M.; Nomura,
M. Tetrahedron Lett. 1999, 40, 5345; (d) Terao, Y.;
Satoh, T.; Miura, M.; Nomura, M. Bull. Chem. Soc. Jpn.
1
3
2
.98–2.08 (m, 1H), 3.48 (ddd, J=2.2, 7.3, 7.7 Hz, 1H),
.81 (s, 3H), 6.90 (d, J=8.8 Hz, 2H), 7.11 (d, J=8.8 Hz,
H), 9.62 (d, J=2.2 Hz, 1H); HRMS m/z (M ) calcd for
+
C H O 234.1620, found 234.1612.
1
5
22
2
1
Compound 8: Oil; H NMR (400 MHz, CDCl ) l=0.86
3
(
t, J=6.9 Hz, 3H), 1.22–1.37 (m, 8H), 1.71–1.81 (m, 1H),
2
7
2
.05–2.15 (m, 1H), 3.53 (ddd, J=2.2, 7.3, 7.5 Hz, 1H),
.26 (d, J=8.7 Hz, 2H), 7.32–7.38 (m, 1H), 7.42–7.48 (m,
1
999, 72, 2345; (e) Terao, Y.; Satoh, T.; Miura, M.;
H), 7.58–7.61 (m, 4H), 9.70 (d, J=2.2 Hz, 1H); HRMS
Nomura, M. Tetrahedron 2000, 56, 1315; (f) Terao, Y.;
Kametani, Y.; Wakui, H.; Satoh, T.; Miura, M.;
Nomura, M. Tetrahedron 2001, 57, 5967.
+
m/z (M ) calcd for C H O 280.1827, found 280.1823.
Compound 9: Oil; H NMR (400 MHz, CDCl ) l=0.85
20
24
1
3
(
t, J=6.9 Hz, 3H), 1.20–1.41 (m, 8H), 1.82–1.93 (m, 1H),
4. (a) Palucki, M.; Buchwald, S. L. J. Am. Chem. Soc. 1997,
2
7
.30–2.40 (m, 1H), 4.25 (ddd, J=1.5, 6.6, 7.3 Hz, 1H),
.33 (d, J=7.0 Hz, 1H), 7.47–7.58 (m, 3H), 7.82 (d,
1
19, 11108; (b) Ahman, J.; Wolfe, J. P.; Troutman, M.
V.; Palucki, M.; Buchwald, S. L. J. Am. Chem. Soc. 1998,
20, 1918; (c) Old, D. W.; Wolfe, J. P.; Buchwald, S. L.
J=8.4 Hz, 1H), 7.90 (d, J=7.0 Hz, 1H), 8.04 (d, J=8.1
Hz, 1H), 9.70 (d, J=1.5 Hz, 1H); HRMS m/z (M ) calcd
1
+
J. Am. Chem. Soc. 1998, 120, 9722; (d) Fox, J. M.;
Huang, X.; Chieffi, A.; Buchwald, S. L. J. Am. Chem.
Soc. 2000, 122, 1360; (e) Moradi, W. A.; Buchwald, S. L.
J. Am. Chem. Soc. 2001, 123, 7996.
for C H O 254.1671, found 254.1678.
1
8
22
1
Compound 11: Mp 143–144°C; H NMR (400 MHz,
CDCl ) l=3.01 (dd, J=7.7, 14.0 Hz, 1H), 3.50 (dd,
3
J=6.9, 14.0 Hz, 1H), 3.87 (ddd, J=1.5, 6.9, 7.7 Hz, 1H),
5
6
. (a) Hamann, B. C.; Hartwig, J. F. J. Am. Chem. Soc.
7
7
1
.07–7.10 (m, 2H), 7.16–7.23 (m, 5H), 7.33–7.37 (m, 1H),
1
997, 119, 12382; (b) Kawatsura, M.; Hartwig, J. F. J.
.41–7.46 (m, 2H), 7.55–7.60 (m, 4H), 9.77 (d, J=1.5 Hz,
Am. Chem. Soc. 1999, 121, 1473; (c) Shaughnessy, K. H.;
Hamann, B. C.; Hartwig, J. F. J. Org. Chem. 1998, 63,
+
H); MS m/z 286 (M ). Anal. calcd for C H O: C,
21 18
6
546; (d) Lee, S.; Beare, N. A.; Hartwig, J. F. J. Am.
88.08; H, 6.34. Found: C, 87.71; H, 6.34.
1
Chem. Soc. 2001, 123, 8410.
Compound 13: Mp 77–79°C; H NMR (400 MHz,
. (a) Muratake, H.; Hayakawa, A.; Natsume, M. Tetra-
hedron Lett. 1997, 38, 7577; (b) Muratake, H.; Natsume,
M. Tetrahedron Lett. 1997, 38, 7581; (c) Muratake, H.;
Nakai, H. Tetrahedron Lett. 1999, 40, 2355.
. Terao, Y.; Satoh, T.; Miura, M.; Nomura, M. Tetra-
hedron Lett. 1998, 39, 6203.
CDCl ) l=1.82 (s, 3H), 7.21–7.46 (m, 10H), 7.57–7.60
3
+
(m, 4H), 9.94 (s, 1H); MS m/z 286 (M ). Anal. calcd for
C H O: C, 88.08; H, 6.34. Found: C, 87.97; H, 6.50.
2
1
18
1
Compound 15; Oil; H NMR (400 MHz, CDCl ) l=0.88
3
7
8
(t, J=6.7 Hz, 3H), 1.00–1.35 (m, 8H), 2.24–2.28 (m, 2H),
7.19 (d, J=7.7 Hz, 4H), 7.26–7.31 (m, 2H), 7.33–7.38 (m,
+
. Pd-catalyzed a-allylation of aldehydes: Kimura, M.;
Horino, Y.; Mukai, R.; Tanaka, S.; Tamaru, Y. J. Am.
Chem. Soc. 2001, 123, 10401.
4H), 9.80 (s, 1H); HRMS m/z (MH ) calcd for C H O
2
0
25
281.1905, found 281.1904.
1
1
1
1. The reaction of ethyl 4-bromobenzoate as an aryl bro-
mide having an electron-withdrawing group reacted with
1a to give the corresponding coupled product (ca. 60% by
GC). However, its chromatographic purification was not
successful due to partial decomposition.
3
9. Typical procedure: In a 100 cm two-necked flask was
placed Cs CO (1.2 mmol, 391 mg), which was then dried
2
3
at 150°C in vacuo for 2 h. Then, Pd(OAc) (0.05 mmol,
2
1
1.2 mg), P(t-Bu) (0.1 mmol, 20.2 mg), 1a (2 mmol, 256
3
mg), 2a (1 mmol, 157 mg), 1-methylnaphthalene (ca. 100
2. Pioneering work using Pd-P(t-Bu) for the amination of
3
3
mg) as internal standard and dioxane (5 cm ) were added.
aryl halides: (a) Nishiyama, M.; Yamamoto, T.; Koie, Y.
Tetrahedron Lett. 1998, 39, 617; (b) Yamamoto, T.;
Nishiyama, M.; Koie, Y. Tetrahedron Lett. 1998, 39,
The resulting mixture was stirred under N2 at 110°C
(bath temperature) for 2 h. After cooling, the reaction
mixture was extracted with diethyl ether and dried over
sodium sulfate. Product 3 (129 mg, 63%) was isolated by
column chromatography on silica gel using hexane–
2367.
3. Dyker, G.; Heiermann, J.; Miura, M.; Inoh, J.-I.; Pivsa-
15 1
Art, S.; Satoh, T.; Nomura, M. Chem. Eur. J. 2000, 6,
diethyl ether (99.5:0.5, v/v) as eluent: oil; H NMR (400
3
426.
4. Littke, A. F.; Fu, G. C. J. Am. Chem. Soc. 2001, 123,
989 and references cited therein.
MHz, CDCl ) l=0.86 (t, J=6.8 Hz, 3H), 1.19–1.33 (m,
3
1
1
1
8
H), 1.68–1.76 (m, 1H), 2.02–2.10 (m, 1H), 3.48 (ddd,
6
J=2.2, 6.2, 6.6 Hz, 1H), 7.19 (d, J=7.7 Hz, 2H), 7.27–
5. Pallaud, R.; Lang, L. N. C. R. Acad. Sci. Ser. C Fr. 1971,
7
.31 (m, 1H), 7.34–7.39 (m, 2H), 9.66 (d, J=2.2 Hz, 1H);
1
3
273, 418.
C NMR (100 MHz, CDCl ) l=14.01, 22.55, 27.03,
3
6. Cavallini, G.; Massarani, E.; Nardi, D.; Mauri, L.;
2
2
9.10, 29.68, 31.56, 59.22, 127.48, 128.76, 129.00, 136.54,
+
Barzaghi, F.; Mantegazza, P. J. Am. Chem. Soc. 1959, 81,
2564.
7. Zimmerman, H. E.; Heydinger, J. A. J. Org. Chem. 1991,
01.07; MS m/z 204 (M ).
1
1
0. Compound 6: Oil; H NMR (400 MHz, CDCl ) l=0.86
3
1
(t, J=6.9 Hz, 3H), 1.14–1.38 (m, 8H), 1.62–1.75 (m, 1H),
1
.98–2.08 (m, 1H), 2.34 (s, 3H), 3.44 (ddd, J=2.2, 7.0, 7.7
56, 1747.
.