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T. Takamura-Enya et al. / Tetrahedron Letters 44 (2003) 5969–5973
6. (a) Wang, Z.; Rizzo, C. J. Org. Lett. 2001, 3, 565–568; (b)
C60H73N6O6Si2: 1029.5130). 5c: 1H NMR (CDCl3, 600
MHz) l: 8.57 (brs, 1H), 8.41 (brs, 1H), 8.16–8.10 (m,
4H), 8.05–7.94 (m, 4H), 7.34 (d, J=7.14, 2H), 7.33–7.17
(m, 12H), 6.76 (d, J=8.2, 4H), 6.24 (brs, 1H), 6.04 (s,
2H), 5.02 (brs, 1H), 4.51 (brs, 1H), 4.12 (m, 1H), 3.91–
3.75 (m, 8H), 2.22 (brs, 1H), 1.64 (brs, 1H), 0.92 (s, 9H),
0.58 (s, 9H), 0.12 (s, 3H), 0.11 (s, 3H), −0.22 (s, 3H),
−0.34 (s, 3H): FAB-HRMS: m/z 1103.5319 ([M+H]+)
(calcd for C66H75N6O6Si2: 1103.5287). 5d: 1H NMR
(CDCl3, 600 MHz) l: 7.88 (s, 1H), 7.70–7.63 (m, 3H),
7.48 (d, J=7.7, 1H), 7.43 (d, J=8.3, 1H), 7.35–7.15 (m,
17H), 6.75 (d, J=9.3, 4H), 6.12 (brs, 1H), 6.04 (s, 2H),
5.02 (brs, 1H), 4.48 (brs, 1H), 4.00–3.80 (m, 5H), 3.85 (s,
6H), 2.64 (brs, 1H), 2.12 (brs, 1H), 0.90 (s, 9H), 0.86 (s,
9H), 0.09 (s, 3H), 0.08 (s, 3H), 0.05 (s, 3H), 0.04 (s, 3H):
FAB-HRMS: m/z 1067.5310 ([M+H]+) (calcd for
C63H75N6O6Si2: 1067.5286). 5e: 1H NMR (CDCl3, 600
MHz) l: 8.78 (d, J=7.1, 1H), 8.47 (d, J=7.1, 1H), 8.43
(brs, 2H), 8.29 (d, J=8.3, 1H), 8.27 (d, J=8.3, 1H), 7.75
(t, J=7.7, 1H), 7.70 (t, J=7.1, 1H), 7.48 (t, J=7.7, 1H),
7.34 (d, J=7.6, 2H), 7.33–7.17 (m, 12H), 6.76 (d, J=8.2,
4H), 6.10 (brs, 1H), 6.08 (s, 1H), 5.02 (brs, 2H), 4.44 (brs,
1H), 4.14 (brs, 1H), 3.91–3.75 (m, 8H), 2.22 (brs, 1H),
1.64 (brs, 1H), 0.91 (s, 9H), 0.61 (s, 9H), 0.099 (s, 6H),
−0.19 (s, 3H), −0.31 (s, 3H): FAB-HRMS: m/z 1103.5319
([M+H]+) (calcd for C67H75N6O7Si2: 1103.5287).
Gillet, L. C.; Scharer, O. D. Org. Lett. 2002, 4, 4205–
4208; (c) Meier, C.; Gra¨sl, S. Synlett 2002, 802–804.
7. Enya, T.; Suzuki, H.; Watanabe, T.; Hirayama, T.; Hisa-
matsu, Y. Environ. Sci. Technol. 1997, 31, 2772–2776.
8. Saneyoshi, M. Chem. Pharm. Bull. 1968, 16, 1616–1619.
9. Soli, E. D.; Manoso, A. S.; Patterson, M. C.; DeShong,
P.; Favor, D. A.; Hirschmann, R.; Smith, A. B., III J.
Org. Chem. 1999, 64, 3171–3177.
10. To compound 1 (2 mmol) dissolved in 20 ml of acetoni-
trile, trimethylsilyl azide (10 mmol) was added via a
syringe followed by addition of 10 ml of 1 M solution of
TBAF in THF. The reaction was heated at 65°C for 8 h
and the mixture was then allowed to return to room
temperature and concentrated in vacuo to give a yellow
oil which was chromatographed (hexane:ethyl acetate,
3:1) to afford 2 as a colorless oil; FAB-HRMS m/z:
785.3096 (calcd for C42H41N8O8: 785.3057), IR w (cm−1):
2148 (N3). This oil was immediately dissolved in
methanol and to this solution was added NaBH4 (50 mg)
at 0°C. After the initial spot on TLC disappeared,
sodium methoxide (300 ml) was added. The reaction
mixture was quenched by the addition of water and
extracted with ethyl acetate. The organic extract was
combined, dried over Na2SO4, and filtered. The solvent
was finally removed in vacuo to yield almost pure desired
1
amine (45% yield from 1). H NMR (CDCl3, 600 MHz)
13. Fully protected dG adduct 5a–e (0.1 mmol) was dissolved
in dichloromethane (2 ml). To this solution was added 1
l: 7.31–7.16 (m, 14H), 6.74 (d, J=8.8, 4H), 6.05 (brs,
2H), 5.10 (brs, 2H), 4.75 (brs, 1H), 4.54 (brs, 1H),
3.92–3.67 (m, 9H), 2.77 (brs, 1H), 2.01 (brs, 1H): FAB-
HRMS: m/z: 675.2977 ([M+H]+) (calcd for C38H39N6O6:
675.2931).
ml of
1 M zinc bromide solution in 2-propanol/
dichloromethane. The reaction was quenched by the
addition of aqueous NaHCO3, and materials were
extracted with dichloromethane. The organic layer was
combined, dried and evaporated, and the residue was
chromatographed on silica gel using hexane–ethylacetate
as an eluent.
11. (a) Wolfe, J. P.; Tomori, H.; Sadighi, J. P.; Yin, J.;
Buchwald, S. L. J. Org. Chem. 2000, 65, 1158–1174; (b)
Lakshman, M. K.; Keeler, J. C.; Hilmer, J. H; Martin, J.
Q. J. Am. Chem. Soc. 1999, 121, 6090–6091; (c) Laksman,
M. K.; Hilmer, J. H.; Martin, J. Q.; Keeler, J. C.; Dinh,
Y. Q. V.; Ngassa, F. N.; Russon, L. M. J. Am. Chem.
Soc. 2001, 123, 7779–7787.
14. Detritylated compounds 5a–e (0.05 mmol) in THF were
hydrogenized under a balloon with palladium black (20
mg). After 30 min, Pd black was filtered off with Celite,
and the filtrate was evaporated. The residue was redis-
solved in THF and triethylamine trihydrogenfluoride
(100ml) was added to this solution with stirring overnight
at room temperature. The next day, triethylamine (88 ml)
was added and the solvent was evaporated. The residue
was dissolved in CH3CN/water and subjected to HPLC
with an ODS column. Elution was performed with a
linear gradient of 15% to 80% acetonitrile containing
0.25% triethylamine-acetate buffer at pH 7.0. A main
peak was collected and freeze-dried. 6a: 1H NMR
(DMSO-d6, 600 MHz) l: 10.56 (brs, 1H), 8.75 (s, 1H),
7.82 (d, J=8.8, 2H), 7.63 (d, J=7.7, 2H), 7.58 (d, J=8.8,
2H), 7.43 (d, J=7.1, 1H), 7.42 (d, J=7.7, 1H), 7.29 (t,
J=7.1, 1H), 6.39 (s, 2H), 6.37 (dd, J=9.9, 6.0, 1H), 5.97
(s, 1H), 5.33 (s, 1H), 4.42 (d, J=5.5, 1H), 3.93 (s, 1H),
3.77 (s, 2H), 2.41 (dd, J=17.3, 7.1, 1H), 2.02 (dd, J=
13.2, 6.0): FAB-HRMS: m/z: 435.1781 ([M+H]+) (calcd
12. Amine 3 (0.1 mmol), arylbromide 4 (0.12 mmol), pota-
sium tert-butoxide (0.15 mmol), Pd2dba3 (0.01 mmol),
and a phosphine ligand (0.024 mmol) were placed in a 5
ml flask and purged with argon. Toluene (1 ml) was
added and the reaction vessel was heated to 100°C for 2
h. The mixture was cooled to 25°C, diluted with chloro-
form and filtered through Celite. The filtrate was concen-
trated and purified by column chromatography on silica
1
gel. 5a: H NMR (CDCl3, 600 MHz) l: 7.61 (d, J=8.2,
1H), 7.55 (d, J=7.1, 1H), 7.49 (d, J=8.2, 1H), 7.42 (s,
1H), 7.39 (t, J=8.2, 1H), 7.34–7.15 (m, 18H), 6.74 (d,
J=8.8, 4H), 6.19 (brs, 1H), 6.03 (s, 2H), 4.45 (brs, 1H),
4.00–3.77 (m, 3H), 3.76 (s, 6H), 2.70 (brs, 1H), 2.10 (brs,
1H), 0.92 (s, 3H), 0.90 (s, 6H), 0.85 (s, 6H), 0.81 (s, 3H),
0.11 (s, 2H), 0.08 (s, 2H), 0.07 (s, 2H), 0.04 (s, 2H), 0.03
(s, 2H), 0.05 (s, 1H), 0.07 (s, 1H): FAB-HRMS: m/z
1055.5236 ([M+H]+) (calcd for C62H75N6O6Si2:
1
for C22H23N6O4: 435.1781). 6b: H NMR (DMSO-d6, 600
1
1055.5287). 5b: H NMR (CDCl3, 600 MHz) l: 8.12 (s,
MHz) l: 10.57 (brs, 1H), 8.83 (s, 1H), 8.34 (s, 1H),
7.81–7.72 (m, 4H), 7.42 (t, J=7.7 1H), 7.31 (t, J=7.7,
1H), 6.37–6.35 (m, 3H), 6.00 (t, J=4.4, 1H), 5.33 (d,
J=3.3, 1H), 4.44 (s, 1H), 3.94 (d, J=1.6, 1H), 3.79 (s,
2H), 2.79 (ddd, J=13.2, 9.9, 6.0, 1H), 2.35 (dd, J=12.6,
6.1, 1H): FAB-HRMS: m/z: 409.1624 ([M+H]+) (calcd for
C20H21N6O4: 409.1624). 6c: 1H NMR (DMSO-d6, 600
1H), 7.77–7.69 (m, 4H), 7.52 (dd, J=8.7, 2.1, 2H), 7.40–
7.17 (m, 14H), 6.74 (d, J=6.6, 4H), 6.19 (brs, 1H), 6.04
(s, 2H), 5.09 (brs, 1H), 4.49 (brs, 1H), 4.00–3.79 (m, 3H),
3.76 (s, 6H), 2.60 (brs, 1H), 2.10 (brs, 1H), 0.89 (s, 9H),
0.87 (s, 9H), 0.08 (s, 3H), 0.06 (s, 3H), 0.04 (s, 3H), 0.03
(s, 3H): FAB-HRMS: m/z 1029.5177 ([M+H]+) (calcd for