Notes
J . Org. Chem., Vol. 64, No. 21, 1999 8039
LiCl (0.020 g, 0.471 mmol) in 2 mL of anhydrous dioxane at room
temperature was added stannane 6b (0.345 g, 0.620 mmol)
dissolved in 7 mL of anhydrous dioxane. The resulting red
reaction mixture was stirred for 6 h at 60 °C. The mixture was
cooled to room temperature and extracted with ether. The
organic layer was washed with water, dried over MgSO4, filtered,
and concentrated. Purification by flash chromatography on silica
eluting with ether/hexane (1:2) provided 0.050 g (35%) of the
bisnaphthopyranyl quinone 10a as a red solid, 0.030 g (37%) of
11 as an orange oil, and 0.020 g (25%) of 8a .
120.40, 122.67, 124.07 (124.12), 124.57 (124.67), 125.41 (125.52),
125.96, 126.16, 127.73, 127.94, 129.01 (129.08), 129.23, 129.79,
130.48, 130.70, 131.11 (131.23), 131.63, 132.12, 134.35, 143.76,
145.19, 146.28 (145.65), 148.13 (147.68), 151.95 (151.89, 151.99),
152.04 (152.11), 152.83 (152.07), 153.38, 154.29, 163.99, 182.85
(182.76), 183.88 (184.67); FT-IR 1718, 1666, 1295 cm-1; MS
(FAB) m/z (relative intensity) 915 (M+, 18), 884 (23), 832 (100);
HRMS (FAB) calcd for C58H61NO9Na (M + Na)+ 938.4244, found
938.4225. Anal. Calcd for C58H61NO9: C, 76.04; H, 6.71. Found:
C, 75.50; H, 6.78.
Analytical data for 10a : mp ) 82-86 °C; Rf ) 0.43 (ether/
hexane, 1:1); 1H NMR (500 MHz)31 δ 1.01 (t, 3H, J ) 6.8 Hz),
1.10 (t, 3H, J ) 6.8 Hz), 1.36-1.39 (m, 6H), 1.48 (s, 3H), 1.54 (s,
3H), 1.59 (s, 3H), 1.64-1.68 (m, 5H), 1.72-1.74 (m, 2H), 2.06-
2.10 (m, 4H), 3.17-3.37 (m, 4H), 3.23 (s, 0.5 H), 3.56 (s, 2.5H),
5.03-5.07 (m, 2H), 5.27 (d, 1H, J ) 6.6 Hz), 5.37 (d, 1H, J ) 6.6
Hz), 5.56-5.60 (m, 2H), 6.74 (d, 1H, J ) 8.7 Hz), 6.82 (d, 1H, J
) 8.8 Hz), 6.89-6.93 (m, 2H), 7.24-7.28 (m, 1H), 7.31-7.35 (m,
2H), 7.39 (d, 1H, J ) 1.8 Hz), 7.51 (s, 1H), 7.61 (s, 0.5 H), 7.75-
7.79 (m, 2H), 7.95 (s, 0.5 H), 8.16-8.22 (m, 2H); 13C NMR (125
MHz)31 δ 13.25, 14.11 (13.93), 17.58, 17.62, 22.69 (22.77), 22.82,
25.60, 25.65, 26.09, 26.16, 40.83, 40.91, 41.71 (41.45), 42.08
(41.91), 56.30 (55.77), 78.36, 78.60, 95.04 (94.84), 102.98 (103.87),
112.41, 112.63 (112.75), 113.28, 116.41, 116.66, 117.82, 118.81,
122.55, 124.06, 124.12, 124.39, 124.64, 126.17, 126.51, 126.67,
127.75, 127.98, 129.10, 129.82, 129.86, 130.49, 130.73, 131.17,
131.27, 131.63, 132.38, 133.60, 133.65, 144.12, 145.02 (145.43),
146.70, 148.09 (147.60), 152.02 (151.94), 152.82 (153.05), 153.37,
154.23, 183.79 (184.59) (two carbons); FT-IR 1725, 1668, 1291
cm-1; MS (FAB) m/z (relative intensity) 885 (M+, 25), 854 (25),
802 (80); HRMS (FAB) calcd for C57H59NO8Li (M + Li)+
892.4240, found 892.4398.
1,4-Dih ydr o-2-[4-m eth oxyph en yl]-3-[9-(m eth oxym eth oxy)-
3-m eth yl-3-(4-m eth yl-3-p en ten yl)-3H-n a p h th o[2,1-b]p yr a n -
8-yl]-1,4-n a p h th a len ed ion e (13). To a suspension of the
triflate 9a (0.509 g, 0.793 mmol), Pd(PPh3)4 (0.241 g, 0.208
mmol), and LiCl (0.253 g, 0.596 mmol) in 20 mL of anhydrous
dioxane was added the stannane 12a 23 (1.17 g, 4.12 mmol)
dissolved in 20 mL of anhydrous dioxane. The resulting suspen-
sion was stirred for 20 h at 65 °C. The mixture was cooled to
room temperature and filtered through a small plug of cotton.
The filtrate was concentrated and the residue purified by flash
chromatography on silica eluting with ether/hexane (1:3), pro-
viding 0.286 g (60%) of the arylnaphthopyranyl quinone 13 as a
1
red powder: mp ) 72-75 °C; Rf ) 0.38 (ether/hexane, 1:1); H
NMR (300 MHz)31 δ 1.42 (d, 3H, J ) 10.3), 1.56 (d, 3H, J ) 3.6
Hz), 1.65 (d, 3H, J ) 1.2 Hz), 1.71-1.82 (m, 2H), 2.09-2.19 (m,
2H), 3.42 (s, 3H), 3.71 (s, 3H), 5.08-5.14 (m, 1H), 5.09 (d, 1H, J
) 6.9 Hz), 5.20 (d, 1H, J ) 6.6 Hz), 5.64 (dd, 1H, J ) 10.7, 1.5
Hz), 6.70 (dd, 2H, J ) 9.0, 0.9 Hz), 6.84 (d, 1H, J ) 8.7 Hz),
6.95 (d, 1H, J ) 10.5 Hz), 7.12 (d, 2H, J ) 8.4 Hz), 7.22 (s, 1H),
7.37 (d, 1H, J ) 9.0 Hz), 7.51 (s, 1 H), 7.76-7.78 (m, 2H), 8.14-
8.19 (m, 1H), 8.21-8.24 (m, 1H); 13C NMR (75 MHz)31 δ 17.95,
22.96 (23.19), 25.97, 26.31 (26.53), 41.06 (41.24), 55.33, 56.41,
78.66, 95.18, 103.56, 112.91, 113.26, 116.62, 116.70, 118.85
(118.95), 123.00, 124.15, 124.24, 124.51, 125.66, 126.56, 126.81,
128.04, 128.10, 129.42, 131.07, 131.28, 131.61, 132.43, 132.55,
133.65, 133.76, 143.97, 146.09, 152.13, 154.27, 159.54, 184.21,
185.05; FT-IR 1664, 1288 cm-1; MS (EI) m/z (relative intensity)
602 (M+2H+, 14), 517 (100); HRMS (EI) calcd for C39H36O6
600.2512, found 600.2497.
Analytical data for 11: Rf ) 0.66 (ether/hexane, 1:1); 1H NMR
(400 MHz)31 δ 1.45 (d, 3H, J ) 4.0 Hz), 1.58 (s, 3H), 1.66 (s,
3H), 1.71-1.81 (m, 2H), 2.08 (s, 3H), 2.13-2.19 (m, 2H), 3.42
(s, 3H), 5.11 (tq, 1H, J ) 7.2 Hz, 1.2 Hz), 5.22 (dd, 2H, J ) 25.4
Hz, 7.2 Hz), 5.68 (d, 1H, J ) 10.4 Hz), 6.95 (d, 1H, J ) 8.8 Hz),
7.00 (d, 1H, J ) 10.0 Hz), 7.45 (s, 1H), 7.56 (d, 1H, J ) 8.8 Hz),
7.61 (s, 1H), 7.73-7.76 (m, 2H), 8.10-8.13 (m, 1H), 8.16-8.19
(m, 1H); 13C NMR (100 MHz)31 δ 14.79, 17.86, 22.98 (22.91),
25.89, 26.29 (26.23), 40.98 (41.03), 56.37, 78.71, 94.91, 103.93,
113.20, 117.11, 118.95 (118.93), 122.46, 124.30 (124.25), 124.67,
126.51, 126.77, 128.38 (128.42), 129.44, 130.50, 131.56, 131.95,
132.49, 132.60, 133.60, 133.78, 144.63, 145.33, 152.40, 153.62,
183.87, 185.95; FT-IR 1663, 1292, 1150, cm-1; MS (FAB) m/z
(relative intensity) 508 (M+, 22), 425 (100); HRMS (FAB) calcd
for C33H32O5Na (M + Na)+ 531.2147, found 531.2150. Repeated
attempts at elemental analysis yielded unsatisfactory results.
1,4-Dih yd r o-6-m eth oxy-3-[9-(m eth oxym eth oxy)-3-m eth -
yl-3-(4-m et h yl-3-p en t en yl)-3H -n a p h t h o[2,1-b]p yr a n -8-yl]-
2-[9-(N,N-dieth ylcar bam oyloxy-3-m eth yl-3-(4-m eth yl-3-pen -
t e n yl)-3H -n a p h t h o[2,1-b]p yr a n -8-yl]-1,4-n a p h t h a le n e -
1,4-Dih yd r o-2-h yd r oxy-3-(4-m et h oxyp h en yl)-1,4-n a p h -
th a len ed ion e (14). To a suspension of the dipole 7a 12 (0.159 g,
0.42 mmol), Pd(PPh3)4 (0.054 g, 0.046 mmol), and CuI (0.059 g,
0.31 mmol) in 3.5 mL of anhydrous DMF at room temperature
was added the 4-methoxyphenyltrimethyl stannane 12a 23 (0.70
g, 2.58 mmol) dissolved in 5.0 mL of anhydrous DMF. The
suspension was stirred for 16 h at room temperature. Ether (10
mL) was added, and the mixture was extracted with 5% aqueous
NaHCO3 (5 × 20 mL) until the aqueous extract was almost
colorless. The combined aqueous layer was acidified to pH ) 2
with concentrated HCl and the mixture extracted with CH2Cl2.
The combined organic layers were washed with water, dried over
MgSO4, filtered, and concentrated to yield a dark red solid. The
product was recrystallized from ether/hexane yielding 0.090 g
(76%) of the hydroxyquinone 14 as red needles: mp ) 170-172
°C (lit.32 mp 175-176 °C); Rf ) 0.37 (ether/hexane, 1:1); 1H NMR
(300 MHz) δ 3.86 (s, 3H), 6.99 (d, 2H, J ) 8.3 Hz), 7.51 (d, 2H,
J ) 8.8 Hz), 7.57 (s, 1H), 7.72-7.82 (m, 2H), 8.12-8.20 (m, 2H);
d ion e (10b). To
a stirred suspension of the triflate 9b
(0.060 g, 0.089 mmol), Pd(PPh3)4 (0.038 g, 0.0329 mmol), and
LiCl (0.030 g, 0.707 mmol) in 2.0 mL of anhydrous dioxane was
added the stannane 6b (0.290 g, 0.521 mmol) dissolved in 3.0
mL of anhydrous dioxane. The reaction mixture was stirred for
13 h at 60 °C. The suspension was cooled to room temperature
and filtered through a small plug of cotton. The filtrate was
concentrated and the product purified by flash chromatography
on silica eluting with ether/hexane (2:3) to afford 0.070 g (86%)
of the bisnaphthopyranyl quinone 10b as a red solid: mp ) 86-
89 °C; Rf ) 0.24 (ether/hexane, 1:1); 1H NMR (500 MHz)31 δ 1.02
(t, 3H, J ) 6.7 Hz), 1.12 (t, 3H, J ) 6.7 Hz), 1.35-1.39 (m, 6H),
1.48 (s, 3H), 1.54 (d, 3H, J ) 2.9 Hz), 1.58 (s, 3H), 1.63-1.67
(m, 5H), 1.69-1.76 (m, 2H), 2.04-2.09 (m, 4H), 3.23 (s, 0.5H),
3.30-3.40 (m, 4H), 3.56 (s, 2.5H), 3.96 (s, 3H), 5.04-5.06 (m,
2H), 5.27 (d, 1H, J ) 6.6 Hz), 5.38 (d, 1H, J ) 6.6 Hz), 5.56-
5.60 (m, 2H), 6.74 (d, 1H, J ) 8.7 Hz), 6.81 (d, 1H, J ) 8.6 Hz),
6.90 (d, 1H, J ) 9.9 Hz), 6.92 (d, 1H, J ) 10.0 Hz), 7.23-7.25
(m, 2H), 7.30-7.34 (m, 2H), 7.37 (d, 1H, J ) 1.6 Hz), 7.51 (s,
1H), 7.60 (d, 1H, J ) 2.8 Hz), 7.76 (s, 1H), 8.14 (d, 1H, J ) 8.6
Hz); 13C NMR (125 MHz)31 δ 13.29, 14.13 (13.97), 17.57, 17.62,
22.64 (22.70), 22.77 (22.82), 25.60, 25.65, 26.09, 26.16 (26.22),
40.83, 40.91, 41.71 (41.45), 42.08 (41.90), 55.92 (55.73), 56.27,
78.33 (78.35, 78.24) 78.58, 95.08 (94.82), 103.00 (103.87), 109.72,
112.31, 112.60, 113.24, 113.32, 116.38 (116.65), 117.76, 118.84,
FT-IR 3362, 1653 cm-1
.
1,4-Dih yd r o-2-(4-m eth oxyp h en yl)-3-[(tr iflu or om eth a n e-
su lfon yl)oxy]-1,4-n a p h th a len ed ion e (15). To a solution of the
hydroxyquinone 14 (0.160 g, 0.571 mmol) and Et3N (0.10 mL,
0.072 g, 0.170 mmol) in 7 mL of dry CH2Cl2 at 0 °C was added
trifluoromethanesulfonic anhydride (0.15 mL, 0.251 g, 0.89
mmol). The resulting purple reaction mixture was stirred for
20 min at 0 °C and then concentrated using a minimum amount
of external heat to avoid decomposition (30-40 °C). Purification
of the residue by flash chromatography on silica eluting with
ether/hexane (1:4) provided 0.173 g (74%) of the triflate 15 as
yellow needles: mp ) 158-160 °C; Rf ) 0.50 (ether/hexane, 1:1);
1H NMR (300 MHz) δ 3.89 (s, 3H), 7.02 (d, 2H, J ) 8.8 Hz), 7.39
(d, 2H, J ) 8.8 Hz), 7.83-7.86 (m, 2H), 8.19-8.26 (m, 2H); 13C
NMR (75 MHz) δ 55.67, 114.02 (two carbons), 119.32, 120.30,
127.09, 127.67, 130.23, 131.81, 132.53 (two carbons), 134.75,
(32) Hewgill, R. F.; Mullings, L. R. Aust. J . Chem. 1975, 28(2), 355-
367.