4040 J . Org. Chem., Vol. 64, No. 11, 1999
Tiedemann et al.
CDCl3) δ 209.8, 209.5, 148.3, 148.1, 135.81, 135.77, 128.0,
127.0, 126.9, 126.4, 120.2, 120.1, 88.24, 88.15, 71.6, 51.8, 51.4,
37.8, 37.6, 34.7, 34.1, 25.1, 25.0, 24.6, 23.9, 23.0, 22.2, 14.3,
13.3, 12.2 11.8; IR (neat) 1769, 1622, 1598 cm-1; HRMS (CI)
calcd for C20H26O2 (M+) 298.1933, found 298.1936.
(t, J ) 7.2, 3H); 13C NMR (125 MHz, CDCl3) δ 202.2, 158.0,
145.6, 128.3, 128.1, 117.3, 113.4, 91.3, 72.5, 72.1, 58.4, 55.2,
44.8, 36.1, 30.8, 23.0, 22.7, 22.2, 21.8, 18.7, 13.5; IR (neat) 1779,
1632, 1607 cm-1; HRMS (CI) calcd for C24H30O3 (M+) 366.2195,
found 366.2193.
Second fraction, 0.043 g (24%) of 54. Isolated from attempts
to purify the corresponding naphthol 52 as a yellow crystalline
solid (mixture of diastereomers 1.8:1): mp 73-74 °C; 1H NMR
(500 MHz, CDCl3) δ 8.09-8.04 (m, 1H), 7.95, 7.85 (each br s,
1H), 7.63-7.58 (m, 2H), 7.46-7.40 (m, 1H), 5.28-5.05 (m, 2H),
4.86-4.79 (m, 2H), 3.22-3.11 (m, 1H), 2.90, 2.88 (each dd, J
) 12.3, J ) 7.6, 1H), 2.59, 2.57 (each dd, J ) 12.8, J ) 7.1,
1H), 1.86-1.58 (m, 2H), 1.46 (d, J ) 6.1, 3H), 1.43, 1.42 (each
d, J ) 6.2, 3H), 1.27, 1.22 (each d, J ) 7.1, J ) 7.0, 3H), 0.86,
0.81 (each t, J ) 7.5, 3H); 13C NMR (125 MHz, CDCl3) δ 185.3,
164.4, 163.9, 140.5, 140.4, 134.1, 134.0, 133.1, 132.9, 132.6,
129.6, 129.5, 128.5, 128.4, 126.53, 126.46, 124.1, 123.9, 120.1,
120.0, 86.3, 75.7, 75.5, 42.7, 42.4, 33.0, 32.9, 29.7, 27.6, 27.1,
23.6, 23.4, 23.3, 18.6, 18.5, 13.0, 12.9; IR (neat) 3348, 1644,
1606, 1574 cm-1; HRMS (CI) calcd for C20H27O4 (MH+)
331.1909, found 331.1908.
4-Allyl-2-ter t-bu tyl-3-m eth oxy-2H-n aph th alen -1-on e (57)
a n d 5-ter t-Bu tyl-4-m eth oxy-3-p h en ylbicyclo[3.2.0]h ep t-
3-en -6-on e (58). A solution of 20j (0.216 g, 0.80 mmol) in
toluene (16 mL, 0.05 M) was heated to reflux under a blanket
of N2 for 14 d. Removal of the volatile components was followed
by 1H NMR analysis which showed a 6:1 ratio of products
favoring the bicycloheptenone over the naphthalenone. Radial
chromatography (100:1 hexanes/EtOAc) gave as first fraction
0.149 g (69%) of bicycloheptenone 58 as a yellow oil: 1H NMR
(500 MHz, CDCl3) δ 7.64-7.62 (m, 2H), 7.37 (t, J ) 7.8, 2H),
7.25 (t, J ) 7.6, 1H), 3.59 (s, 3H), 3.14 (dd, J ) 17.9, J ) 9.1,
1H), 3.00 (dd, J ) 16.1, J ) 7.8, 1H), 2.86 (dd, J ) 18.1, J )
5.8, 1H), 2.73-2.67 (m, 2H), 1.12 (s, 9H); 13C NMR (125 MHz,
CDCl3) δ 209.5, 152.1, 135.4, 128.2, 127.3, 127.0, 122.9, 88.8,
58.4, 51.1, 37.1, 34.6, 26.4, 26.3; IR (neat) 1763, 1618, 1596
cm-1; HRMS (CI) calcd for C18H22O2 (M+) 270.1620, found
270.1623.
3-Meth oxy-6-m eth oxym eth yl-2,4-(3,4-dim eth oxyph en yl)-
p h en ol (62). 4-Allenyl-3-methoxy-2,4-(3,4-dimethoxyphenyl)-
2-cyclobutenone (44d ) (0.103 g, 0.25 mmol, 1 equiv) was
dissolved in acetonitrile (6 mL, 0.03 M) and treated with
anhydrous methanol (1.02 mL, 25.2 mmol, 100 equiv). The
resulting solution was heated to gentle reflux for 2 h. Removal
of the volatile components provided an orange oil which was
purified by flash silica gel chromatography (19:1 CH2Cl2/
EtOAc) to furnish 0.061 g (55%) of 62 as a white crystalline
1
solid: mp 158-159 °C; H NMR (500 MHz, CDCl3) δ 7.14-
7.13 (m, 2H), 7.07 (dd, J ) 8.0, J ) 2.0, 1H), 7.03-6.99 (m,
3H), 6.91 (d, J ) 8.0, 1H), 6.79 (s, 1H), 4.64 (s, 2H), 3.94 (s,
3H), 3.92 (s, 3H), 3.903 (s, 3H), 3.900 (s, 3H), 3.48 (s, 3H), 3.21
(s, 3H); 13C NMR (125 MHz, CDCl3) δ 155.6, 152.6, 148.9,
148.5, 148.4, 147.9, 131.3, 129.8, 126.5, 125.7, 123.2, 122.7,
121.2, 118.7, 113.6, 112.4, 111.1, 110.9, 72.4, 60.5, 58.4, 55.94,
55.90, 55.8; IR (neat) 3436, 1592 cm-1; HRMS (EI) calcd for
C
25H28O7 (M+) 440.1835, found 440.1830.
3-(1-H exyn yl)-4-m et h yl-5-p h en ylb icyclo[3.2.0]h ep t -3-
en -6-on e (63). A solution of 32a (0.147 g, 0.53 mmol) in
toluene (11 mL, 0.05 M) was heated to reflux under a blanket
of N2 for 3 h. Removal of the volatile components followed by
radial chromatography (20:1 hexanes/EtOAc) furnished 0.131
g (89%) of 63 as a water white oil: 1H NMR (500 MHz, CDCl3)
δ 7.34-7.23 (m, 5H), 3.35-3.28 (m, 1H), 3.20-3.15 (m, 1H),
2.92-2.85 (m, 2H), 2.58 (d, J ) 16.7, 1H), 2.40 (t, J ) 7.0,
2H), 1.67 (s, 3H), 1.56 (quintet, J ) 7.0, 2H), 1.46 (hextet, J )
7.4, 2H), 0.95 (t, J ) 7.2, 3H); 13C NMR (125 MHz, CDCl3) δ
206.1, 142.8, 138.2, 128.4, 127.0, 125.8, 120.8, 95.6, 87.7, 76.7,
51.2, 43.2, 34.2, 30.8, 21.9, 19.2, 13.6, 12.7; IR (neat) 2217,
1770, 1602 cm-1; HRMS (EI) calcd for C20H22O (M+) 278.1671,
found 278.1684.
Second fraction, 0.029 g (13%) of 57 as a yellow oil: 1H NMR
(500 MHz, CDCl3) δ 7.77 (dd, J ) 7.8, J ) 1.4, 1H), 7.48 (dt,
J ) 7.8, J ) 1.4, 1H), 7.33 (d, J ) 7.6, 1H), 7.21 (dt, J ) 7.6,
J ) 1.0, 1H), 5.92 (ddt, J ) 17.1, J ) 10.1, J ) 5.6, 1H), 5.13
(dq, J ) 17.1, J ) 1.6, 1H), 5.04 (dq, J ) 10.1, J ) 1.6, 1H),
3.63 (s, 3H), 3.45 (ddt, J ) 15.9, J ) 5.4, J ) 2.0, 1H), 3.34-
3.28 (m, 1H), 3.20 (s, 1H), 0.97 (s, 9H); 13C NMR (125 MHz,
CDCl3) δ 201.9, 155.5, 139.8, 136.2, 133.8, 131.3, 126.1, 125.8,
124.1, 118.6, 115.5, 58.8, 58.0, 37.9, 29.1, 28.4; IR (neat) 1682,
1644, 1634, 1598 cm-1; HRMS (EI) calcd for C18H22O2 (M+)
270.1620, found 270.1620.
2-(1-H e xyn yl)-3-isop r op oxy-7-m e t h oxy-4-(2-m e t h yl-
a llyl)-n a p h th ol (59a ) a n d 5-(1-Hexyn yl)-4-isop r op oxy-3-
(4-m et h oxyp h en yl)-1-m et h yl-b icyclo[3.2.0]h ep t -3-en -6-
on e (60a ). A solution of 21a (0.175 g, 0.48 mmol) in toluene
(9.5 mL, 0.05 M) was heated to reflux under a blanket of N2
for 3 h. Removal of the volatile components was followed by
1H NMR analysis which showed a 1.4:1 ratio of products
favoring the naphthol over the bicycloheptenone. Radial chro-
matography (100:1 pentane/EtOAc) gave as first fraction 0.103
g (59%) of naphthol 59a as a yellow oil: 1H NMR (500 MHz,
CDCl3) δ 7.70 (d, J ) 9.3, 1H), 7.47 (d, J ) 2.5, 1H), 7.13 (dd,
J ) 9.2, J ) 2.5, 1H), 6.37 (s, 1H), 4.76 (s, 1H), 4.68 (septet, J
) 6.1, 1H), 4.36 (s, 1H), 3.93 (s, 3H), 3.69 (s, 2H), 2.59 (t, J )
7.1, 2H), 1.82 (s, 3H), 1.68 (quintet, J ) 7.3, 2H), 1.54 (hextet,
J ) 7.4, 2H), 1.34 (d, J ) 6.2, 6H), 0.99 (t, J ) 7.3, 3H); 13C
NMR (125 MHz, CDCl3) δ 156.3, 152.6, 150.6, 144.7, 128.5,
126.4, 121.2, 119.5, 118.8, 111.1, 101.8, 101.3, 100.7, 75.7, 73.1,
55.3, 33.8, 30.8, 23.2, 22.5, 22.1, 19.7, 13.6; IR (neat) 3486,
1599, 1575 cm-1; HRMS (CI) calcd for C24H30O3 (MH+)
366.2195, found 366.2191.
5-(1-H exyn yl)-2,3-d ih yd r o-6-h yd r oxy-4-isop r op oxy-2-
tr iisop r op ylsilyl-7,8-d im eth oxy-1H-p h en a len e (68). A so-
lution of 42 (0.067 g, 0.13 mmol) in toluene (6 mL, 0.02 M)
was heated to reflux under a blanket of N2 for 45 min. Removal
of the solvent was followed by flash silica gel chromatography
(9:1 hexanes/EtOAc) which furnished 0.057 g (60%) of 68 as a
water white oil: 1H NMR (500 MHz, CDCl3) δ 10.29 (s, 1H),
6.96 (s, 1H), 4.73 (septet, J ) 6.0, 1H), 4.04 (s, 3H), 3.95 (s,
3H), 3.49-3.45 (m, 1H), 3.09-3.01 (m, 2H), 2.69-2.63 (m, 1H),
2.59 (t, J ) 7.0, 2H), 1.67 (quintet, J ) 7.5, 2H), 1.55-1.46
(m, 3H), 1.33 (d, J ) 6.0, 6H), 1.31-1.18 (m, 3H), 1.15 (d, J )
7.0, 18H), 0.96 (t, J ) 7.5, 3H); 13C NMR (125 MHz, CDCl3) δ
154.2, 150.1, 146.0, 140.7, 134.5, 126.1, 119.1, 114.7, 113.6,
103.1, 99.1, 75.2, 73.9, 62.1, 56.8, 34.1, 31.1, 26.7, 22.7, 22.5,
22.2, 19.9, 19.2, 13.7, 11.0; IR (neat) 3297, 1606 cm-1; HRMS
(EI) calcd for C33H50O4Si (M+) 538.3478, found 538.3464.
2-(1-Hexyn yl)-3-isop r op oxy-5-t r iisop r op ylsilyl-8,9-d i-
m eth oxy-p h en a len on e (69). A solution of 42 (0.045 g, 0.08
mmol) in toluene (3.3 mL, 0.5 M) was heated to reflux under
a blanket of N2 for 45 min. After cooling to room temperature,
the pale yellow reaction mixture was treated with 2,3-dichloro-
5,6-dicyano-1,4-benzoquinone (0.040 g, 0.18 mmol). After 5
min, the crude, red reaction mixture was filtered through a
silica plug and concentrated to afford a dark yellow solid. Flash
silica gel chromatography (4:1 hexanes/EtOAc) furnished 0.032
g (72%) of 69 as a yellow crystalline solid: mp 168-170 °C;
1H NMR (500 MHz, CDCl3) δ 8.28 (d, J ) 1.0, 1H), 8.02 (d, J
) 1.0, 1H), 7.51 (s, 1H), 4.52 (septet, J ) 6.0, 1H), 4.09 (s,
3H), 4.04 (s, 3H), 2.58 (t, J ) 7.0, 2H), 1.66 (quintet, J ) 7.0,
2H), 1.56-1.48 (m, 5H), 1.43 (d, J ) 6.5, 6H), 1.15 (d, J ) 7.0,
18H), 0.95 (t, J ) 7.0, 3H); 13C NMR (125 MHz, CDCl3) δ 183.0,
166.0, 156.0, 153.4, 138.3, 132.3, 131.2, 128.4, 125.1, 122.5,
119.8, 113.7, 111.7, 101.7, 76.0, 73.7, 61.4, 56.2, 30.9, 22.9, 22.2,
19.9, 18.6, 13.7, 10.8; IR (neat) 1631, 1577, 1562 cm-1; HRMS
(CI) calcd for C33H47O4Si (MH+) 535.3243, found 535.3233.
Second fraction, 0.071 g (40%) of 60a as a yellow oil: 1H
NMR (500 MHz, CDCl3) δ 7.67 (d, J ) 8.8, 2H), 6.87 (d, J )
8.8, 2H), 4.80 (septet, J ) 6.0, 1H), 3.81 (s, 3H), 3.29 (d, J )
17.7, 1H), 2.91 (d, J ) 17.7, 1H), 2.88 (s, 2H), 2.29 (t, J ) 7.0,
2H), 1.51 (quintet, J ) 7.0, 2H), 1.42 (hextet, J ) 7.2, 2H),
1.40 (s, 3H), 1.38 (d, J ) 6.0, 3H), 1.14 (d, J ) 6.0, 3H), 0.90