Padwa et al.
methyl[4-(2-formyl)phenyl]-2-butenoate45 was treated with 12
mL (5.9 mmol) of a 0.5 M solution of ethynylmagnesium
bromide in THF to give 0.6 g (47%) of 4-[2-(1-hydroxyprop-2-
ynyl)phenyl]but-2-enoic acid methyl ester (36) as a pale yellow
oil: IR (neat) 3431, 3289, 1709, 1652, 1275 cm-1; 1H NMR (300
MHz, CDCl3) δ 2.63 (d, 1H, J ) 2.1 Hz), 2.73 (brs, 1H), 3.67
(s, 3H), 3.65-3.71 (m, 2H), 5.53 (d, 1H, J ) 2.1 Hz), 5.73 (dt,
1H, J ) 15.9, 1.7 Hz), 7.06-7.15 (m, 2H), 7.24-7.30 (m, 2H),
7.65-7.68 (m, 1H); 13C NMR (75 MHz, CDCl3) δ 34.9, 51.5,
62.0, 75.2, 83.2, 122.1, 127.2, 127.3, 129.0, 130.5, 135.6, 137.9,
147.4, 166.9.
A 0.6 g (2.7 mmol) of 36 was treated with 0.44 g (3.0 mmol)
of benzenesulfenyl chloride to give 0.7 g (80%) of a 3:2
diastereomeric mixture of allene 37 as a pale yellow oil: IR
(neat) 1930, 1716, 1439, 1275, 1040 cm-1; 1H NMR (300 MHz,
CDCl3) δ 3.53-3.57 (m, 2H), 3.68 (s, 3H), 5.64 (d, 1H, J ) 15.6
Hz), 6.40 and 6.41 (d, 1H, J ) 6.0 Hz), 6.71 and 6.75 (d, 1H,
J ) 6.0 Hz), 6.99-7.25 (m, 5H), 7.47-7.52 (m, 3H), 7.63-7.67
(m, 2H); 13C NMR (75 MHz, CDCl3) δ 35.8, 51.5, 98.8, 105.8,
122.5, 124.2, 127.5, 128.5, 128.8, 128.9, 129.3, 130.6, 131.3,
135.3, 144.5, 146.4, 166.6, 204.9. Anal. Calcd for C20H18SO3:
C, 70.99; H, 5.37. Found: C, 70.84; H, 5.22.
salt of (tert-butyldimethylsilyloxy)-2-butyn-1-ol was treated
with 0.5 mL (4.2 mmol) of methyl 2-(bromomethyl)acrylate.
Standard workup afforded a residue which was treated with
5 mL (5.1 mmol) of TBAF to give 0.5 g (69%) of 2-(4-
hydroxybut-2-ynyloxymethyl)acrylic acid methyl ester (42) as
a pale yellow oil: IR (neat) 3431, 2954, 1716, 1439, 1090 cm-1
;
1H NMR (300 MHz, CDCl3) δ 1.84 (brs, 1H), 3.75 (s, 3H), 4.21-
4.29 (m, 6H), 5.87 (s, 1H), 6.30 (s, 1H); 13C NMR (75 MHz,
CDCl3) δ 50.9, 51.9, 58.1, 68.0, 81.3, 85.0, 126.7, 136.5, 166.3.
A 2.4 mmol sample of the mesylate of 42 was treated with
freshly prepared NaSPh (2.4 mmol) to give 0.5 g (76%) of 2-(4-
phenylsulfanylbut-2-ynyloxymethyl)acrylic acid methyl ester
as a pale yellow oil: IR (neat) 2947, 1723, 1439, 1090, 741
1
cm-1; H NMR (300 MHz, CDCl3) δ 3.64 (t, 2H, J ) 2.0 Hz),
3.74 (s, 3H), 4.16-4.17 (m, 4H), 5.80 (d, 1H, J ) 1.2 Hz), 6.27
(d, 1H, J ) 1.2 Hz), 7.18-7.31 (m, 3H), 7.40-7.43 (m, 2H);
13C NMR (75 MHz, CDCl3) δ 22.9, 51.9, 58.1, 67.7, 79.0, 82.6,
124.4, 126.6, 126.9, 128.9, 130.1, 130.7, 135.1, 136.5, 166.1.
A 0.3 g (1.02 mmol) sample of the above compound was
oxidized with 1.4 g (2.2 mmol) of Oxone to give 0.3 g (88%) of
43 as a clear oil: IR (neat) 1717, 1439, 1318, 1140, 1083 cm-1
;
1H NMR (300 MHz, CDCl3) δ 3.75 (s, 3H), 3.99 (t, 2H, J ) 2.1
Hz), 4.13 (t, 2H, J ) 1.2 Hz), 4.15 (t, 2H, J ) 2.1 Hz), 5.81 (d,
1H, J ) 1.4 Hz), 6.29 (d, 1H, J ) 1.4 Hz), 7.56 (t, 2H, J ) 7.5
Hz), 7.67 (t, 1H, J ) 7.5 Hz), 7.96 (d, 2H, J ) 7.5 Hz); 13C
NMR (75 MHz, CDCl3) δ 48.7, 51.9, 57.9, 68, 74.3, 83.7, 126.6,
4-[2-(3-P h en ylsu lfon ylp r op a -1,2-d ien yl)p h en yl]bu t-2-
en oic Acid Meth yl Ester (38). A 0.5 g (1.6 mmol) sample of
37 was oxidized with 1.0 g (1.7 mmol) of Oxone to give 0.5 g
(87%) of 38, which was obtained as a clear oil after purification
by silica gel chromatography: IR (neat) 1937, 1716, 1439, 1311,
128.8, 129.2, 134.2, 136.3, 137.7, 166.0. Anal. Calcd for C15H16
SO5: C, 58.43; H, 5.23. Found: C, 58.51; H, 5.37.
-
1
1147 cm-1; H NMR (300 MHz, CDCl3) δ 3.52 (d, 1H, J ) 1.1
Hz), 3.54 (d, 1H, J ) 1.1 Hz), 3.69 (s, 3H), 5.62 (dt, 1H, J )
15.6, 1.7 Hz), 6.58 (d, 1H, J ) 6.0 Hz), 6.84 (d, 1H, J ) 6.0
Hz), 7.01 (dt, 1H, J ) 15.6, 6.0 Hz), 6.83-7.27 (m, 4H), 7.51
(t, 2H, J ) 7.5 Hz), 7.61 (t, 1H, J ) 7.5 Hz), 7.92 (d, 2H, J )
7.5 Hz); 13C NMR (75 MHz, CDCl3) δ 35.9, 51.5, 100.3, 104.1,
122.5, 127.6, 127.7, 128.9, 129.2, 129.4, 130.6, 133.7, 135.6,
141.1, 146.2, 166.6, 208.1. Anal. Calcd for C20H18SO4: C, 67.78;
H, 5.12. Found: C, 67.61; H, 5.01.
6-P h en ylsu lfon yl-4,6a -d ih yd r o-1H-cyclop en ta [c]fu r a n -
3a -ca r boxylic Acid Meth yl Ester (44). To a 0.2 g (0.7 mmol)
sample of 43 and 0.1 mL (0.7 mmol) of triethylamine in 10
mL of dry THF was added 0.1 g (0.7 mmol) of the sodium salt
of benzenesulfinic acid. The mixture was stirred for 10 h at
room temperature, diluted with CH2Cl2, and filtered through
a pad of Celite. The filtrated was washed with water and dried
over anhydrous Na2SO4. Concentration under reduced pres-
sure followed by silica gel column chromatography afforded
0.15 g (65%) of 44. Cycloadduct 44 showed the following
spectroscopic properties: IR (neat) 1730, 1446, 1304, 1211,
(3-P h en ylsu lfon ylvin ylid en ein d a n -2-yl)a cet ic Acid
Met h yl E st er (41). A 0.35 g (1.0 mmol) sample of 38 was
stirred in 12 mL of dry THF with 0.16 g (1.0 mmol) of the
sodium salt of bezenesulfinic acid and 0.14 g (1.0 mmol) of K2-
CO3 for 10 h at room temperature. The mixture was diluted
with CH2Cl2 and filtered through a pad of Celite. The filtrate
was washed with water and dried over anhydrous Na2SO4.
Concentration under reduced pressure followed by purification
afforded 0.3 g (88%) of a 1:1 mixture of the diastereomers of
41 which were separated by silica gel chromatography. Dias-
tereomer 41a showed the following spectrqal properties: IR
(neat) 1944, 1730, 1439, 1318, 1147 cm-1; 1H NMR (300 MHz,
CDCl3) δ 2.50 (dd, 1H, J ) 16.7, 9.5 Hz), 2.65 (dd, 1H, J )
16.7, 5.4 Hz), 2.79 (dd, 1H, J ) 16.7, 5.4 Hz), 3.34 (dd, 1H, J
) 16.7, 8.4 Hz), 3.64-3.75 (m, 1H), 3.69 (s, 3H), 6.61 (d, 1H,
J ) 4.2 Hz), 7.07-7.30 (m, 4H), 7.49 (t, 2H, J ) 7.5 Hz), 7.59
(t, 1H, J ) 7.5 Hz), 7.90 (d, 2H, J ) 7.5 Hz); 13C NMR (75
MHz, CDCl3) δ 37.9, 38.9, 39, 51.8, 106.6, 121.3, 123.6, 125.3,
127.5, 127.8, 129.2, 129.9, 133.5, 141.4, 143.9, 172.3, 201.8.
Anal. Calcd for C20H18SO4: C, 67.78; H, 5.12. Found: C, 67.70;
H, 4.98.
Diastereomer 41b: IR (neat) 1944, 1730, 1439, 1310, 1147
cm-1; 1H NMR (300 MHz, CDCl3) δ 2.51 (dd, 1H, J ) 16.3, 8.7
Hz), 2.59 (dd, 1H, J ) 16.3, 6.0 Hz), 2.77 (dd, 1H, J ) 16.3,
5.3 Hz), 3.32 (dd, 1H, J ) 16.3, 8.4 Hz), 3.61-3.69 (m, 1H),
3.64 (s, 3H), 6.64 (d, 1H, J ) 2.1 Hz), 7.07-7.28 (m, 4H), 7.50
(t, 2H, J ) 7.4 Hz), 7.59 (t, 1H, J ) 7.4 Hz), 7.92 (d, 2H, J )
7.4 Hz); 13C NMR (75 MHz, CDCl3) δ 37.8, 38.8, 39.0, 51.7,
106.7, 121.1, 123.6, 125.2, 127.5, 127.7, 129.2, 129.9, 133.5,
135.0, 141.2, 143.8, 171.8, 201.6. Anal. Calcd for C20H18SO4:
C, 67.78; H, 5.12. Found: C, 67.55; H, 4.92.
1154 cm-1 1H NMR (300 MHz, CDCl3) δ 2.65 (dt, 1H, J )
;
19.3, 2.5 Hz), 3.17 (dd, 1H, J ) 19.3, 2.1 Hz), 3.64-3.73 (m,
2H), 3.66 (s, 3H), 3.82 (dd, 1H, J ) 9.3, 7.2 Hz), 3.91 (dd, 1H,
J ) 9.3, 3.3 Hz), 4.00 (d, 1H, J ) 9.3 Hz), 6.59 (d, 1H, J ) 0.9
Hz), 7.54 (t, 2H, J ) 7.5 Hz), 7.64 (t, 1H, J ) 7.5 Hz), 7.87 (d,
2H, J ) 7.5 Hz); 13C NMR (75 MHz, CDCl3) δ 41.8, 52.7, 55.2,
61.2, 72.1, 78.0, 128.0, 129.4, 133.8, 139.4, 141.9, 143.5, 173.9.
Anal. Calcd for C15H16SO5: C, 58.43; H, 5.23. Found: C, 58.36;
H, 5.05.
3-P h en ylsu lfon ylm eth yl-4-vin ylid en etetr a h yd r ofu r a n -
3-ca r boxylic Acid Meth yl Ester (45). In addition to cycload-
duct 44, 0.04 g (20%) of allene 45 was also isolated from the
silica gel column and exhibited the following spectroscopic
1
properties: IR (neat) 1958, 1730, 1446, 1311, 1147 cm-1; H
NMR (300 MHz, CDCl3) δ 3.41 (d, 1H, J ) 14.3 Hz), 3.64 (s,
3H), 3.97 (d, 1H, J ) 14.3 Hz), 4.07 (d, 1H, J ) 9.8 Hz), 4.32
(dt, 1H, J ) 12.0, 4.3 Hz), 4.42 (dt, 1H, J ) 12.0, 4.3 Hz), 4.68
(d, 1H, J ) 9.8 Hz), 5.03 (t, 2H, J ) 4.3 Hz), 7.55 (t, 2H, J )
7.4 Hz), 7.65 (t, 1H, J ) 7.4 Hz), 7.88 (d, 2H, J ) 7.4 Hz); 13
C
NMR (75 MHz, CDCl3) δ 52.9, 53.4, 61.2, 68, 73.7, 82.9, 104.6,
128.0, 129.3, 133.9, 140.2, 170.3, 199.6. Anal. Calcd for C15H16
SO5: C, 58.43; H, 5.23. Found: C, 58.40; H, 5.16.
-
1-Allyl-2-(1-p h en ylsu lfon ylp r op a -1,2-d ien yl)b en zen e
(56). A 3.1 g (11 mmol) of 2-iodobenzyl bromide46 was used
for the preparation of 1.6 g (61%) of 1-allyl-2-iodobenzene:47
IR (neat) 1461, 1427, 1006, 910, 738 cm-1; 1H NMR (300 MHz,
CDCl3) δ 3.48 (d, 2H, J ) 6.6 Hz), 5.04-5.14 (m, 2H), 5.87-
6.01 (m, 1H), 6.86-6.91 (m, 1H), 7.19-7.30 (m, 2H), 7.80-
2-(4-P h en ylsu lfon ylbu t-2-yn yloxym eth yl)a cr ylic Acid
Meth yl Ester (43). A 0.85 g (4.2 mmol) sample of the sodium
(46) Berk, S. C.; Knochel, P.; Yeh, M. C. P. J . Org. Chem. 1988, 53,
5789.
(45) Schnatter, W. F. K.; Almarsson, O.; Bruice, T. C. Tetrahedron
1991, 47, 8687.
(47) Knight, J .; Parsons, P. J . J . Chem. Soc., Perkin Trans. 1 1989,
979.
6248 J . Org. Chem., Vol. 68, No. 16, 2003