Three-Component Conjugate-Nucleophilic Addition
TABLE 6. Rea ction of Acetylen ic Su lfon es w ith P h en ylselen om a gn esiu m Br om id e a n d r,â-Un sa tu r a ted Ar om a tic
a
Keton es
time
(h)
yield of Z-14 (%)
R1
R2
Ar
(Z/E)
b
entry
1
2
3
4
5
6
7
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
4.5
4
4
3.5
3
3.5
3.5
63 (Z-14a , >95/5)
69 (Z-14b, >96/4)
68 (Z-14c, >95/5)
57 (Z-14d , >96/4)
55 (Z-14e, >96/4)
70 (Z-14f, 96/4)
p-CH3OC6H4
Ph
p-CH3C6H4
Ph
p-CH3OC6H4
Ph
p-CH3OC6H4
p-ClC6H4
CH3
Ph
Ph
n-C5H11
n-C5H11
57 (Z-14g, >95/5)
a
b
Mixture of 1 (0.5 mmol), 2 (0.6 mmol), and 13 (0.5 mmol) in 5 mL of THF/CH2Cl2 (1/4 v/v) was stirred at -20 °C. Isolated yield of
purified Z-14 based on 1. The ratio of Z/E was determined by 400 MHz 1H NMR spectra of the unpurified reaction mixture.
SCHEME 5
The reaction mixture turned to a pale yellow solution, which
was maintained stirring at -20 °C for 50-90 min. After the
reaction was complete (monitored by TLC), the reaction was
1.42 (m, 2H), 1.26-1.18 (m, 2H), 1.12 (s, 3H), 0.72 (t, J ) 7.26
Hz, 3H); 13C NMR (100 MHz, CDCl
) δ 152.8, 143.8, 142.1,
3
139.4, 137.6, 137.5, 129.6, 129.1, 128.5, 128.4, 128.1, 127.7,
127.6, 127.3, 127.0, 126.7, 78.4, 45.1, 30.8, 21.7, 17.0, 13.9; IR
quenched with saturated NH
The organic phase was washed with saturated brine and dried
over MgSO . After filtration and removal of the solvent in
4 2 2
Cl and extracted with CH Cl .
-
1
+
(KBr) 3549, 1276, 1139 cm ; MS (EI) m/z (%) 343 (14.1, M
+
+
4
- PhSe,), 187 (13.9, M - PhSeH - SO
2
Tol), 91 (100, PhCH
2
).
vacuo, the crude product was purified with flash chromatog-
raphy (silica/hexanes-ethyl acetate 8:1 v/ v) and the desired
tandem adduct 6 was obtained. (Z)-3-Phenyl-3-phenylseleno-
Anal. Calcd for C26
62.39; H, 5.92.
28 3
H O SSe: C, 62.52; H, 5.65. Found: C,
(Z)-3-(p-Nitr ostyr yl)-2-(p-tolylsu lfon yl)-1-p h en yl-1-ph e-
1
2
1
2
-(p-tolylsulfonyl)-1-(p-nitrophenyl)-2-propen-1-ol (Z-6a ): mp
n ylselen o-1-bu ten -3-ol (Z-12a ): mp 136-138 °C; H NMR
1
80-181°C; H NMR (400 MHz, CDCl
3
) δ 7.98 (d, J ) 8.8 Hz,
3
(400 MHz, CDCl ) δ 8.17 (d, J ) 8.3 Hz, 2H), 8.04 (d, J ) 8.8
H), 7.79 (d, J ) 8.3 Hz, 2H), 7.34 (d, J ) 8.2 Hz, 2H), 7.23 (d,
Hz, 2H), 7.41 (d, J ) 8.0 Hz, 2H), 7.12 (d, J ) 8.8 Hz, 2H),
7.03-6.99 (m, 2H), 6.86-6.82 (m, 3H), 6.75-6.69 (m, 3H), 6.58
(t, J ) 7.5 Hz, 1H), 6.45 (d, J ) 8.5 Hz, 1H), 6.33 (d, J ) 16.0
Hz, 1H), 5.96 (d, J ) 16.0 Hz, 1H), 5.12 (s, 1H), 2.51 (s, 3H),
J ) 8.0 Hz, 2H), 7.12-7.08 (m, 1H), 7.02-6.93 (m, 8H), 6.82
(s, 1H), 5.56 (d, J ) 11.0 Hz, 1H), 4.32 (d, J ) 11.1 Hz, 1H),
13
2
1
1
1
2
3
.44 (s, 3H); C NMR (100 MHz, CDCl ) δ 159.2, 148.4, 146.9,
44.9, 138.0, 137.0, 136.8, 136.2, 129.3, 128.8, 128.5, 128.2,
27.8, 127.7, 126.5, 123.1, 73.1, 21.6; IR (KBr) 3478, 1517,
1.59 (s, 3H); 13C NMR (100 MHz, CDCl
3
) δ 154.3, 146.2, 143.7,
142.6, 141.1, 139.2, 138.4, 137.0, 136.6, 128.7, 128.4, 128.3,
128.1, 127.7, 127.4, 127.3, 127.2, 126.8, 126.5, 126.4, 124.5,
123.0, 76.3, 30.1, 21.2; IR (KBr) 3460, 1516, 1341, 1281, 1134
-
1
+
343, 1260, 1134 cm ; MS (EI) m/z (%) 408 (24.0, M - PhSe),
+
+
2 6 5 2
Tol), 91 (100, C H CH ). Anal.
52 (59.2, M - PhSeH - SO
SSe: C, 59.58; H, 4.11; N, 2.48. Found:
-
1
+
+
Calcd for C28
H
23NO
5
cm ; MS (EI) m/z (%) 448 (3.12, M - PhSe), 292 (20.33, M
+
2 2 27
Tol), 91 (100, PhCH ). Anal. Calcd for C31H -
C, 59.40; H, 4.25; N, 2.52.
- PhSeH - SO
NO SSe: C, 61.59; H, 4.50; N, 2.31. Found: C, 61.32; H, 4.81;
N, 2.42.
(Z)-1,3,5-Tr ip h en yl-4-(p-tolylsu lfon yl)-5-p h en ylselen o-
Th e Th r ee-Com p on en t Rea ction of P h en ylselen om -
a gn esiu m Br om id e w ith Acetylen ic Su lfon es a n d Ke-
ton es. P r ep a r a tion of 9, 12, or 14. Gen er a l P r oced u r e.
To a colorless solution of phenylselenomagnesium bromide (0.6
5
1
4-p en ten -1-on e (Z-14a ): mp 150-151 °C; H NMR (400 MHz,
mmol) in THF/CH
2
Cl
2
(v/v ) 1:4, 5 mL) were added acetylenic
CDCl ) δ 7.87 (d, J ) 8.4 Hz, 2H), 7.59-7.53 (m, 3H), 7.43-
3
sulfone (0.5 mmol) and ketone (0.5 mmol) at -20 °C with
stirring. The reaction mixture turned to a pale yellow solution,
which was maintained stirring at -20 °C for 2.5-5 h. After
usual workup, the desired tandem adduct 9, 12, or 14 was
obtained.
7.39 (m, 2H), 7.11-7.0 (m, 8H), 6.94-6.90 (m, 7H), 6.75-6.67
(br, 2H), 4.84 (dd, J ) 9.7 Hz, 3.9 Hz, 1H), 4.37-4.30 (m, 1H),
1
3
3.40 (dd, J ) 18.1 Hz, 3.9 Hz, 1H), 2.36 (s, 3H); C NMR (100
MHz, CDCl ) δ 196.7, 154.5, 143.9, 139.7, 139.1, 138.6, 137.5,
3
137.4, 136.6, 133.0, 129.1, 128.9, 128.5, 128.4, 128.3, 128.2,
128.0, 127.9, 127.8, 127.7, 127.3, 126.2, 43.1, 41.4, 21.5; IR
(
Z)-3-Met h yl-2-(p -t olylsu lfon yl)-1-p h en yl-1-p h en ylse-
1
-1
+
len o-1-h exen -3-ol (Z-9a ): mp 121-123 °C; H NMR (400
(KBr) 1685, 1301, 1141 cm ; MS (EI) m/z (%) 465 (8.0, M
-
+
+
MHz, CDCl
3
) δ 8.13 (d, J ) 8.3 Hz, 2H), 7.38 (d, J ) 8.0 Hz,
H), 7.07 (t, J ) 7.6 Hz, 1H), 6.93-6.81 (m, 7H), 6.75 (s, 1H),
.64 (d, J ) 6.34 Hz, 1H), 4.48 (br, 1H), 2.48 (s, 3H), 1.47-
PhSe), 309 (12.1, M - PhSeH - SO
2
Tol), 105 (100, PhCO ).
2
6
Anal. Calcd for C36
69.40; H, 4.98.
H
30
O
3
SSe: C, 69.56; H, 4.86. Found: C,
J . Org. Chem, Vol. 67, No. 25, 2002 8899