Pd-Catalyzed Sulfinylzincation
361 (MH+). HRMS (FAB) calcd for C19H21O3S2 (MH+) 361.0932,
found 361.0935.
(t. J ) 3.1 Hz, 1H), 2.05 (ddtd, J ) 13.4, 9.7, 6.4, 6.4 Hz, 1H),
2.32 (ddd, J ) 9.7, 6.4, 3.1 Hz, 2H), 2.84 (ddd, J ) 13.4, 9.7,
5.5 Hz, 1H), 3.29 (ddd, J ) 13.4, 9.7, 6.4 Hz, 1H), 3.76 (s, 3H),
4.53 (d, J ) 11.6 Hz, 1H), 4.60 (d, J ) 11.6 Hz, 1H), 4.81 (dd,
J ) 15.9, 2.4 Hz, 1H), 4.98 (dd, J ) 15.9, 1.8 Hz, 1H), 6.55
(dd, J ) 2.4, 1.8 Hz, 1H), 7.30-7.38 (m, 5H). 13C NMR δ 17.5,
21.0, 51.7, 51.9, 66.9, 69.7, 73.7, 82.5, 119.3, 127.9 (2C), 128.2,
128.6 (2C), 136.8, 162.7, 164.7. IR: 2118, 1716, 1092. MS (FAB)
m/z 321 (MH+). HRMS (FAB) calcd for C17H21O4S (MH+)
321.1160, found 321.1154.
Meth yl (E)-4-(N-ben zyl-N-m eth yla m in o)-3-(p-tolylsu l-
fin yl)-2-bu ten oa te (12j): Yellow oil. 1H NMR δ 2.03 (s, 3H),
2.38 (s, 3H), 2.88 (dd, J ) 15.0, 2.5 Hz, 1H), 3.20 (d, J ) 12.5
Hz, 1H), 3.72 (d, J ) 12.5 Hz, 1H), 3.78 (s, 3H), 4.20 (d, J )
15.0 Hz, 1H), 6.89 (d, J ) 2.5 Hz, 1H), 7.22-7.55 (m, 9H). 13C
NMR δ 21.5, 41.9, 51.9, 54.2, 61.5, 119.1, 126.2 (2C), 127.3,
128.3 (2C), 129.2 (2C), 129.9 (2C), 137.9, 139.5, 142.2, 165.3,
165.6. IR 1720, 1086. MS (FAB) m/z 358 (MH+). HRMS (FAB)
calcd for C20H24NO3S (MH+) 358.1477, found 358.1480.
Met h yl (E)-4-(5-Met h oxyca r b on yl-4-p en t yloxy)-3-(p -
tolylsu lfin yl)-2-bu ten oa te (14): Yellow oil. 1H NMR δ 1.79
(tt, J ) 6.7, 6.1 Hz, 2H), 2.35-2.39 (m, 2H), 2.40 (s, 3H), 3.36
(dt, J ) 9.2, 6.1 Hz, 1H), 3.49 (dt, J ) 9.2, 6.1 Hz, 1H), 3.77 (s,
3H), 3.78 (s, 3H), 4.02 (dd, J ) 14.6, 1.8 Hz, 1H), 5.01 (dd,
J ) 14.6, 1.8 Hz, 1H), 6.81 (t, J ) 1.8 Hz, 1H), 7.30 (d, J ) 7.9
Hz, 2H), 7.55 (d, J ) 7.9 Hz, 2H). 13C NMR δ 15.4, 21.5, 27.4,
52.0, 52.6, 66.1, 69.1, 73.3, 88.5, 118.3, 126.1 (2C), 130.1 (2C),
139.0, 142.6, 154.1, 163.6, 164.9. IR 2237, 1716, 1643, 1084.
MS (FAB) m/z 379 (MH+). HRMS (FAB) calcd for C19H23O6S
(MH+) 379.1215, found 379.1228
N,N-Dim et h yl (E)-4-b en zyloxy-3-(p -t olylsu lfin yl)-2-
1
bu ten a m id e (12q): Pale yellow oil. H NMR δ 2.39 (s, 3H),
2.98 (s, 3H), 3.12 (s, 3H), 3.98 (dd, J ) 14.3, 1.8 Hz, 1H), 4.31
(d, J ) 11.6 Hz, 1H), 4.46 (d, J ) 11.6 Hz, 1H), 4.86 (dd, J )
14.3, 1.2 Hz, 1H), 7.15 (dd, J ) 1.8, 1.2 Hz, 1H), 7.22-7.35
(m, 7H), 7.51 (d, J ) 8.5 Hz, 2H). 13C NMR δ 21.5, 35.1, 37.9,
65.9, 73.0, 120.7, 126.1 (2C), 127.8 (3C), 128.4 (2C), 130.0 (2C),
137.1, 138.9, 142.3, 156.5, 164.9. IR 1651, 1086. MS (FAB) m/z
358 (MH+). HRMS (FAB) calcd for C20H24NO3S (MH+) 358.1477,
found 358.1474.
(E)-4-Ben zyloxy-3-(p-tolylsu lfin yl)-2-bu ten on itr ile (12r ):
1
Yellow oil. H NMR δ 2.43 (s, 3H), 3.86 (d, J ) 14.0 Hz, 1H),
Meth yl (E)-4-ben zyloxy-3-[(p-m eth oxyp h en yl)su lfin yl]-
4.30 (d, J ) 11.6 Hz, 1H), 4.43-4.46 (m, 2H), 7.15 (s, 1H), 7.17-
7.42 (m, 9H). 13C NMR δ 21.5, 65.9, 73.3, 100.0, 114.1, 125.9
(2C), 128.1 (2C), 128.3, 128.6 (2C), 130.4 (2C), 136.2, 137.4,
143.4, 169.1. IR 2224, 1099. MS (FAB) m/z 312 (MH+). HRMS
(FAB) calcd for C18H18NO2S (MH+) 312.1058, found 312.1060.
1
2-bu ten oa te (12k ): Yellow oil. H NMR δ 3.76 (s, 3H), 3.83
(s, 3H), 4.05 (dd, J ) 15.3, 1.8 Hz, 1H), 4.32 (d, J ) 11.6 Hz,
1H), 4.49 (d, J ) 11.6 Hz, 1H), 5.09 (dd, J ) 15.3, 1.2 Hz, 1H),
6.83 (dd, J ) 1.8, 1.2 Hz, 1H), 6.91-6.94 (m, 2H), 7.22-7.24
(m, 2H), 7.29-7.36 (m, 3H), 7.53-7.56 (m, 2H). 13C NMR δ
52.0, 55.5, 65.7, 73.1, 114.8 (2C), 118.1, 127.9 (2C), 128.0, 128.2
(2C), 128.4 (2C), 133.1, 136.9, 162.4, 163.9, 164.9. IR 1716,
1087. MS (EI) m/z 361 (MH+). HRMS (EI) calcd for C19H21O5S
(MH+) 361.1110, found 361.1098.
Meth yl (Z)-4-(ter t-Bu tyldim eth ylsilyloxy)-3-(p-tolylth io)-
2-bu ten oa te (15). Following the same procedure for 5 from
1a , 11e (113 mg, 0.497 mmol) was converted into 15 (140 mg,
1
80%). Yellow oil. H NMR δ -0.07 (s, 6H), 0.82 (s, 9H), 2.37
(s, 3H), 3.76 (s, 3H), 3.90 (s, 2H), 6.21 (s, 1H), 7.12 (d, J ) 8.0
Hz, 2H), 7.42 (d, J ) 8.0 Hz, 2H). 13C NMR δ -5.6 (2C), 18.2,
21.2, 25.7 (3C), 51.2, 64.8, 109.2, 125.1, 129.8 (2C), 135.8 (2C),
139.9, 158.9, 167.0. IR 1708. MS (FAB) m/z 353 (MH+). HRMS
(FAB) calcd for C18H29O3SSi (MH+) 353.1606, found 353.1610.
Meth yl (E)-4-ben zyloxy-3-(p h en ylsu lfin yl)-2-bu ten oa te
1
(12l): Yellow oil. H NMR δ 3.76 (s, 3H), 4.07 (dd, J ) 15.3,
1.8 Hz, 1H), 4.34 (d, J ) 11.6 Hz, 1H), 4.50 (d, J ) 11.6 Hz,
1H), 5.12 (dd, J ) 15.3, 1.2 Hz, 1H), 6.84 (dd, J ) 1.8, 1.2 Hz,
1H), 7.23-7.65 (m, 10H). 13C NMR δ 52.0, 65.7, 73.1, 118.1,
126.0 (2C), 127.9 (2C), 128.0, 128.4 (2C), 129.3 (2C), 131.7,
136.9, 142.3, 163.9, 164.8. IR 1720, 1086. MS (FAB) m/z 331
(MH+). HRMS (FAB) calcd for C18H19O4S (MH+) 331.1011,
found 331.1004.
Met h yl (Z)-4-(ter t-b u t yld im et h ylsilyloxy)-3-(p -t olyl-
su lfin yl)-2-bu ten oa te [(Z)-12e]: Colorless oil. 1H NMR δ
-0.03 (s, 3H), 0.01 (s, 3H), 0.85 (s, 9H), 2.39 (s, 3H), 3.82 (s,
3H), 4.35 (dd, J ) 18.0, 2.2, Hz, 1H), 4.79 (dd, J ) 18.0, 2.2
Hz, 1H), 6.46 (t, J ) 2.2, Hz, 1H), 7.28 (d, J ) 8.3 Hz, 2H),
7.70 (d, J ) 8.3 Hz, 2H). 13C NMR δ -5.6, -5.5, 18.2, 21.3,
25.7 (3C), 52.2, 57.7, 119.7, 124.5 (2C), 129.9 (2C), 140.3, 141.3,
164.6, 165.2. IR 1716, 1047. MS (FAB) m/z 369 (MH+). HRMS
(FAB) calcd for C18H29O4SSi (MH+) 369.1556, found 369.1544.
Met h yl (E)-4-ben zyloxy-3-[(p -ch lor op h en yl)su lfin yl]-
1
2-bu ten oa te (12m ): Yellow oil. H NMR δ 3.76 (s, 3H), 4.14
(dd, J ) 15.3, 1.8 Hz, 1H), 4.35 (d, J ) 11.6 Hz, 1H), 4.52 (d,
J ) 11.6 Hz, 1H), 5.10 (dd, J ) 15.3, 1.2 Hz, 1H), 6.80 (dd,
J ) 1.8, 1.2 Hz, 1H), 7.24-7.26 (m, 2H), 7.31-7.41 (m, 5H),
7.55-7.57 (m, 2H). 13C NMR δ 52.1, 65.9, 73.3, 118.2, 127.4
(2C), 128.0 (2C), 128.2, 128.5 (2C), 129.5 (2C), 136.6, 137.9,
140.9, 163.7, 164.7. IR 1720, 1088. MS (FAB) m/z 365 (MH+).
HRMS (FAB) calcd for C18H18ClO4S (MH+) 365.0615, found
365.0606.
Met h yl (E)-2-Allyl-4-b en zyloxy-3-(p -t olylsu lfin yl)-2-
bu ten oa te (16). Et2Zn (1.01 M in n-hexane) (0.44 mL, 0.449
mmol) was added slowly to a stirred solution of 11c (91.7 mg,
0.449 mmol), 1f (49.4 mg, 0.224 mmol), and Pd2(dba)3‚CHCl3
(4.64 mg, 0.00449 mmol) in THF (0.22 mL) at -78 °C. After
15 min, the stirring was continued at room temperature for 5
h. Then, a solution of CuCN‚2LiCl [prepared by drying a
mixtute of CuCN (20.1 mg, 0.224 mmol) and LiCl (19.0 mg,
0.449 mmol) at 140 °C for 2 h in situ] in THF (0.22 mL) was
added to the mixture. After the addition of allyl bromide (58
µL, 0.673 mmol), the reaction mixture was stirred at 0 °C for
1 h. The reaction was quenched with saturated NH4Cl and
extracted with Et2O. The organic layer was washed with brine
prior to drying and solvent evaporation. The residue was
chromatographed on silica gel with hexane-AcOEt (5:1) to give
16 (64.1 mg, 74%) as a yellow oil. 1H NMR δ 2.40 (s, 3H), 3.63
(dd, J ) 15.8, 6.7 Hz, 1H), 3.64 (s, 3H), 3.72 (dd, J ) 15.8, 6.7
Hz, 1H), 4.17 (d, J ) 11.6 Hz, 1H), 4.18 (d, J ) 12.8, 1H), 4.22
(d, J ) 11.6 Hz, 1H), 4.28 (d, J ) 12.8, 1H), 5.19 (dd, J ) 10.4,
1.5 Hz, 1H), 5.21 (dd, J ) 17.1, 1.5 Hz, 1H), 5.85 (dddd, J )
17.1, 10.4, 6.7, 6.7 Hz, 1H), 7.12 (d, J ) 8.5 Hz, 2H), 7.21-
7.30 (m, 5H), 7.46 (d, J ) 8.5 Hz, 2H). 13C NMR δ 21.3, 34.8,
52.2, 61.1, 72.2, 118.4, 124.3 (2C), 127.4, 127.6 (2C), 128.1 (2C),
129.9 (2C), 132.7, 137.5, 138.2, 140.3, 141.2, 145.3, 167.5. IR
1732, 1051. MS (FAB) m/z 385 (MH+). HRMS (FAB) calcd for
Meth yl (E)-4-ben zyloxy-3-[(p-n itr op h en yl)su lfin yl]-2-
bu ten oa te (12n ): Yellow crystals. Mp 89.5-90.5 °C. 1H NMR
δ 3.77 (s, 3H), 4.26 (dd, J ) 15.6, 2.4 Hz, 1H), 4.40 (d, J )
11.6 Hz, 1H), 4.57 (d, J ) 11.6 Hz, 1H), 5.12 (dd, J ) 15.6, 1.8
Hz, 1H), 6.81 (dd, J ) 2.4, 1.8 Hz, 1H), 7.26-7.28 (m, 2H),
7.34-7.40 (m, 2H), 7.80-7.83 (m, 3H), 8.21-8.24 (m, 2H). 13
C
NMR δ 52.2, 66.0, 73.5, 118.6, 124.2 (2C), 126.8 (2C), 128.1
(2C), 128.4, 128.6 (2C), 136.3, 149.5, 149.9, 163.2, 164.4. IR
1720, 1525, 1091. MS (FAB) m/z 376 (MH+). HRMS (FAB)
calcd for C18H18NO6S (MH+) 376.0855, found 376.0851.
Meth yl (E)-4-ben zyloxy-3-m eth ylsu lfin yl-2-bu ten oa te
1
(12o): Colorless oil. H NMR δ 2.78 (s, 3H), 3.76 (s, 3H), 4.52
(d, J ) 11.8 Hz, 1H), 4.60 (d, J ) 11.8 Hz, 1H), 4.85 (dd, J )
15.8, 2.0 Hz, 1H), 4.98 (dd, J ) 15.8, 2.0 Hz, 1H), 6.61 (t, J )
2.0 Hz, 1H), 7.26-7.40 (m, 5H). 13C NMR δ 41.1, 52.0, 66.8,
73.8, 118.5, 127.9 (2C), 128.2, 128.6 (2C), 136.7, 164.5, 164.8.
IR 1720, 1078. MS (FAB) m/z 269 (MH+). HRMS (FAB) calcd
for C13H17O4S (MH+) 269.0848, found 269.0836.
Meth yl (E)-4-(ben zyloxy)-3-(4-p en tyn ylsu lfin yl)-2-bu -
ten oa te (12p ): Yellow oil. 1H NMR δ 1.81-1.91 (m, 1H), 1.93
C
22H25O4S (MH+) 385.1473, found 385.1459.
J . Org. Chem, Vol. 68, No. 14, 2003 5557