Zhou et al.
2-(Eth ylth io)-2-p h en yl-4-p en ten oic a cid m eth yl ester :
colorless oil (86% yield); 1H NMR (400 MHz, CDCl3) δH 7.23-
7.41 (m, 5H), 5.62-5.70 (m, 1H), 4.96-5.01 (m, 2H), 3.77 (s,
3H), 2.88 (d, 1H, J ) 7.1 Hz), 2.42-2.48 (m, 1H), 2.32-2.39
(m, 1H), 1.13 (t, 3H, J ) 7.5 Hz); 13C NMR (100 MHz, CDCl3)
δC 172.8 (s), 139.1 (s), 132.8 (d), 128.1 (d), 127.6 (d), 127.2 (d),
118.5 (t), 60.4 (s), 52.4 (q), 43.1 (t), 24.0 (t), 13.4 (q); IR (neat,
cm-1) 2938, 1728, 1439, 1218, 699; MS (EI) 250 [M+]; HRMS
(EI) calcd for C14H18SO2 250.1027, found 250.1016.
2-(P h en ylth io)-2-ph en yl-4-pen ten oic acid m eth yl ester :
25 colorless solid (66% yield); mp 71-73 °C; 1H NMR (300 MHz,
CDCl3) δH 7.06-7.28 (m, 10H), 5.76-5.90 (m, 1H), 5.01-5.06
(m, 2H), 3.62 (s, 3H), 2.77-2.86 (m, 2H); 13C NMR (75 MHz,
CDCl3) δC 172.3 (s), 139.7 (s), 136.8 (d), 133.1 (d), 130.6 (s),
129.2 (d), 128.5 (d), 128.4 (d), 128.0 (d), 127.4 (d), 118.7 (t),
64.4 (s), 52.6 (q), 40.6 (t); IR (KBr disk, cm-1) 3077, 2955, 1732,
1439, 1217, 751, 693; MS (EI) 298 [M+]; HRMS (EI) calcd for
J ) 7.2 Hz), 2.96 (d, 1H, J ) 10.4 Hz), 2.34-2.39 (m, 1H),
2.36 (s, 6H), 1.29 (t, 3H, J ) 7.2 Hz), 0.98 (d, 3H, J ) 6.6 Hz);
13C NMR (75 MHz, CDCl3) δC 170.8 (s), 141.0 (d), 114.3 (t),
72.7 (d), 59.8 (t), 41.4 (q), 37.4 (d), 17.5 (q), 14.5 (q); IR (neat,
cm-1) 2921, 1730, 1227; MS (EI) 140 [M+ - OEt]; HRMS (EI)
calcd for C8H14NO 140.1075, found 140.0851. For the minor
1
isomer: colorless oil (21% yield); H NMR (300 MHz, CDCl3)
δH 5.62-5.79 (m, 1H), 5.00-5.09 (m, 2H), 4.15 (q, 2H, J ) 7.2
Hz), 2.89 (d, 1H, J ) 10.4 Hz), 2.58-2.64 (m, 1H), 2.33 (s, 6H),
1.26 (t, 3H, J ) 7.2 Hz), 1.07 (d, 3H, J ) 6.7 Hz); 13C NMR (75
MHz, CDCl3) δC 170.9 (s), 140.2 (d), 115.5 (t), 72.4 (d), 59.6
(t), 41.4 (q), 37.7 (d), 16.9 (q), 14.6 (q); IR (neat, cm-1) 2919,
1717; MS (EI) 140 [M+ - OEt]; HRMS (EI) calcd for C8H14NO
140.1075, found 140.0840.
4-(N ,N -D im e t h y la m in o )-2,5-d im e t h y l-6-h e p t e n -3-
on e.27 Obtained as a 5:1 mixture of anti- and syn-isomers.
Purification of the crude mixture on a silica gel column
resulted in some epimerization and gave the product as an
inseparable 1:1 diastereomeric mixture and as a colorless oil
(81% yield): 1H NMR (400 MHz, CDCl3) δH 5.80-5.89 (m, 1H),
5.59-5.68 (m, 1H), 4.94-5.11 (m, 4H), 3.20 (d, 1H, J ) 9.8
Hz), 3.15 (d, 1H, J ) 9.9 Hz), 2.62-2.77 (m, 3H), 2.50-2.57
(m, 1H), 2.38 (s, 6H), 2.36 (s, 6H), 1.03-1.09 (m, 12H), 0.99
(d, 3H, J ) 6.9 Hz), 0.88 (d, 3H, J ) 6.7 Hz); 13C NMR (100
MHz, CDCl3) δC 213.9 (s), 212.6 (s), 141.8 (d), 140.6 (d), 115.4
(t), 114.1 (t), 74.3 (d), 74.1 (d), 41.7 (q), 41.6 (q), 37.1 (d), 36.4
(d), 21.4 (t), 18.9 (t), 17.9 (q), 17.6 (q), 17.4 (q), 17.1 (q), 17.0
(q); IR (neat, cm-1) 2936, 1651, 1466; MS (EI) 128 [M+ - C4H7];
HRMS (EI) calcd for C7H14NO 128.1075, found 128.1076.
4-(N,N-Dim eth yla m in o)-2-m eth yl-6-h ep ten -3-on e:27 col-
orless oil (85% yield); 1H NMR (400 MHz, CDCl3) δH 5.66-
5.75 (m, 1H), 5.00-5.09 (m, 2H), 3.31 (dd, 1H, J ) 8.8, 4.8
Hz), 2.83-2.91 (m, 1H), 2.41-2.48 (m, 1H), 2.30 (s, 6H), 2.24-
2.33 (m, 1H), 1.07 (d, 3H, J ) 6.8 Hz), 1.04 (d, 3H, J ) 7.0
Hz); 13C NMR (100 MHz, CDCl3) δC 213.8 (s), 135.3 (d), 116.9
(t), 70.9 (d), 41.8 (q), 38.8 (d), 28.9 (t), 18.5 (q), 17.8 (q); IR
(neat, cm-1) 2932, 1651; MS (EI) 128 [M+ - C3H5]; HRMS (EI)
calcd for C7H14NO 128.1075, found 128.1091.
C
18H18SO2 298.1027, found 298.1026.
2-(P h en ylth io)-4-p en ten oic a cid eth yl ester : colorless
1
oil (60% yield); H NMR (300 MHz, CDCl3) δH 7.28-7.48 (m,
5H), 5.75-5.84 (m, 1H), 5.08-5.16 (m, 2H), 4.11 (q, 2H, J )
7.2 Hz), 3.70 (dd, 1H, J ) 8.6, 6.4 Hz), 2.47-2.65 (m, 2H), 1.16
(t, 3H, J ) 7.2 Hz); 13C NMR (75 MHz, CDCl3) δC 171.5 (s),
133.8 (d), 133.0 (d), 129.9 (s), 128.8 (d), 127.9 (d), 117.9 (t),
61.0 (t), 50.2 (d), 35.7 (t), 14.4 (q); IR (neat, cm-1) 2988, 1732,
1439, 1259, 1157, 691; MS (EI) 236 [M+]; HRMS (EI) calcd for
C
13H16SO2 236.0871, found 236.0870.
2-(N,N-Dim eth yla m in o)-4-p en ten oic a cid eth yl ester :8
colorless oil (87% yield); 1H NMR (300 MHz, CDCl3) δH 5.73-
5.82 (m, 1H), 5.04-5.14 (m, 2H), 4.18 (q, 2H, J ) 7.1 Hz), 3.20
(dd, 1H, J ) 8.3, 6.6 Hz), 2.38-2.50 (m, 2H), 2.36 (s, 6H), 1.25
(t, 3H, J ) 7.1 Hz); 13C NMR (75 MHz, CDCl3) δC 171.5 (s),
134.2 (d), 117.2 (t), 67.5 (d), 60.1 (t), 41.6 (q), 34.1 (t), 14.4 (q);
IR (neat, cm-1) 2923, 1744, 1472, 1221; MS (EI) 130 [M+
-
C3H5]; HRMS (EI) calcd for C6H12NO2 130.0868, found 130.0862.
2-(N,N-Dim et h yla m in o)-3,4-p en t a d ien oic a cid et h yl
1
ester :26 colorless oil (88% yield); H NMR (400 MHz, CDCl3)
δH 5.26 (dt, 1H, J ) 8.6, 6.7 Hz), 4.83 (dd, 2H, J ) 6.7, 1.0
Hz), 4.22 (q, 2H, J ) 7.2 Hz), 3.63(d, 1H, J ) 8.6 Hz), 2.34 (s,
3H), 1.29(t, 3H, J ) 7.2 Hz); 13C NMR (100 MHz, CDCl3) δC
209.4 (s), 170.9 (s), 86.2 (d), 76.1 (t), 68.8 (d), 60.8 (t), 42.1 (q),
Gen er a l P r oced u r e of th e In tr a m olecu la r Su lfon iu m /
Am m on iu m Ylid e [2,3]-Sigm a tr op ic Rea r r a n gem en t Re-
a ction s. To a solution of [RuII(TTP)(CO)] (5 µmol) in dry
toluene (4 mL) was added dropwise an appropriate diazo
compound (0.5 mmol) in dry toluene (4 mL) via a syringe pump
over 2 h at 50 °C. After complete substrate consumption based
on TLC monitoring, the solvent was removed by vacuum and
the crude residue was chromatographed on a silica gel column
using a hexanes-ethyl acetate mixture as eluant.
14.2 (q); IR (neat, cm-1) 2922, 1722, 1234; MS (EI) 124 [M+
-
ÃΕt]; HRMS (EI) calcd for C7H10NO 124.0762, found 124.0763.
2-(N-Met h yl-N-p h en yla m in o)-4-p en t en oic a cid et h yl
ester : colorless oil (73% yield); 1H NMR (300 MHz, CDCl3) δH
7.19-7.26 (m, 2H), 6.72-6.82 (m, 3H), 5.70-5.82 (m, 1H),
5.03-5.18 (m, 2H), 4.42 (dd, 1H, J ) 8.9, 5.6 Hz), 4.11-4.19
(m, 2H), 2.90 (s, 3H), 2.67-2.75 (m, 1H), 2.57-2.65 (m, 1H),
1.22 (t, 3H, J ) 7.1 Hz); 13C NMR (75 MHz, CDCl3) δC 172.1
(s), 150.0 (s), 134.2 (d), 129.1 (d), 117.6 (d), 117.5 (t), 113.5 (d),
61.6 (d), 60.7 (t), 34.1 (t), 32.9 (q), 14.2 (q); IR (neat, cm-1) 2922,
1732, 1601, 1505, 1184, 749, 691; MS (EI) 233 [M+]; HRMS
(EI) calcd for C14H19NO2 233.1415, found 233.1412.
2-Allyld ih yd r oth iop h en -3-on e (2a ):29 colorless oil (92%
yield); 1H NMR (300 MHz, CDCl3) δH 5.74-5.88 (m, 1H), 5.01-
5.17 (m, 2H), 3.44 (dd, 1H, J ) 8.7, 4.4 Hz), 2.96 (dd, 2H, J )
8.1, 6.9 Hz), 2.54-2.77 (m, 3H), 2.29-2.39 (m, 1H); 13C NMR
(75 MHz, CDCl3) δC 213.2 (s), 134.3 (d), 117.5 (t), 51.1 (d), 39.3
(t), 36.0 (t), 23.4 (t); IR (neat, cm-1) 2928, 1736, 1406, 1132,
1003, 918; MS (EI) 142 [M+]; HRMS (EI) calcd for C7H10SO
142.0452, found 142.0458.
2-(N-Ben zyl-N-m et h yla m in o)-4-p en t en oic a cid et h yl
ester : colorless oil (82% yield); 1H NMR (400 MHz, CDCl3) δH
7.21-7.34 (m, 5H), 5.77-5.87 (m, 1H), 5.03-5.13 (m, 2H),
4.15-4.24 (m, 2H), 3.80 (d, 1H, J ) 13.6 Hz), 3.60 (d, 1H, J )
13.6 Hz), 3.39 (t, 1H, J ) 7.6 Hz), 2.45-2.57 (m, 2H), 2.28 (s,
3H), 1.30 (t, 3H, J ) 7.2 Hz); 13C NMR (100 MHz, CDCl3) δC
171.8 (s), 139.3 (s), 134.8 (d), 128.6 (d), 128.1 (d), 126.9 (d),
116.8 (t), 65.6 (d), 60.0 (t), 58.3 (t), 37.9 (q), 34.0 (t), 14.5 (q);
IR (neat, cm-1) 2992, 1731, 1455, 1178, 1027, 915, 736, 698;
MS (EI) 247 [M+]; HRMS (EI) calcd for C15H21NO2 247.1572,
found 247.1572.
2-Allyld ih yd r oth iop yr a n -3-on e (2b):28 colorless oil (94%
yield); 1H NMR (400 MHz, CDCl3) δH 5.87-5.85 (m, 1H), 5.05-
5.14 (m, 2H), 3.49 (t, 1H, J ) 7.0 Hz), 2.89-2.96 (m, 1H), 2.64-
2.75 (m, 2H), 2.50-2.56 (m, 2H), 2.33-2.39 (m, 2H), 2.20-
2.27 (m, 1H); 13C NMR (100 MHz, CDCl3) δC 205.1 (s), 134.4
(d), 117.3 (t), 49.6 (d), 41.9 (t), 34.7 (t), 32.8 (t), 28.9 (t); IR
(neat, cm-1) 2928, 1707, 1435, 1003, 918; MS (EI) 156 [M+];
HRMS (EI) calcd for C8H12SO 156.0608, found 156.0609.
N-Meth yl-2-a llyl-3-p yr r olid in on e (4a ):12c colorless oil
(87% yield); 1H NMR (300 MHz, CDCl3) δH 5.68-5.79 (m, 1H),
5.03-5.14 (m, 2H), 3.31-3.36 (m, 1H), 2.43-2.49 (m, 5H),
2-(N,N-Dim eth ylam in o)-3-m eth yl-4-pen ten oic Acid Eth -
yl Ester .8 Separable 3:1 mixture of anti- and syn-isomers. For
the major isomer: colorless oil (64% yield); 1H NMR (300 MHz,
CDCl3) δH 5.73-5.85 (m, 1H), 5.04-5.12 (m, 2H), 4.19 (q, 2H,
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Commun. 1990, 46.
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