J.W. Cran et al. / Tetrahedron 67 (2011) 9922e9943
9935
30.7, 28.8. IR (NaCl, cmꢁ1): 3055, 2990, 2923, 1668, 1651, 1621, 1597,
1578, 1447, 1352, 1288, 1224, 1180, 1002, 916. HRMS (CIþ) calcd for
C13H15O2: 203.10721, Found: 203.10713. Anal. Calcd for C13H14O2: C,
77.20; H, 6.98. Found: C, 76.91; H, 6.95.
Ar H), 7.05 (dt, J¼15.4, 6.6 Hz, 1H), 6.91 (dt, J¼15.4, 1.5 Hz, 1H), 2.66
(AB, JAB¼5.1 Hz, 1H), 2.62 (AB, JAB¼5.1 Hz, 1H), 2.40e2.47 (m, 2H),
1.77e1.84 (m, 2H), 1.36 (s, 3H). 13C NMR (CDCl3, 75 MHz):
d 189.9,
148.0, 137.3, 132.2, 128.1, 128.0, 125.7, 55.8, 53.2, 34.6, 27.9, 20.5. IR
(NaCl, cmꢁ1): 3039, 2928, 1668, 1651, 1622, 1598, 1578, 1448, 1390,
1336, 1288, 1222, 1180, 1072, 1002. HRMS (CIþ) calcd for C14H17O2:
217.12286, Found: 217.12279. Anal. Calcd for C14H16O2: C, 77.75; H,
7.46. Found: C, 77.65; H, 7.48.
6.4.11. Alcohol 14. 1H NMR (CDCl3, 500 MHz):
d 7.61e7.65 (m, 2H, Ar
H), 7.46e7.53 (m,1H, Ar H), 7.39e7.44 (m, 2H, Ar H), 6.58 (ddd, J¼5.6,
4.1, 1.5 Hz, 1H), 4.14 (dddd, J¼8.5, 8.5, 4.9, 3.2 Hz, 1H), 2.83 (ABddd,
JAB¼15.8 Hz, J¼4.9, 2.9, 1.5 Hz, 1H), 2.50 (ABdddd, JAB¼19.8 Hz, J¼8.1,
6.1, 4.1, 2.4 Hz, 1H), 2.29e2.44 (m, 2H), 1.87e1.95 (m, 1H), 1.69e1.78
6.4.17. Alcohol 19. 1H NMR (CDCl3, 500 MHz):
d 7.61e7.65 (m, 2H,
(m, 1H). 13C NMR (CDCl3, 75 MHz):
d
197.6, 143.2, 138.3, 135.9, 131.3,
Ar H), 7.47e7.52 (m, 1H, Ar H), 7.39e7.44 (m, 2H, Ar H), 6.59e6.63
(m, 1H), 2.46e2.61 (m, 3H), 2.28e2.37 (m, 1H), 1.73e1.81 (m, 1H),
129.0, 127.9, 65.9, 32.7, 29.2, 23.9. IR (NaCl, cmꢁ1): 3418, 3058, 2928,
1634, 1575, 1446, 1267, 1127, 1067, 1000, 958. HRMS (FABþ) calcd for
C13H14O2Na: 225.0892, Found: 225.0897. Anal. Calcd for C13H14O2: C,
77.20; H, 6.98. Found: C, 77.53; H, 6.93.
1.59e1.67 (m, 1H), 1.37 (s, 3H). 13C NMR (CDCl3, 75 MHz):
d 197.6,
142.7, 138.5, 136.4, 131.4, 129.1, 128.0, 68.4, 38.1, 34.0, 29.2, 24.0. IR
(NaCl, cmꢁ1): 3435, 3057, 2964, 2927, 1637, 1597, 1577, 1446, 1421,
1374, 1277, 1254, 1141, 1107, 1027, 1001, 972. HRMS (CIþ) calcd for
C14H17O2: 217.12286, Found: 217.12301. Anal. Calcd for C14H16O2: C,
77.75; H, 7.46. Found: C, 77.58; H, 7.32.
6.4.12. Alcohol 15. 1H NMR (CDCl3, 500 MHz):
d 7.71e7.76 (m, 2H,
Ar H), 7.52e7.58 (m, 1H, Ar H), 7.42e7.48 (m, 2H, Ar H), 6.63e6.67
(m, 1H), 3.75 (ABd, JAB¼10.7 Hz, J¼4.1 Hz, 1H), 3.70 (ABd,
JAB¼10.7 Hz, J¼7.6 Hz, 1H), 3.29e3.38 (m, 1H), 2.50e2.68 (m, 2H),
2.25 (dddd, J¼13.2, 9.0, 9.0, 6.4 Hz, 1H),1.77 (ddt, J¼13.2, 9.0, 5.9 Hz,
6.4.18. Epoxide 20. Epoxide 20 was prepared by the typical cross-
metathesis procedure using 2-(1,1-dimethyl-but-3-enyl)-oxirane59
and methyl vinyl ketone (64% yield). 1H NMR (CDCl3, 500 MHz):
1H). 13C NMR (CDCl3, 75 MHz):
d 196.2, 150.6, 145.8, 138.7, 132.2,
129.1, 128.2, 66.1, 48.3, 32.5, 27.4. IR (NaCl, cmꢁ1): 3417, 3059, 2929,
1643, 1634, 1598, 1576, 1446, 1431, 1351, 1316, 1285, 1179, 1158, 1130,
1075, 1055, 1028, 975. HRMS (CIþ) calcd for C13H15O2: 203.10721,
Found: 203.10735. Anal. Calcd for C13H14O2: C, 77.20; H, 6.98.
Found: C, 77.05; H, 6.86.
d
6.85 (dt, J¼16.1, 8.1 Hz, 1H), 6.10 (d, J¼16.1 Hz, 1H), 2.78 (dd, J¼4.4,
2.9 Hz, 1H), 2.66 (dd, J¼4.4, 4.4 Hz, 1H), 2.61 (dd, J¼4.4, 2.9 Hz, 1H),
2.19e2.29 (obscured m, 2H), 2.25 (obscured s, 3H), 0.93 (s, 3H), 0.90
(s, 3H). 13C NMR (CDCl3, 75 MHz):
d 196.9, 143.2, 132.9, 58.1, 42.7,
42.3, 33.4, 26.0, 22.0. IR (NaCl, cmꢁ1): 3053, 3002, 2965, 2932, 2876,
1697, 1673, 1627, 1473, 1430, 1405, 1364, 1255, 1188, 983, 914. HRMS
(CIþ) calcd for C10H17O2: 169.12286, Found: 169.12258. Anal. Calcd
for C10H16O2: C, 71.39; H, 9.59. Found: C, 71.24; H, 9.59.
6.4.13. 2-But-3-enyl-2-methyl-oxirane58. This was prepared by the
typical epoxidation procedure using 2-methyl-1,5-hexadiene (73%
yield). 1H NMR (CDCl3, 500 MHz):
d
5.82 (ddt, J¼16.8, 10.3, 6.6 Hz,
1H), 5.04 (ddt, J¼16.8, 1.5, 1.5 Hz, 1H), 4.97 (dd, J¼10.3, 1.5 Hz, 1H),
2.62 (AB, JAB¼5.1 Hz, 1H), 2.58 (AB, JAB¼5.1 Hz, 1H), 2.13e2.20 (m,
2H), 1.71 (ddd, J¼13.9, 8.8, 6.6 Hz, 1H), 1.60 (ddd, J¼13.9, 8.8, 7.3 Hz,
6.4.19. Alcohol 21. 1H NMR (CDCl3, 500 MHz):
d 6.80e6.85 (m, 1H),
3.60 (dd, J¼5.1, 5.1 Hz, 1H), 2.57 (dm, J¼2.2 Hz, 1H), 2.23e2.32 (ob-
scured m, 2H), 2.30 (s, 3H), 2.05 (dm, J¼2.2 Hz,1H), 0.95 (s, 3H), 0.93
1H), 1.32 (s, 3H). 13C NMR (CDCl3, 75 MHz):
d
137.5, 114.3, 56.0, 53.2,
(s, 3H). 13C NMR (CDCl3, 75 MHz):
d 198.8, 139.5, 136.1, 73.0, 37.6,
35.5, 29.0, 20.5. IR (NaCl, cmꢁ1): 3076, 3040, 2980, 2928, 2858,
1642, 1489, 1450, 1390, 1262, 1108, 1068, 995, 911. HRMS (CIþ) calcd
for C7H13O: 113.09665, Found: 113.09706.
33.1, 29.5, 25.8, 25.1, 22.5. IR (NaCl, cmꢁ1): 3444, 3050, 2956, 1667,
1651,1470,1422,1392,1354, 1329,1255,1199,1176,1133,1056,1012,
981. HRMS (CIþ) calcd for C10H17O2: 169.12286, Found: 169.12257.
Anal. Calcd for C10H16O2: C, 71.39; H, 9.59. Found: C, 71.42; H, 9.50.
6.4.14. Epoxide 16. Epoxide 16 was prepared by the typical cross-
metathesis procedure using 2-but-3-enyl-2-methyl-oxirane and
6.4.20. Epoxide 22. Epoxide 22 was prepared by the typical cross-
metathesis procedure using 2-(1,1-dimethyl-but-3-enyl)-oxirane
and 1-phenylbut-2-en-1-one (52% yield). 1H NMR (CDCl3,
methyl vinyl ketone (62% yield). 1H NMR (CDCl3, 500 MHz):
d 6.79
(dt, J¼16.1, 6.6 Hz, 1H), 6.09 (dt, J¼16.1, 1.5 Hz, 1H), 2.63 (AB,
JAB¼4.4 Hz, 1H), 2.60 (AB, JAB¼4.4 Hz, 1H), 2.33 (ddt, J¼7.3, 1.5,
7.3 Hz, 2H), 2.24 (s, 3H), 1.75 (ABt, JAB¼13.9 Hz, J¼7.3 Hz, 1H), 1.72
(ABt, JAB¼13.9 Hz, J¼7.3 Hz, 1H), 1.34 (s, 3H). 13C NMR (CDCl3,
500 MHz):
d 7.91e7.96 (m, 2H, Ar H), 7.53e7.59 (m, 1H, Ar H),
7.44e7.50 (m, 2H, Ar H), 7.09 (dt, J¼15.4, 8.1 Hz, 1H), 6.91 (dt,
J¼15.4, 1.5 Hz, 1H), 2.82 (dd, J¼4.4, 2.9 Hz, 1H), 2.67 (dd, J¼4.4,
4.4 Hz, 1H), 2.64 (dd, J¼4.4, 2.9 Hz, 1H), 2.37 (ABdd, JAB¼13.9 Hz,
J¼8.1, 1.5 Hz, 1H), 2.31 (ABdd, JAB¼13.9 Hz, J¼8.1, 1.5 Hz, 1H), 0.96
75 MHz):
d 197.0, 146.4, 130.6, 55.2, 52.5, 34.1, 27.2, 25.9, 20.0. IR
(NaCl, cmꢁ1): 3039, 2928, 1697, 1674, 1627, 1430, 1391, 1362, 1255,
1190, 981. HRMS (CIþ) calcd for C9H15O2: 155.10721, Found:
155.10757. Anal. Calcd for C9H14O2: C, 70.10; H, 9.15. Found: C,
69.96; H, 9.24.
(s, 6H). 13C NMR (CDCl3, 75 MHz):
d 190.1, 145.2, 137.6, 132.5,
128.4, 128.3, 58.8, 43.7, 43.1, 34.2, 22.9, 22.9, 22.4. IR (NaCl,
cmꢁ1): 3057, 2965, 2931, 2874, 1668, 1651, 1621, 1598, 1579, 1471,
1448, 1404, 1365, 1348, 1280, 1222, 1180, 1158, 1072, 1011, 983,
914. HRMS (ESIþ) calcd for C15H18O2Na: 253.12045, Found:
253.12025. Anal. Calcd for C15H18O2: C, 78.23; H, 7.88. Found: C,
78.05; H, 7.92.
6.4.15. Alcohol 17. 1H NMR (CDCl3, 500 MHz):
d
6.93 (ddd, J¼6.3,
3.4, 1.7 Hz, 1H), 2.46e2.57 (m, 1H), 2.40 (ABm, JAB¼18.1 Hz, 1H),
2.24e2.37 (obscured m, 2H), 2.31 (s, 3H), 1.72 (dddd, J¼13.2, 6.1, 4.1,
1.7 Hz, 1H), 1.54 (ddd, J¼13.2, 8.8, 6.1 Hz, 1H), 1.31 (s, 3H). 13C NMR
(CDCl3, 75 MHz):
d
198.9, 139.9, 137.4, 68.2, 37.1, 33.7, 29.2, 25.2,
6.4.21. Alcohol 23. 1H NMR (CDCl3, 500 MHz):
d 7.60e7.65 (m, 2H,
23.9. IR (NaCl, cmꢁ1): 3418, 3051, 2966, 2929,1667,1651,1644,1634,
1428, 1385, 1250, 1204, 1104, 1078, 1022, 959. HRMS (EIþ) calcd for
C9H14O2: 154.09938, Found: 154.09941. Anal. Calcd for C9H14O2: C,
70.10; H, 9.15. Found: C, 69.93; H, 9.05.
Ar H), 7.48e7.56 (m, 1H, Ar H), 7.39e7.44 (m, 2H, Ar H), 6.51 (ddd,
J¼3.7, 2.2, 1.5 Hz, 1H), 3.70 (dd, J¼5.9, 5.1 Hz, 1H), 2.78 (ABdt,
JAB¼18.3 Hz, J¼2.2, 5.1 Hz, 1H), 2.46 (ABddd, JAB¼18.3 Hz, J¼5.9,
3.7, 2.2 Hz, 1H), 2.29 (ABdt, JAB¼19.8 Hz, J¼2.2, 3.7 Hz, 1H), 2.07
(ABdt, JAB¼19.8 Hz, J¼2.2, 4.4 Hz, 1H), 1.00 (s, 3H), 0.99 (s, 3H). 13
C
6.4.16. Epoxide 18. Epoxide 18 was prepared by the typical cross-
metathesis procedure using 2-but-3-enyl-2-methyl-oxirane and
1-phenylbut-2-en-1-one (48% yield). 1H NMR (CDCl3, 500 MHz):
NMR (CDCl3, 75 MHz): d 197.4, 142.5, 138.3, 135.1, 131.3, 129.0,
127.9, 73.0, 37.8, 33.2, 30.4, 25.9, 22.5. IR (NaCl, cmꢁ1): 3458, 3058,
2957, 1633, 1597, 1577, 1471, 1446, 1422, 1383, 1268, 1200, 1178,
1116, 1057, 982. HRMS (ESIþ) calcd for C15H18O2Na: 253.12045,
d
7.90e7.95 (m, 2H, Ar H), 7.53e7.59 (m,1H, Ar H), 7.44e7.50 (m, 2H,