+
+
Ring Opening-Ring Closing Metathesis of Cyclic Olefins
J. Am. Chem. Soc., Vol. 118, No. 28, 1996 6639
(neat, cm-1) 3078, 3014, 2978, 2931, 2854, 1081; HRMS calcd for
C9H13O2 (MH+) 153.0916, found 153.0915.
3078, 3016, 2982, 29313, 2858, 1082; HRMS calcd for C14H23O2 (MH+)
223.1698, found 223.1704.
cis-3,8-Cyclooctenediol Bis((E/Z)-2-butenyl) Ether (7b). The ether
7b was prepared in a manner similar to 4 using crotyl bromide and,
cis-3,8-cyclooctenediol was prepared by the method of Ba¨ckvall. 7b
was isolated as a clear, colorless oil (74%): 1H NMR (C6D6, 300 MHz)
δ 5.74-5.47 (m, 6H), 4.17-3.96 (m, 4H), 3.84-3.91 (m, 2H), 1.99-
1.89 (m, 2H), 1.56-1.18 (m, 18H); 13C NMR (C6D6, 75 MHz) δ 134.3,
134.2, 134.1, 128.6, 127.6, 126.4, 75.6, 75.3, 69.1, 36.3, 36.2, 23.8,
17.5; IR (neat, cm-1) 3018, 2932, 2857, 1095; HRMS calcd for
C16H27O2 (MH+) 251.2011, found 251.2013.
meso-1,4-Bis(5-oxa-2-cyclopentenyl)butane (14). Bicyclic ether
14 was obtained as a clear, colorless oil (71%) under conditions
analogous to the reaction producing 10: 1H NMR (C6D6, 300 MHz) δ
5.48-5.43 (m, 4H), 4.80-4.77 (m, 2H), 4.52-4.44 (m, 2H), 1.54-
1.32 (m, 8H) 13C NMR (C6D6, 75 MHz) δ 130.2, 126.7, 86.1, 75.0,
36.5, 25.8; IR (neat, cm-1) 3077, 2932, 2853, 1078; HRMS calcd for
C12H19O2 (MH+) 195.1385, found 195.1383.
cis-3,4-Cyclopentenediol Bis(allyl) Ether (8). The ether 8 was
prepared in a manner similar to 4 using allyl bromide, and cis-3,4-
cyclopentenediol was prepared by the method of Sharpless from
cyclopentadiene. 8 was isolated as a clear, colorless oil (52%): 1H
NMR (C6D6, 300 MHz) δ 5.99-5.83 (m, 2H), 5.74-5.70 (m, 1H),
5.66-5.63 (m, 1H), 5.35-5.25 (m, 2H), 5.06-5.01 (m, 2H), 4.20-
3.77 (m, 6H), 2.46-2.38 (m, 1H), 2.23-2.15 (m, 1H); 13C NMR (C6D6,
75 MHz) δ 136.4, 135.9, 133.5, 130.2, 115.6, 115.4, 80.4, 79.0, 70.8,
69.7, 37.0; IR (neat, cm-1) 3077, 3014, 2982, 2917, 2855, 1124; HRMS
calcd for C11H17O2 (MH+) 181.1228, found 181.1238.
4-(5-Oxa-2-cyclopentenyl)-5-oxacyclohexene (17). Bicyclic ether
15 was obtained as a clear, colorless oil (92%) under conditions
analogous to the reaction producing 10: 1H NMR (C6D6, 300 MHz) δ
5.88-5.84 (m, 1H), 5.66-5.60 (m, 1H), 5.51-5.48 (m, 1H), 5.41-
5.36 (m, 1H), 4.84-4.81 (m, 1H), 4.48-4.43 (m, 2H), 4.03-3.96 (m,
2H), 3.47-3.40 (m, 1H), 2.18-2.00 (m, 2H); 13C NMR (C6D6, 75 MHz)
δ 127.8, 127.7, 126.6, 124.1, 88.8, 76.6, 75.7, 65.8, 27.7; IR (neat,
cm-1) 3035, 2919, 2848, 1090; HRMS calcd for C9H13O2 (MH+)
153.0916, found 153.0916.
cis-3,4-Cyclobutenediol Bis(allyl) Ether (2). Substrate 2 was
prepared in a fashion analogous to cyclobutene 3. 2 was isolated as a
clear oil (40%): 1H NMR (C6D6, 300 MHz) δ 6.08 (d, J ) 0.9 Hz,
2H), 5.95-5.84 (m, 2H), 5.33-5.26 (m, 2H), 5.06-5.00 (m, 2H), 4.42
(d, J ) 0.9 Hz, 2H), 4.11-3.94 (m, 4H); 13C NMR (C6D6, 75 MHz) δ
141.9, 136.0, 115.6, 81.9, 69.4; IR (neat, cm-1) 3125, 3078, 3051, 3015,
2983, 2861, 1122; HRMS calcd for C10H15O2 (MH+) 167.1072, found
167.1068.
meso-1,1′-Bi(5-oxa-2-cyclopentene) (10). Bicyclic ether 10 was
obtained as a clear, colorless oil (82%) under conditions analogous to
the reaction producing 11: 1H NMR (C6D6, 300 MHz) δ 5.81-5.77
(m, 2H), 5.49-5.45 (m, 2H), 4.80-4.76 (m, 2H), 4.52-4.40 (m, 4H);
13C NMR (C6D6, 75 MHz) δ 128.2, 127.7, 89.3, 75.8; IR (neat, cm-1
)
3079, 2852, 1082; HRMS calcd for C8H11O2 (MH+) 139.0759, found
139.0754.
cis-3,6-Cyclohexenediol Bis(allyl) Ether (5a). The ether 5a was
prepared in a manner similar to 4 using allyl bromide, and cis-3,6-
cyclohexenediol was prepared by the method of Ba¨ckvall. 5a was
isolated as a clear, colorless oil (78%): 1H NMR (C6D6, 300 MHz) δ
5.91-5.78 (m, 4H), 5.28-5.20 (m, 2H), 5.05-5.00 (m, 2H), 3.88-
3.75 (m, 4H), 3.63-3.59 (m, 2H), 1.91-11.82 (m, 2H), 1.51-1.42
(m, 2H); 13C NMR (C6D6, 75 MHz) δ 136.1, 131.0, 115.6, 72.3, 69.2,
25.3; IR (neat, cm-1) 3079, 3031, 2946, 2854, 1086; HRMS calcd for
C12H19O2 (MH+) 195.1385, found 195.1391.
cis-3,6-Cyclohexenediol Bis((E/Z)-2-butenyl) Ether (5b). The
ether 5b was prepared in a manner similar to 4 using crotyl bromide,
and cis-3,6-cyclohexenediol was prepared by the method of Ba¨ckvall.
5b was isolated as a clear, colorless oil (87%): 1H NMR (C6D6, 300
MHz) δ 5.93-5.90 (m, 2H), 5.70-5.45 (m, 4H), 3.99-3.79 (m, 4H),
3.69-3.67 (m, 2H), 1.97-1.88 (m, 2H), 1.57-1.44 (m, 8H); 13C NMR
(C6D6, 75 MHz) δ 131.1, 131.0, 129.1, 128.6, 126.4, 72.2, 71.9, 69.0,
64.0, 25.4, 17.8, 13.2; IR (neat, cm-1) 3027, 2939, 2854, 1092.
meso-1,2-Bis(5-oxa-2-cyclopentenyl)ethane (12). Bicyclic ether 12
was obtained as a clear, colorless oil (73%) under conditions analogous
to the reaction producing 10: 1H NMR (C6D6, 300 MHz) δ 5.45-5.40
(m, 4H), 4.84-4.81 (m, 2H), 4.47-4.45 (m, 4H), 1.78-1.56 (m, 4H);
13C NMR (C6D6, 75 MHz) δ 130.0, 126.8, 86.2, 75.1, 32.1; IR (neat,
cm-1) 3076, 3025, 2930, 1086.
meso-1,1′-Bi(6-oxa-2-cyclohexene) (15). Bicyclic ether 15 was
obtained as a clear, colorless oil (70%) under conditions analogous to
the reaction producing 10: 1H NMR (C6D6, 300 MHz) δ 5.76-5.69
(m, 2H), 4.13 (s, 2H), 3.85-3.78 (m, 2H), 3.47-3.38 (m, 2H), 2.07-
1.98 (m, 2H), 1.56-1.47 (m, 2H); 13C NMR (C6D6, 75 MHz) δ 128.4,
125.5, 76.4, 63.5, 25.6; IR (neat, cm-1) 3040, 2960, 2918, 2852, 1091;
HRMS calcd for C10H15O2 (MH+) 167.1080, found 167.1072.
endo,endo-5,6-Bis(2-oxa-4-pentenyl)bicyclo[2.2.1]hept-2-ene (9).
The ether 9 was prepared in a manner similar to 4 using allyl bromide
and endo,endo-5-norbornene-2,3-dimethanol. 9 was isolated as a clear,
colorless oil (55%): 1H NMR (C6D6, 300 MHz) δ 6.09-6.08 (m, 2H),
5.91-5.78 (m, 2H), 5.28-5.20 (m, 2H), 5.06-5.01 (m, 2H), 3.78-
3.73 (m, 4H), 3.27-3.22 (m, 2H), 3.02-2.93 (m, 4H), 2.52-2.46 (m,
2H), 1.50-1.46 (m, 1H), 1.18-1.14 (m, 1H); 13C NMR (C6D6, 75 MHz)
cis-3,7-Cycloheptenediol Bis(allyl) Ether (6a). The ether 6a was
prepared in a manner similar to 4 using allyl bromide, and cis-3,7-
cycloheptenediol was prepared by the method of Ba¨ckvall. 6a was
isolated as a clear, colorless oil (52%): 1H NMR (C6D6, 300 MHz) δ
5.90-5.78 (m, 4H), 5.26 (dd, J ) 17.2, 1.7 Hz, 2H), 5.04 (dd, J )
10.4, 1.3 Hz, 2H), 3.88-3.73 (m, 6H), 1.82-1.66 (m, 3H), 1.50-1.29
(m, 3H); 13C NMR (C6D6, 75 MHz) δ 135.8, 135.2, 115.6, 79.0, 69.3,
32.9, 25.1; IR (neat, cm-1) 3079, 3015, 2982, 2932, 2856, 1082; HRMS
calcd for C13H21O2 (MH+) 209.1542, found 209.1538.
cis-3,7-Cycloheptenediol Bis((E/Z)-2-butenyl) Ether (6b). The
ether 6b was prepared in a manner similar to 4 using crotyl bromide,
and cis-3,7-cycloheptenediol was prepared by the method of Ba¨ckvall.
6b was isolated as a clear, colorless oil (73%): 1H NMR (C6D6, 300
MHz) δ 5.94-5.90 (m, 2H), 5.72-5.45 (m, 4H), 3.98-3.78 (m, 6H),
1.88-1.34 (m, 12H); 13C NMR (C6D6, 75 MHz) δ 135.5, 135.4, 128.8,
δ 135.9, 135.5, 115.8, 71.9, 70.7, 49.3, 46.1, 42.0; IR (neat, cm-1
)
3059, 2961, 2919, 2864, 1092; HRMS calcd for C15H23O2 (MH+)
235.1698, found 235.1698.
cis,cis-5,10-Dioxatricyclo[8.5.0.08,14]pentadeca-2,12-diene (16). Tri-
cyclic ether 14 was obtained as a clear, colorless oil (68%) under
conditions analogous to the reaction producing 10: 1H NMR (C6D6,
300 MHz) δ 5.46-5.39 (m, 2H), 5.17-5.11 (m, 2H), 4.16-4.08 (m,
2H), 3.95-3.74 (m, 2H), 3.46-3.39 (m, 2H), 2.53-2.36 (m, 4H), 1.92-
1.84 (m, 1H), 1.37-1.26 (m, 2H); 13C NMR (C6D6, 75 MHz) δ 130.8,
127.1, 71.2, 69.6, 47.5, 42.1, 41.9; IR (neat, cm-1) 3003, 2928, 2873,
2817, 1124; HRMS calcd for C13H19O2 (MH+) 207.1385, found
207.1375.
126.6, 78.9, 78.7, 69.2, 64.2, 33.0, 25.3, 17.8, 13.2; IR (neat, cm-1
3023, 2933, 2856, 1093.
)
meso-1,3-Bis(5-oxa-2-cyclopentenyl)propane (13). Bicyclic ether
13 was obtained as a clear, colorless oil (57%) under conditions
analogous to the reaction producing 10: 1H NMR (C6D6, 300 MHz) δ
5.47-5.42 (m, 4H), 4.82-4.76 (m, 2H), 4.54-4.42 (m, 4H), 1.65-
1.43 (m, 6H); 13C NMR (C6D6, 75 MHz) δ 130.2, 126.7, 86.1, 75.0,
36.5, 21.6; IR (neat, cm-1) 3076, 3025, 2930, 1086.
Diallyl trans-1,4-Dihydronapthalene 1,4-Dicarboxylate (18). To
a stirring solution of trans-1,4-dihydronapthalene 1,4-dicarboxylic acid
(655 mg, 3 mmol) and allyl alcohol (0.48 mL, 7 mmol) in CH2Cl2 (15
mL) at ambient temperature was added DCC (1.4 g, 7 mmol). The
reaction mixture was allowed to stir 12 h. After purification on silica
gel (CH2Cl2 elution) the product 18 (70 mg, 8%) was isolated as a
white crystalline solid: 1H NMR (C6D6, 300 MHz) δ 7.25-7.22 (m,
2H), 7.05-7.02 (m, 2H), 6.01-5.99 (m, 2H), 5.67-5.54 (m, 2H), 5.02-
4.86 (m, 4H), 4.35-4.32 (m, 4H), 4.22-4.21 (m, 2H); 13C NMR
cis-3,8-Cyclooctenediol Bis(allyl) Ether (7a). The ether 7a was
prepared in a manner similar to 4 using allyl bromide, and cis-3,8-
cyclooctenediol was prepared by the method of Ba¨ckvall. 7a was
isolated as a clear, colorless oil (62%): 1H NMR (C6D6, 300 MHz) δ
5.95-5.82 (m, 2H), 5.57-5.54 (m, 2H), 5.27 (dd, J ) 17.2, 1.9 Hz,
2H), 5.05 (dd, J ) 10.4, 2.0 Hz, 2H), 4.10-3.96 (m, 4H), 3.82-3.74
(m, 2H), 1.94-1.86 (m, 2H), 1.54-1.20 (m, 6H); 13C NMR (C6D6, 75
MHz) δ 135.9, 134.3, 115.9, 76.0, 69.6, 36.4, 24.0; IR (neat, cm-1
)