Tandem Self-Cross and Ring-Closing Metathesis
Diprop-2-en-1-yl (1R,2S)-Cyclohexane-1,2-dicarboxylate (4g): Col-
(400 MHz, CDCl3): δ = 6.21–6.20 (m, 4 H, =CH), 5.89–5.74 (m, 4
H, =CH), 4.73–4.60 (m, 8 H, CH2) ppm. 13C NMR (100 MHz,
CDCl3): δ = 164.7 (C=O), 164.6 (C=O), 129.8 (=CH), 129.7
orless viscous oil (250 mg, 85%). IR (neat): ν
= 3056, 2940,
˜
max
1728, 1650, 1450, 1378, 1349, 1245, 1243, 1193, 1028, 937 cm–1. 1H
NMR (400 MHz, CDCl3): δ = 5.89–5.79 (m, 2 H, =CH), 5.27–5.14 (=CH), 129.6 (=CH), 128.06 (=CH), 65.8 (CH2), 64.5 (CH2), 29.7
(m, 4 H, =CH2), 4.52 (m, 4 H, OCH2), 2.82 (s, 2 H), 1.97–1.72 (m,
(CH2) ppm. HRMS (ESI+): calcd. for C16H16O8Na [M + Na]+
4 H), 1.49–1.36 (m, 4 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 359.0743; found 359.0749.
173.2 (C=O), 132.2 (=CH), 118.9 (=CH2), 65.0 (OCH2), 42.6 (CH),
Macrotetralide 5c: Semisolid (75 mg, 87%). IR (neat): νmax = 2929,
˜
26.2 (CH2), 23.7 (CH2) ppm. HRMS (ESI+): calcd. for
1735, 1415, 1382, 1272, 1252, 1081, 972 cm–1. 1H NMR (400 MHz,
CDCl3): δ = 5.77–5.64 (m, 4 H, =CH), 4.66–4.52 (m, 8 H, CH2),
2.63–2.58 (m, 8 H, OCH2) ppm. 13C NMR (100 MHz, CDCl3): δ
= 171.6 (C=O), 171.5 (C=O), 171.4 (C=O), 127.8 (=CH), 127.4
(=CH), 127.2 (=CH), 64.0 (CH2), 60.4 (CH2), 29.7 (CH2), 29.6
(CH2), 22.5 (CH2) ppm. HRMS (ESI+): calcd. for C16H20O8Na [M
+ Na]+ 363.1056; found 363.1063.
C14H20O4Na [M + Na]+ 275.1259; found 275.1248.
Diprop-2-en-1-yl 4-Methylcyclohexane-1,2-dicarboxylate (4h): Col-
orless viscous oil (250 mg, 87%). IR (neat): ν
= 2955, 2870,
˜
max
1734, 1648, 1522, 1376, 1255, 1092, 866 cm–1. 1H NMR (400 MHz,
CDCl3): δ = 5.85–5.77 (m, 2 H, =CH), 5.20–5.13 (m, 2 H, =CH2),
5.11–5.10 (m, 2 H, =CH2), 4.50–4.47 (m, 4 H, OCH2), 3.20–3.18
(m, 1 H, CH), 2.43–1.88 (m, 6 H, CH2), 1.96–1.92 (m, 2 H, CH),
0.87–0.80 (m, 3 H, CH3) ppm. 13C NMR (100 MHz, CDCl3): δ =
172.8 (C=O), 172.5 (C=O), 132.3 (=CH), 117.7 (=CH2), 117.4
(=CH2), 64.7 (OCH2), 64.6 (OCH2), 43.4 (CH), 41.5 (CH), 40.7
(CH), 36.1 (CH2), 31.8 (CH2), 30.4 (CH2), 27.9 (CH2), 22.1 (CH3)
ppm. HRMS (ESI+): calcd. for C15H22O4Na [M + Na]+ 289.1416;
found 289.1429.
Macrotetralide 5d: Colorless solid (74 mg, 85%); m.p. 182 °C. IR
(neat): νmax = 2920, 1732, 1641, 1440, 1390, 1351, 1295, 1246, 1195,
˜
1
1041, 947 cm–1. H NMR (400 MHz, CDCl3): δ = 5.78–5.66 (m, 4
H, =CH), 4.63–4.50 (m, 8 H, OCH2), 2.36–2.30 (m, 8 H, CH2),
1.94–1.97 (m, 4 H, CH2) ppm. 13C NMR (100 MHz, CDCl3): δ =
172.5 (C=O), 172.4 (C=O), 172.3 (C=O), 128.1 (=CH), 128.0
(=CH), 127.6 (=CH), 65.1 (CH2), 63.8 (CH2), 63.7 (CH2), 63.5
(CH2), 33.2 (CH2), 33.1 (CH2), 29.6 (CH2), 20.3 (CH2), 20.0 (CH2),
19.9 (CH2) ppm. HRMS (ESI+): calcd. for C18H24O8Na [M +
Na]+ 391.1369; found 391.1357.
Diprop-2-en-1-yl Biphenyl-2,2Ј-dicarboxylate (4i): Semisolid
(240 mg, 92%). IR (neat): ν
= 3005, 2957, 1734, 1625, 1438,
˜
max
1412, 1339, 1279, 1149, 1024, 953 cm–1. 1H NMR (400 MHz,
CDCl3): δ = 7.55–7.51 (m, 2 H, Ar), 7.46–7.42 (m, 4 H, Ar), 7.24–
7.22 (m, 4 H, Ar), 5.74–5.64 (m, 2 H, =CH), 5.18–5.11 (m, 2 H,
=CH), 5.10–5.00 (m, 2 H, =CH), 4.53–4.51 (m, 4 H, CH2) ppm.
13C NMR (100 MHz, CDCl3): δ = 166.7 (C=O), 143.3 (Ar), 131.9
(=CH), 131.5 (=CH), 130.3 (=CH), 130.0 (=CH), 129.5 (Ar), 118.0
(=CH2), 65.4 (OCH2) ppm. HRMS (ESI+): calcd. for C20H18O4Na
[M + Na]+ 345.1103; found 345.1116.
Macrotetralide 5e: Semisolid (80 mg, 90%). IR (neat): νmax = 3064,
˜
2942, 1724, 1648, 1600, 1448, 1362, 1274, 1122, 966 cm–1. 1H NMR
(400 MHz, CDCl3): δ = 7.71–7.63 (m, 4 H, Ar), 7.51–7.47 (m, 4 H,
Ar), 5.93–5.80 (m, 4 H, =CH), 4.84–4.82 (m, 4 H, OCH2), 4.75–
4.37 (m, 4 H, OCH2) ppm. 13C NMR (100 MHz, CDCl3): δ = 166.4
(C=O), 166.2 (C=O), 131.9 (Ar), 130.7 (Ar), 130.6 (Ar), 130.4
(=CH), 130.3 (=CH), 130.3 (=CH), 130.2 (=CH), 128.4 (=CH),
128.0 (=CH), 127.9 (=CH), 126.9 (=CH), 126.8 (=CH), 126.0 (Ar),
64.1 (OCH2), 63.9 (OCH2), 60.6 (OCH2), 60.4 (OCH2) ppm.
HRMS (ESI+): calcd. for C24H20O8Na [M + Na]+ 459.1056; found
459.1043.
Diprop-2-en-1-yl Benzene-1,3-dicarboxylate (6): Semisolid (270 mg,
87%). IR (neat): ν
= 3033, 2950, 2882, 1728, 1428, 1450, 1373,
˜
max
1278, 1126, 1071, 967 cm–1. 1H NMR (400 MHz, CDCl3): δ = 8.61
(s, 1 H, Ar), 8.60–8.11 (m, 2 H, Ar), 7.42 (t, J = 7 Hz, 1 H, Ar),
5.99–5.89 (m, 2 H, =CH), 5.34–5.18 (m, 4 H, =CH), 4.75–4.73 (m,
2 H, CH2) ppm. 13C NMR (100 MHz, CDCl3): δ = 165.2 (C=O),
133.8 (=CH), 132.0 (=CH), 131.5 (=CH), 130.7 (=CH), 130.6 (Ar),
129.0 (=CH), 118.5 (=CH2), 65.8 (OCH2) ppm. HRMS (ESI+):
calcd. for C14H14O4Na [M + Na]+ 269.0790; found 269.0798.
Macrotetralide 5f: Semisolid (78 mg, 88%). IR (neat): νmax = 2929,
˜
1733, 1654, 1439, 1377, 1273, 1247, 1188, 1028, 937 cm–1. 1H NMR
(400 MHz, CDCl3): δ = 5.76–5.72 (m, 4 H, =CH), 5.62 (s, 4 H,
=CH), 4.60–4.43 (m, 8 H), 3.07–3.04 (m, 4 H), 2.49–2.26 (m, 8 H)
ppm. 13C NMR (100 MHz, CDCl3): δ = 172.8 (C=O), 172.7
(C=O), 127.6 (=CH), 127.5 (=CH), 125.1 (=CH), 125.0 (=CH),
64.1 (OCH2), 63.9 (OCH2), 39.1 (CH), 39.0 (CH), 25.8 (CH2), 25.7
(CH2) ppm. HRMS (ESI+): calcd. for C24H28O8Na [M + Na]+
467.1682; found 467.1695.
Tandem Self-Cross and Ring-Closing Metathesis Reactions of Com-
pounds 4: In an oven-dried round-bottom flask, diolefin
4
(0.3 mmol) and Ti(OiPr)4 (20 mol-%) were dissolved in dry toluene
(100 mL) under an inert gas, and the reaction mixture was then
warmed to 80 °C. To this warm solution was slowly added Grubbs’
second-generation catalyst (5 mol-%) in dry toluene (5 mL) by a
syringe pump over 30 min, and the reaction mixture was stirred for
the appropriate time at 80 °C. The reaction was monitored by TLC.
Then, the mixture was filtered, and the solvent was evaporated un-
der reduced pressure. The residue was subjected to column
chromatography using silica gel (100–200 mesh, EtOAc/hexane) to
furnish the respective macrotetralide 5.
Macrotetralide 5g: Semisolid (79 mg, 89%). IR (neat): νmax = 2951,
˜
2887, 1728, 1448, 1281, 1124, 1078, 738 cm–1. 1H NMR (400 MHz,
CDCl3): δ = 5.90–5.79 (m, 4 H, =CH), 4.73–4.37 (m, 8 H, OCH2),
2.93 (s, 4 H, CH), 1.97–1.71 (m, 4 H, CH2), 1.49–1.35 (m, 4 H,
CH2), 0.81–0.78 (m, 8 H, CH2) ppm. 13C NMR (100 MHz,
CDCl3): δ = 172.2 (C=O), 172.1 (C=O), 126.4 (=CH), 126.2
(=CH), 62.9 (OCH2), 62.7 (OCH2), 52.4 (CH2), 41.7 (CH), 41.6
(CH), 28.7 (CH2), 25.3 (CH2), 25.2 (CH2), 22.6 (CH2) ppm. HRMS
(ESI+): calcd. for C24H32O8Na [M + Na]+ 471.1995; found
471.1988.
Macrotetralide 5a: Colorless solid (82 mg, 96%); m.p. 159 °C. IR
(neat): ν
= 2926, 1730, 1455, 1383, 1274, 1249, 1148, 1072,
˜
max
978 cm–1. 1H NMR (400 MHz, CDCl3): δ = 5.80–5.74 (m, 4 H,
=CH2), 4.70–4.59 (m, 8 H, CH2), 3.37 (s, 4 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 164.9 (C=O), 164.6 (C=O), 126.7 (=CH),
125.9 (=CH), 125.8 (=CH), 63.5 (CH2), 59.4 (CH2), 40.9 (CH2)
ppm. HRMS (ESI+): calcd. for C14H16O8Na [M + Na]+ 335.0743;
found 335.0752.
Macrotetralide 5h: Semisolid (77 mg, 86%). IR (neat): νmax = 2925,
˜
1728, 1650, 1455, 1371, 1349, 1294, 1243, 1193, 1036, 937 cm–1. 1H
NMR (400 MHz, CDCl3): δ = 5.77–5.23 (m, 4 H, =CH), 4.62–4.33
(m, 8 H, =CH2), 3.29–3.23 (m, 2 H, OCH2), 2.47–2.17 (m, 4 H,
CH2), 2.15–2.13 (m, 4 H, CH), 1.96–1.71 (m, 4 H), 0.88–0.77 (m,
6 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 172.3 (C=O), 172.2
Macrotetralide 5b: Semisolid (77 mg, 90%). IR (neat): νmax = 2921,
˜
2852, 1732, 1625, 1527, 1376, 1255, 1092, 866 cm–1. 1H NMR (C=O), 171.8 (C=O), 126.7 (=CH), 126.4 (=CH), 126.3 (=CH),
Eur. J. Org. Chem. 2014, 363–370
© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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