Ring-Rearrangement Metathesis by Ru-Indenylidene Complexes
(CH), 117.9 (CH2), 80.9 (CH), 79.5 (C), 68.8 (CH2), 65.3 (CH2),
1 H, CH2-NTs] 3.51 [dd, J(H,H) = 9.2 and 5.2 Hz, CH-CO], 3.36
54.1 (CH), 52.9 (CH), 25.5 (CH3) ppm. HRMS (ESI): m/z: calcd. [d, J(H,H) = 9.2 Hz, 1 H, CH-CO], 3.17 [d, J(H,H) = 17.2 Hz, 1
for C13H15NO4 + H: 250.1079 [M+ + H]; found 250.1073.
H, CH2-NTs], 3.02 [d, J(H,H) = 12.4 Hz, 1 H, CH2-NTs], 2.32 (s,
3 H, CH3Ts) ppm. 13C NMR (75 MHz, CDCl3): δ = 175.3 (C),
173.4 (C), 144.3 (C), 137.6 (CH), 133.5 (C), 131.8 (C), 130.2 (CH),
129.7 (CH), 129.4 (CH), 129.2 (CH), 128.2 (CH), 127.5 (CH), 126.9
(CH), 118.2 (CH2), 80.1 (CH), 80.7 (C), 54.8 (CH), 53.0 (CH), 48.2
(CH2), 44.7 (CH2), 22.0 (CH3) ppm. HRMS (ESI): m/z: calcd. for
C25H24N2O5S + Na: 487.1304 [M+ + Na]; found 487.1296.
(1S,3R,3aS,6aR)-5-Methyl-3-vinyl-2Ј,3,3a,6Ј-tetrahydrospiro[furo-
[3,4-c]pyrrole-1,3Ј-pyran]-4,6(5H,6aH)-dione (16): According to the
general procedure for metathesis, the title compound was isolated
as a colorless oil (74%). 1H NMR (300 MHz, CDCl3): δ = 5.97 [d,
J(H,H) = 10.4 Hz, 1 H, CH=CH], 5.82 [ddd, J(H,H) = 17.0, 10.4
and 6.7 Hz, 1 H, CH2=CH], 5.57 [d, J(H,H) = 10.4 Hz, 1 H,
CH2=CH], 5.35 [d, J(H,H) = 17.0 Hz, 1 H, CH-O], 5.24 [d, J(H,H)
(1S,3ЈR,3aЈR,6aЈS)-3Ј-Vinyl-3ЈH-spiro[cyclohept[2]ene-1,1Ј-
= 6.7 Hz, 1 H, CH-O], 4.57 [d, J(H,H) = 7.1 Hz, 1 H, CH-CH2- furo[3,4-c]furan]-4Ј,6Ј(3aЈH,6aЈH)-dione (24): Following the general
O], 4.14 (s, 2 H, CH-CH2-O), 3.73 [d, J(H,H) = 10.9 Hz, 1 H, C- procedure for metathesis, the title compound was isolated as a col-
1
CH2-O], 3.56 [d, J(H,H) = 10.9 Hz, 1 H, C-CH2-O], 3.44 [t, J(H,H) orless oil (79%). H NMR (300 MHz, CDCl3): δ = 5.97–5.86 (m,
= 7.8 Hz, 1 H, CH-CO], 3.35 [d, J(H,H) = 7.8 Hz, 1 H, CH-CO], 2 H, CH=CH2 and CH=CH), 5.53 [dd, J(H,H) = 11.6 and 1.1 Hz,
2.91 (s, 3 H, CH3) ppm. 13C NMR (75 MHz, CDCl3): δ = 175.2
(C), 175.1 (C), 133.0 (CH), 130.5 (CH), 125.6 (CH), 119.1 (CH2),
79.4 (CH), 79.1 (C), 70.7 (CH2), 65.9 (CH2), 53.5 (CH), 50.4 (CH),
1 H, CH=CH], 5.38 [dt, J(H,H) = 17.2 and 1.0 Hz, 1 H, CH2=CH],
5.22 [dt, J(H,H) = 11.3 and 1.0 Hz, 1 H, CH2=CH], 4.67–4.63 (m,
1 H, CH-CH=CH2), 3.56 (s, 2 H, CH-CO), 2.23–2.06 (m, 2 H,
25.4 (CH3) ppm. HRMS (ESI): m/z: calcd. for C13H15NO4 + H: CH2), 1.91–1.64 (m, 5 H, CH2), 1.57–1.50 (m, 1 H, CH2) ppm. 13
C
250.1079 [M+ + H]; found 250.1077.
NMR (75 MHz, CDCl3): δ = 170.8 (C), 168.7 (C), 136.5 (CH),
136.2 (CH), 134.0 (CH), 118.4 (CH2), 87.7 (C), 80.5 (CH), 59.0
(CH), 53.5 (CH), 31.6 (CH2), 27.0 (CH2), 26.3 (CH2), 23.0 (CH2)
ppm.
(1S,3ЈR,3aЈR,6aЈS)-5Ј-Methyl-3Ј-vinyl-3Ј,3aЈ-dihydrospiro[cyclo-
pent[2]ene-1,1Ј-furo[3,4-c]pyrrole]-4Ј,6Ј(5ЈH,6aЈH)-dione (18): Ac-
cording to the general procedure for metathesis, the title compound
was isolated as a colorless oil (90%). 1H NMR (300 MHz, CDCl3):
δ = 6.00 [dt, J(H,H) = 5.6 and 2.4 Hz, 1 H, CH=CH], 5.92 [ddd,
(1S,4R)-Diisopropyl 1-{(E)-8-[(1R,4S)-2,3-Bis(isopropoxycarbonyl)-
7-oxa-2,3-diazabicyclo[2.2.1]hept-5-en-1-yl]oct-4-enyl}-7-oxa-2,3-di-
J(H,H) = 17.2, 10.5 and 5.8 Hz, 1 H, CH=CH2], 5.57 [dt, J(H,H) azabicyclo[2.2.1]hept-5-ene-2,3-dicarboxylate (28): According the
= 5.6 and 2.1 Hz, 1 H, CH=CH], 5.35 [d, J(H,H) = 17.2 Hz, 1 H, general procedure for metathesis, the title compound was isolated
1
CH2=CH], 5.20 [d, J(H,H) = 10.5 Hz, 1 H, CH2=CH], 4.50 [t, as a yellow oil (36%). H NMR (300 MHz, CDCl3): δ = 6.98 (s br,
J(H,H) = 5.8 and 1.0 Hz, 1 H, CH-O], 3.34 (m, 2 H, CH2-C-O),
2.93 (s, 3 H, CH3), 2.49–2.27 (m, 2 H, CH-CH2-CH2), 2.10 [ddd,
J(H,H) = 13.7, 8.1 and 4.6 Hz, 1 H, CH-CO], 1.77 [ddd, J(H,H) =
2 H, CH=CH), 6.11 (s br, 2 H, CH=CH), 5.88 [d, J(H,H) = 3.1 Hz,
2 H, CH-O], 5.34–5.32 (m, 2 H, CH=CH), 4.94–4.86 [m, 4 H,
CH(CH3)2], 2.49 [t, J(H,H) = 7.6 Hz, 4 H, C-CH2], 1.97–1.93 (m,
13.7, 8.1 and 4.6 Hz, 1 H, CH-CO] ppm. 13C NMR (75 MHz, 4 H, CH-CH2), 1.60 [quint, J(H,H) = 7.1 Hz, 4 H, CH2-CH-CH2],
CDCl3): δ = 177.1 (C), 176.1 (C), 137.6 (CH), 136.7 (CH), 134.2
1.20 [d, J(H,H) = 7.1 Hz, 12 H, CH(CH3)2], 1.17 [d, J(H,H) =
(CH), 117.9 (CH2), 96.3 (C), 80.3 (CH), 54.3 (CH), 53.1 (CH), 32.7 7.1 Hz, 12 H, CH(CH3)2] ppm. 13C NMR (75 MHz, CDCl3): δ =
(CH2), 31.8 (CH2), 25.3 (CH3) ppm. HRMS (ESI): m/z: calcd. for 153.6 (C), 145.4 (C), 130.6 (CH), 130.1 (CH), 106.8 (CH), 105.4
for C13H15NO3 + H: 234.1130 [M+ + H]; found 234.1132.
(CH), 71.8 (CH), 70.4 (CH), 32.2 (CH2), 28.0 (CH2), 27.8 (CH2),
22.4 (CH3), 22.2 (CH3) ppm. HRMS (ESI): m/z: calcd. for
C32H48N4O10 + Na: 671.3268 [M+ + Na]; found 671.3260.
(1S,3ЈR,3aЈS,6aЈR)-5Ј-Methyl-3Ј-vinyl-3Ј,3aЈ-dihydrospiro[cyclo-
pent[2]ene-1,1Ј-furo[3,4-c]pyrrole]-4Ј,6Ј(5ЈH,6aЈH)-dione (20): Fol-
lowing the general procedure for metathesis, the title compound
was isolated as a colorless oil (60%). 1H NMR (300 MHz, CDCl3):
δ = 6.11 [dt, J(H,H) = 5.7 and 2.3 Hz, 1 H, CH=CH], 5.84 [ddd,
J(H,H) = 17.1, 10.4 and 6.8 Hz, 1 H, CH=CH2], 5.62 [dt, J(H,H) isolated as a white solid (93%). H NMR (300 MHz, CDCl3): δ =
= 5.7 and 2.3 Hz, 1 H, CH=CH], 5.35 [dt, J(H,H) = 17.1 and 7.42–7.29 (m, 3 H, HPh), 7.26–7.14 (m, 2 H, HPh), 5.93 [dt, J(H,H)
1.2 Hz, 1 H, CH2=CH], 5.24 [dt, J(H,H) = 10.4 and 1.2 Hz, 1 H, = 10.2 and 2.3 Hz, 1 H, C-CH=CH], 5.84–5.75 (m, 2 H, Me-
CH2=CH], 4.48 [t, J(H,H) = 7.2 Hz, 1 H, CH-O], 3.39 [t, J(H,H) CH=CH and CH=CH-C), 5.51 [ddq, J(H,H) = 15.2, 6.8 and
= 7.6 Hz, 1 H, CH2-C-O], 3.16 [d, J(H,H) = 7.6 Hz, 1 H, CH2-C- 1.6 Hz, 1 H, CH=CH-Me], 4.61 [t, J(H,H) = 5.8 Hz, 1 H, CH-O],
(1S,3R,3aR,6aS)-5-Phenyl-3-[(E)-prop-1-enyl]-2Ј,3,3a,6Ј-tetrahydro-
spiro[furo[3,4-c]pyrrole-1,3Ј-pyran]-4,6(5H,6aH)-dione (32): Accord-
ing to the general procedure for metathesis, the title compound was
1
O], 2.90 (s, 3 H, CH3), 2.49–2.41 (m, 2 H, CH-CH2-CH2), 2.10–
2.01 (m, 1 H, CH-CO), 1.96–1.88 (m, 1 H, CH-CO) ppm. 13C
NMR (75 MHz, CDCl3): δ = 175.6 (C), 175.1 (C), 137.3 (CH),
4.05 [qt, J(H,H) = 9.2 and 2.4 Hz, 2 H, CH-CH2-O], 3.89 [d,
J(H,H) = 11.9 Hz, 1 H, CH-CO], 3.75 [dd, J(H,H) = 11.9 and
0.7 Hz, 1 H, CH-CO], 3.43 [dd, J(H,H) = 9.2 and 4.9 Hz, 1 H, C-
132.8 (CH), 130.0 (CH), 118.8 (CH2), 95.3 (C), 78.7 (CH), 54.8 CH2-O], 3.35 [d, J(H,H) = 9.2 Hz, 1 H, C-CH2-O], 1.67 [dd,
(CH), 50.2 (CH), 36.9 (CH2), 31.1 (CH2), 25.0 (CH3) ppm. HRMS
(ESI): m/z: calcd. for C13H15NO3 + H: 234.1130 [M+ + H]; found
234.1136.
J(H,H) = 6.5 and 0.8 Hz, 1 H, CH3] ppm. 13C NMR (75 MHz,
CDCl3): δ = 175.3 (C), 173.0 (C), 131.5 (C), 130.5 (CH), 130.1
(CH), 129.8 (CH), 129.5 (CH), 129.3 (CH), 128.8 (CH), 128.0
(CH), 126.4 (CH), 80.8 (CH), 79.2 (C), 68.0 (CH2), 65.0 (CH2),
53.9 (CH), 53.1 (CH), 17.8 (CH3) ppm. HRMS (ESI): m/z: calcd.
for C19H19NO4 + Na: 348.1212 [M+ + Na]; found 348.1201.
(1S,3R,3aR,6aS)-5-Phenyl-1Ј-tosyl-3-vinyl-2Ј,3,3a,6Ј-tetrahydro-
1ЈH-spiro[furo[3,4-c]pyrrole-1,3Ј-pyridine]-4,6(5H,6aH)-dione (22):
Following the general procedure for metathesis, the title compound
1
was isolated as a white solid (69%). H NMR (300 MHz, CDCl3):
Dispiro Compound 34: Following the general procedure for metath-
δ = 7.56 [d, J(H,H) = 8.2 Hz, 2 H, HTs], 7.43–7.34 (m, 3 H, HPh),
esis, the title compound was isolated as a white solid (58%). 1H
7.23–7.19 (m, 4 H, HPh and HTs), 5.97–5.86 (m, 1 H, CH=CH2), NMR (300 MHz, CDCl3): δ = 7.50–7.46 (m, 2 H, HPh), 7.44–7.39
5.83–5.79 (m, 1 H, CH=CH), 5.68 [d, J(H,H) = 10.1 Hz, 1 H, (m, 1 H, HPh), 7.34–7.30 (m, 2 H, HPh), 5.99 [dt, J(H,H) = 10.2 and
CH=CH], 5.33 [d, J(H,H) = 17.2 Hz, 1 H, CH2=CH], 5.20 [d, 3.6 Hz, 2 H, CH2-CH=CH], 5.66 [dt, J(H,H) = 10.2 and 2.0 Hz, 2
J(H,H) = 10.4 Hz, 1 H, CH2=CH], 4.78 [t, J(H,H) = 5.1 Hz, 1 H,
H, C-CH=CH], 3.51 (s, 2 H, CH-CO), 2.13–2.07 (m, 4 H, CH2),
CH-O], 3.89–3.83 (m, 1 H, CH2-NTs), 3.66 [d, J(H,H) = 12.4 Hz, 2.03–1.96 (m, 4 H, CH2) 1.92–1.81 (m, 4 H, CH2) ppm. 13C NMR
Eur. J. Org. Chem. 2010, 937–943
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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