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DOI: 10.1055/s-0029-1218574
Carbon-Carbon Double-Bond Isomerization and Diels-Alder Reaction of Dimethyl 5-Methylene-4-isopropylidene-2-cycloheptene-1,1-dicarboxylate with Dienophiles
Publikationsverlauf
Publikationsdatum:
11. Dezember 2009 (online)
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Abstract
Tricyclic compounds were obtained as a single diastereomer via carbon-carbon double-bond isomerization-Diels-Alder reaction of dimethyl 5-methylene-4-isopropylidene-2-cycloheptene-1,1-dicarboxylate with dienophiles under the catalysis of [RhCl(cod)2]2/dppe/AgOTf. Further experiments provided the proof of isomerization of carbon-carbon double bond. Meanwhile a sequential double Diels-Alder reaction took place without carbon-carbon double-bond isomerization when 4-phenyl-4H-1,2,4-triazole-3,5-dione used as a dienophile.
Key words
Diels-Alder reactions - isomerizations - rhodium - stereoselectivity - carbocycles
- Supporting Information for this article is available online:
- Supporting Information
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References and Notes
Crystal Data for
Compound 4a
C21H27NO6, MW = 389.44,
monoclinic, Pc, final R indices
[I > 2σ(I)], R1 = 0.0549, wR2 = 0.1248, R indices (all data): R1 = 0.0633, wR2 = 0.1299, a = 13.7051
(13) Å, b = 11.8187
(11) Å, c = 12.9999
(12) Å, β = 103.869
(2)˚, V = 2044.3
(3) ų, T = 293
(2) K, Z = 4,
reflections collected/unique: 11758/4448 (R
int = 0.1361),
number of observations [>2σ(I)] 3626, parameters, 531. Supplementary crystallographic
data have been deposited at the Cambridge Crystallographic Data
Centre: CCDC 635123.
Crystal Data for
4e
C23H25N3O6, MW = 439.46,
triclinic, P-1, final R indices
[I > 2σ(I)], R1 = 0.0394, wR2 = 0.1111, R indices (all data): R1 = 0.0498, wR2 = 0.1212, a = 8.4388
(4) Å, b = 8.5666 (4) Å, c = 16.3077
(7) Å, α = 99.1060
(10)˚, β = 100.0250 (10)˚, γ = 105.3230
(10)˚, V = 1093.44 (9) ų, T = 296 (2) K, Z = 2. Reflections
collected/unique: 12810/ 3839 (R
int = 0.0204),
number of observations [>2σ(I)] 3118, parameters, 289. Supplementary
crystallographic data have been deposited at the Cambridge Crystallographic
Data Centre: CCDC 750106.
Crystal Data for
7
C33H34Cl4N6O8 (M + 2CH2Cl2), MW = 784.46,
monoclinic, P2 (1)/c, final R indices [I > 2σ(I)], R1 = 0.0827, wR2 = 0.2345, R indices (all data): R1 = 0.1191, wR2 = 0.2521, a = 15.8125
(15) Å, b = 11.7056
(11) Å, c = 19.5084
(18) Å, β = 93.543
(2)˚, V = 3604.0(6) ų, T = 293 (2)
K, Z = 4.
Reflections collected/unique: 18430/6687 (R
int = 0.1120),
number of observations [>2σ(I)] 3630, parameters, 464. Supplementary
crystallographic data have been deposited at the Cambridge Crystallographic
Data Centre: CCDC 738018.