Carbon-Carbon Double-Bond Isomerization and Diels-Alder Reaction of Dimethyl 5-Methylene-4-isopropylidene-2-cycloheptene-1,1-dicarboxylate with Dienophiles

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

References and Notes

• 1a Jacobsen EN. Pfaltz A. Yamamoto H. Comprehensive Asymmetric Catalysis   Vol. 1-3:  Springer; Berlin: 1999. 
• 1b Yamamoto H. Lewis Acids in Organic Synthesis   Vol. 1-2:  Wiley-VCH; New York: 2000. 
• 1c Kobayashi S. Jørgensen KA. Cycloaddition Reaction in Organic Synthesis   Wiley-VCH; New York: 2002. 
• 1d Jørgensen KA. Angew. Chem. Int. Ed.  2000,  39:  3558 
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9

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) Å^³, 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.

10

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) Å^³, 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.

11

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) Å^³, 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.