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DOI: 10.1055/s-2003-42127
CpRuCl(PPh3)2/MeI Catalyst System for the [2+2] Cycloaddition of Norbornenes with Disubstituted Alkynes
Publikationsverlauf
Publikationsdatum:
07. November 2003 (online)
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Abstract
CpRu(PPh3)2I generated in situ by mixing CpRu(PPh3)2Cl and methyl iodide catalyzed the [2+2] cycloaddition of norbornene (or norbornadiene) and disubtituted alkynes to afford functionalized cyclobutenes.
Key words
ruthenium catalyst - cycloaddition - alkynes - bicyclic alkenes - cyclobutenes
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References
Tenaglia, A.; Giordano, L. submitted for publication.
14The structure of CpRuI(PPh3)2 was secured by an X-ray analysis and deposited with the Cambridge Crystallographic Data Centre (CCDC 219110). The coordinates can be obtained, on request, from the Director, Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge, CB2, 1EZ, UK.
17Typical Procedure: A solution of CpRuCl(PPh3)2 (36.3 mg, 0.05 mmol) and methyl iodide (49.6 mg, 22 µL, 0.35 mmol) in dioxane (2 mL) was stirred for 10 min in a Schlenk tube under an Ar atmosphere. A solution of norbornene 1 (282 mg, 3 mmol) and alkyne (1 mmol) in dioxane (6 mL) was added and the mixture was heated at 90 °C until completion (TLC monitoring). Dioxane was evaporated in vacuo and the crude product was purified by SiO2 column chromato-graphy.
18All new compounds exhibited satisfactory 1H and 13C NMR and IR spectral data as well as satisfactory combustion analysis. The following physical data are representative:
Tricyclo[4.2.1.0
[2]
[5]
]non-3-ene-3,4-diyldimethanol 4a. White solid, Rf = 0.73 (CH2Cl2/MeOH 9/1). Mp 57-58 °C. IR (KBr): 3307, 2946, 1665 cm-1. 1H NMR (200 MHz, CDCl3): δ = 1.01 (m, 3 H), 1.51 (m, 3 H), 1.96 (m, 2 H), 2.31 (br s, 2 H), 2.84 (m, 2 H, OH), 4.11 (br s, 4 H). 13C NMR (50 MHz, CDCl3): δ = 28.1 (t), 30.3 (t), 33.6 (d), 46.3 (d), 58.7 (t), 140.2 (s). Anal. Calcd for C11H16O2: C, 73.30; H, 8.95. Found: C, 73.12; H, 8.84.
Tricyclo[4.2.1.0
[2]
[5]
]nona-3,7-diene-3,4-diyldimethanol 5a. White solid, Rf = 0.70 (CH2Cl2/MeOH 9/1). Mp 59-60 °C. IR (KBr): 3293, 3056, 2966, 1654 cm-1. 1H NMR (200 MHz, CDCl3): δ = 1.31 (br d, J = 9.0 Hz, 1 H), 1.43 (br d, J = 9.0 Hz, 1 H), 2.18 (br s, 2 H), 2.43 (br s, 2 H), 3.68 (m, 2 H, OH), 4.20 (br s, 4 H), 6.10 (t, J = 1.6 Hz, 2 H). 13C NMR (50 MHz, CDCl3): δ = 38.2 (d), 39.6 (t), 42.6 (d), 59.1 (t), 135.4 (d), 140.2 (s). Anal. Calcd for C11H14O2: C, 74.13; H, 7.92. Found: C, 73.93; H, 7.78.