[5+1] Cocyclization of (Cyclopropylmethylene)cyclopropanes and other Vinylcyclopropanes with Carbon Monoxide Catalyzed by Octacarbonyldicobalt [1]

Abstract

Vinylcyclopropanes react with octacarbonyldicobalt ­stoichiometrically under mild conditions to give cyclohex-3-enones in moderate to good yields (51-75%). Catalytic amounts of the cobalt­carbonyl complex or a rhodiumcarbonyl complex also ­mediate [5+1] cocyclizations of vinylcyclopropanes with carbon monoxide (under CO balloon pressure) to give cyclohex-3-enones in good yields (up to 95%).

cycloaddition - cobalt - transition metals

References

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For recent reviews on the Pauson-Khand reaction see:

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4d Brummond KM. Kent JL. Tetrahedron  2000,  56:  3263 

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13

Representative Procedure.
To a solution of octacarbonyldicobalt (17 mg, 0.05 mmol) in THF (10 mL) was added vinylcyclopropane 1a (108 mg, 1 mmol), and the mixture was heated at 60 °C for 12 h under an atmosphere of CO provided in a balloon. The cooled reaction mixture was diluted with Et₂O (20 mL) and stirred under air for 1 h. Filtration through a pad of Celite and purification by Kugelrohr distillation gave 2a (92 mg, 0.68 mmol, 68%) as a pale yellow oil. R _f = 0.22 (hexane-Et₂O 10:1). ¹H NMR (500 MHz, CDCl₃): δ = 1.11 (dd, J = 7.4, 4.0 Hz, 2 H), 1.35 (dd, J = 7.4, 4.0 Hz, 2 H), 1.47 (m, 3 H), 2.38 (m, 2 H), 2.49 (m, 2 H), 5.72 (m, 1 H). ¹³C NMR (125 MHz, CDCl₃): δ = 16.2 (cPr-C), 17.6 (CH₃), 22.5 (CH₂), 31.9 (C), 38.5 (CH₂), 120.0 (CH), 133.8 (C), 210.7 (CO). IR (neat): 3002, 2965, 2922, 2854, 1701, 1437, 1414, 1354, 1182, 1115, 1031, 950, 848, 668 cm^-1. MS: m/z = 137/136/135 (10/100/48) [M⁺], 121 (62) [M⁺ - Me], 185 (10), 93 (61), 79 (50), 77 (44). Anal. Calcd for C₉H₁₂O (136.2): C, 79.37; H, 8.88. Found: C, 79.22; H, 8.76.