TY - JOUR
T1 - Reactions of coordinated cyclic polyolefins. Regio- and stereo-specific cycloadditions of ketenes and tricarbonyl(η4-polyene)iron complexes. Structural evidence for a concerted 2 + 2 mechanism
AU - Goldschmidt, Zeev
AU - Antebi, Shlomo
AU - Cohen, Drora
AU - Goldberg, Israel
PY - 1984/10/2
Y1 - 1984/10/2
N2 - The cycloaddition of ketenes R1R2CCO (R1 = Me, R2 = Ph; R1 = R2 = Ph; R1 = Ph, R2 = p-tolyl) (III) and tricarbonyl(η4-cycloheptatriene)iron (II) at room temperature gave regiospecifically the cyclobutanones IV, in which the carbonyl is bonded to the uncoordinated terminal of the conjugated triene. Tricarbonyl(η4-cyclooctatetraene)iron, VI, similarly reacts with dipenylketene to give the regioisomeric cyclobutanone VIII. Single crystal X-ray analysis of tricarbonyl[(η-2,3,4,5)-9-methyl-9-phenylbicyclo[5.2.0]nonan-2,4-dien-8-one]iron (IVa) confirmed the presence of the phenyl group at the endo position, providing a stereochemical evidence for a concerted 2s + 2a cycloaddition mechanism. The adducts IV undergo cyclobutanone ring cleavage catalyzed by acid to give the isomeric ketones VII. The diaryl adducts (IVb and IVc) rearrange thermally to the σ,π-allylic complexes IX, which may also be obtained directly upon heating cycloheptatriene complex II and the diarylketenes.
AB - The cycloaddition of ketenes R1R2CCO (R1 = Me, R2 = Ph; R1 = R2 = Ph; R1 = Ph, R2 = p-tolyl) (III) and tricarbonyl(η4-cycloheptatriene)iron (II) at room temperature gave regiospecifically the cyclobutanones IV, in which the carbonyl is bonded to the uncoordinated terminal of the conjugated triene. Tricarbonyl(η4-cyclooctatetraene)iron, VI, similarly reacts with dipenylketene to give the regioisomeric cyclobutanone VIII. Single crystal X-ray analysis of tricarbonyl[(η-2,3,4,5)-9-methyl-9-phenylbicyclo[5.2.0]nonan-2,4-dien-8-one]iron (IVa) confirmed the presence of the phenyl group at the endo position, providing a stereochemical evidence for a concerted 2s + 2a cycloaddition mechanism. The adducts IV undergo cyclobutanone ring cleavage catalyzed by acid to give the isomeric ketones VII. The diaryl adducts (IVb and IVc) rearrange thermally to the σ,π-allylic complexes IX, which may also be obtained directly upon heating cycloheptatriene complex II and the diarylketenes.
UR - http://www.scopus.com/inward/record.url?scp=0008522758&partnerID=8YFLogxK
U2 - 10.1016/0022-328x(84)80549-5
DO - 10.1016/0022-328x(84)80549-5
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AN - SCOPUS:0008522758
SN - 0022-328X
VL - 273
SP - 347
EP - 359
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 3
ER -