TY - JOUR
T1 - Reactions of coordinated cyclic polyolefins. A novel perispecific Diels-Alder reaction of tricarbonyl(η4-cycloheptatriene)iron and (carbomethoxy)maleic anhydride controlled by secondary orbital overlap
AU - Goldschmidt, Zeev
AU - Antebi, Shlomo
AU - Gottlieb, Hugo E.
AU - Cohen, Drora
AU - Shmueli, Uri
AU - Stein, Zafra
N1 - Funding Information:
We thank Mrs. Sima Alfi for her assistance in the experimental work. Support by the Planning and Grant Committee of the Council for Higher Education for the purchase of the Bruker AM300 NMR spectrometer, and financial assistance from the Andre Narboni and Leon Recanati Scholarship Funds (to S-A.) are gratefully acknowledged.
PY - 1985/3/12
Y1 - 1985/3/12
N2 - The cycloaddition reactions of (carbomethoxy)maleic anhydride (CMA) with (η4-cycloheptatriene)Fe(CO)3 and with uncoordinated cycloheptatriene were investigated. Both reactions are highly stereospecific and give single Diels-Alder adducts. The structure of the metal-bonded adduct X was determined by single-crystal X-ray diffraction. A full analysis of the 1H and 13C NMR spectra of X is described. The corresponding uncomplexed adduct XI was obtained by Diels-Alder reaction of CMA with norcaradiene. The unusual Diels-Alder periselectivity and the stereochemical consequences of the 4 + 2 cycloaddition to X are best rationalized in terms of a concerted reaction controlled by secondary orbital interactions in the transition state.
AB - The cycloaddition reactions of (carbomethoxy)maleic anhydride (CMA) with (η4-cycloheptatriene)Fe(CO)3 and with uncoordinated cycloheptatriene were investigated. Both reactions are highly stereospecific and give single Diels-Alder adducts. The structure of the metal-bonded adduct X was determined by single-crystal X-ray diffraction. A full analysis of the 1H and 13C NMR spectra of X is described. The corresponding uncomplexed adduct XI was obtained by Diels-Alder reaction of CMA with norcaradiene. The unusual Diels-Alder periselectivity and the stereochemical consequences of the 4 + 2 cycloaddition to X are best rationalized in terms of a concerted reaction controlled by secondary orbital interactions in the transition state.
UR - http://www.scopus.com/inward/record.url?scp=0008493564&partnerID=8YFLogxK
U2 - 10.1016/0022-328X(85)87196-5
DO - 10.1016/0022-328X(85)87196-5
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AN - SCOPUS:0008493564
SN - 0022-328X
VL - 282
SP - 369
EP - 381
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 3
ER -