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

Zeev Goldschmidt; Shlomo Antebi; Hugo E. Gottlieb; Drora Cohen; Uri Shmueli; Zafra Stein

doi:10.1016/0022-328x(85)87196-5

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

Zeev Goldschmidt, Shlomo Antebi, Hugo E. Gottlieb, Drora Cohen, Uri Shmueli, Zafra Stein

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

14 Scopus citations

Abstract

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.

Original language	English
Pages (from-to)	369-381
Number of pages	13
Journal	Journal of Organometallic Chemistry
Volume	282
Issue number	3
DOIs	https://doi.org/10.1016/0022-328x(85)87196-5
State	Published - 12 Mar 1985

Bibliographical note

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.

Funding

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.

Funders	Funder number
Council for Higher Education

Access to Document

10.1016/0022-328x(85)87196-5

Cite this

Goldschmidt, Z., Antebi, S., Gottlieb, H. E., Cohen, D., Shmueli, U., & Stein, Z. (1985). 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. Journal of Organometallic Chemistry, 282(3), 369-381. https://doi.org/10.1016/0022-328x(85)87196-5

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title = "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",

abstract = "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.",

author = "Zeev Goldschmidt and Shlomo Antebi and Gottlieb, {Hugo E.} and Drora Cohen and Uri Shmueli and Zafra Stein",

note = "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.",

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doi = "10.1016/0022-328x(85)87196-5",

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Goldschmidt, Z, Antebi, S, Gottlieb, HE, Cohen, D, Shmueli, U & Stein, Z 1985, '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', Journal of Organometallic Chemistry, vol. 282, no. 3, pp. 369-381. https://doi.org/10.1016/0022-328x(85)87196-5

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. / Goldschmidt, Zeev; Antebi, Shlomo; Gottlieb, Hugo E. et al.
In: Journal of Organometallic Chemistry, Vol. 282, No. 3, 12.03.1985, p. 369-381.

Research output: Contribution to journal › Article › peer-review

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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

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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.

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