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Volumn 2, Issue 1, 1996, Pages 88-97

Alkenyl fischer carbene complexes and α,β-unsaturated imine derivatives: Synthesis of azepines and mechanistic NMR studies

Author keywords

Azadienes; Azepines; Cycloadditions; Fischer carbenes complexes; Reaction mechanisms

Indexed keywords

AZADIENES; AZEPINES; CYCLOADDITIONS; FISCHER CARBENES; REACTION MECHANISM;

EID: 0010704461     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.19960020116     Document Type: Article
Times cited : (55)

References (88)
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    • the [3 + 3] annulation of alkynylcarbene tungsten complexes with an analogous azadiene leading to the pyridine ring is known
    • b) the [3 + 3] annulation of alkynylcarbene tungsten complexes with an analogous azadiene leading to the pyridine ring is known: R. Aumann, K. Roths, M. Grehl, Synlett 1993, 669.
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    • Carbenes derived from (-)-8-phenylmenthol gave slightly higher d.e.'s but much poorer chemical yields. For the preparation of these complexes, see
    • Carbenes derived from (-)-8-phenylmenthol gave slightly higher d.e.'s but much poorer chemical yields. For the preparation of these complexes, see: J. Barluenga, J. M. Montserrat, J. Flórez, S. García-Granda, E. Martín, Chem. Eur. J. 1995, 1, 236-242.
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    • note
    • To our delight the reduction of the oxime is effected exclusively by this methyl-carbene, thus avoiding to consume excess of the chiral carbene 11.
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    • i) For synthesis of unbranched ω-functionalized aldehydes by hydroformylation of functionalized olefins, see: G. D. Cuny, S. L. Buchwald, J. Am. Chem. Soc. 1993, 115, 2066.
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    • 2)/3. Total number of parameters 273. Further details of the crystal structure investigation may be obtained from the director of the Cambridge Crystallographic Data Centre, 12 Union Road, GB-Cambridge, CB21EZ (UK), on quoting the full journal citation.
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    • Fischer and Dötz have invoked a 1,2-pentacarbonylmetal migration for the cyclodimerization of alkynylcarbene complexes promoted by aryllithium and diethylzinc, respectively. See
    • Fischer and Dötz have invoked a 1,2-pentacarbonylmetal migration for the cyclodimerization of alkynylcarbene complexes promoted by aryllithium and diethylzinc, respectively. See: a) H. Fischer, T. Meisner, J. Hofmann, Chem. Ber. 1990, 123, 1799;
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    • note
    • The NMR characterization was carried out at -80°C in order to slow down the rate of decomposition to other compounds.
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    • note
    • Compound A can be mantained inaltered over 24 h at -80°C.
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    • note
    • 8]THF and only about a 30 % of A is formed in 2 h, i.e., an equilibrium between A and the starting materials is established. At -40°C the reaction can not be stopped at stage A and the mixture of complexes B and C is obtained.
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    • note
    • 13C HMQC, and HMBC correlation spectra.
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    • 2 as solvent.
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    • note
    • NMR studies involving α,β-unsaturated oximes and tungsten alkenyl Fischer carbenes are still to be carried out.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.