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Volumn 35, Issue 50, 1994, Pages 9465-9468

The tandem insertion of allyl carbenoids and aldehydes or ketones into zirconacyclopentanes: Variation of the allyl Moiety and functionalisation of the final carbon-zirconium bond

Author keywords

[No Author keywords available]

Indexed keywords

CYCLOPENTANE DERIVATIVE; ZIRCONIUM DERIVATIVE;

EID: 0028124817     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(00)78572-8     Document Type: Article
Times cited : (15)

References (30)
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  • 8
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    • Aldehyde insertion
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    • Copéret1    Negishi2    Xi3    Takahashi4
  • 14
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    • Elaboration of zirconacyclopentanes by sequential insertion of lithium chloroallylide and ketones or aldehydes
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    • Reaction of zirconocene dichloride with alkyllithiums or alkyl grignard reagents as a convenient method for generating a “zirconocene” equivalant and its use in zirconium-promoted cyclization of alkenes, alkynes, dienes, enynes, and diynes
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    • 2O reactions) to a mixture of the metallacycle (3 or 4), and the allyl precursor (1.2 eq).
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    • 13C NMR, IR, MS and either HRMS or elemental analysis. All yields are for isolated compounds based on the starting dienes 1 or 2. 10b and d were formed as 2 : 1 mixtures of diastereomers between the side chain and ring stereocentres.
  • 20
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    • Molecular structure of ((.ETA.5-C5H5)2Zr(CH2...C(CH3)...CH-CH2)-C(CH3)=C(CH3)) prepared by regioselective insertion of 2-butyne to Zr(.ETA.5-C5H5)2(isoprene).
    • The (E)-stereochemistry of 7a and 8a is certain (ref 3), that of the trisubstituted alkene analogues b – e is not, but is in accord with that assigned for lower homologues (formed by diene - alkene or diene - alkyne coupling on the metal), one of which has been proven by X-ray crystallography
    • (1982) Chemistry Letters , pp. 1979
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  • 21
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    • The ketone insertion products of 7a were erroneously assigned as the (E)-alkene adducts in our previous communication (ref 3). This must be corrected to (Z) on the basis of the carbon-13 shifts of the allylic carbons, and an 11Hz cis-coupling revealed by high field NMR studies on the benzophenone adduct.
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    • Regio- and stereochemistry in the sequential insertion of carbonyl compounds into zirconium-diene complexes
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    • 13C NMR signals - the ratios were not determined. The ratio of the four side chain isomers were obtained by integration of the distinct benzyl proton signals. The alkene signals gave the Z : E ratio of the erythro-isomers. The overall erythro : threo ratio was proven by ozonolysis / reduction to give the erythro and threo diols 20 and 21 which were identified by NMR studies on their acetonides, Although the threo-isomer was present as a 3 : 2 mixture of double bond isomers we did not determine which was the major.
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.