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Volumn 10, Issue 21, 2004, Pages 5493-5506

Regioselective samarium diiodide induced couplings of carbonyl compounds with 1,3-diphenylallene and alkoxyallenes: A new route to 4-hydroxy-1-enol ethers

Author keywords

Allenes; Cyclopentanols; Enol ethers; Radical reactions; Samarium diiodide

Indexed keywords

CHEMICAL ANALYSIS; CHEMICAL REACTIONS; COMPOSITION; CONFORMATIONS; DERIVATIVES; SYNTHESIS (CHEMICAL);

EID: 8344247712     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/chem.200400418     Document Type: Article
Times cited : (26)

References (81)
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    • note
    • By analogy to the coupling of 8b with 12, this result can be explained by assuming that the sterically more demanding samarium alkoxy and tert-butyl groups of the intermediate ketyl radical are in equatorial positions before addition to 7.
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    • There has been no general success in replacing HMPA by less toxic cosolvents. In individual examples related additives (e.g. N-methylpyrrolidinone or other phosphoramide derivatives) were efficient, but unfortunately no rule has yet been recognized describing cases in which these additives are applicable. M. Berndt, S. Groß, A. Hölemann, H.-U. Reißig, unpublished results.
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    • 1H NMR spectra.
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    • Two equivalents of samarium diiodide are probably necessary for efficient generation of ketyl radical anions in high concentration.
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    • Owing to the interaction of the σ* orbital of the C-OMe bond with the π* orbital of the terminal double bond this moiety should be able to react with nucleophiles at the terminal carbon atom. In accordance with this electronic situation, cuprates add to C-3 of alkoxyallenes: I. Marek, A. Alexakis, P. Mangeney, J.-F. Normant, Bull. Soc. Chim. Fr. 1992, 729, 171-190.
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    • 1H NMR spectrum (E isomer: δ = 6.37; Z isomer: δ= 6.06).
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    • 18]HMPA have not been performed because of the high price of this reagent.
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    • and references therein
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    • note
    • The relative configuration of the two diastereomers could not be directly established by NMR experiments. The assignment was only possible by further transformation of 13 h into the corresponding γ-lactones (cf. 13b). See refs. [7,14]. The slight preference of the trans isomer can be rationalized by assuming that the sterically demanding samarium alkoxy and methyl groups prefer equatorial positions in the intermediate ketyl radical before adding to 12; however, since the methyl group is only a small substituent the preference for this conformation is not very large.
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.