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Volumn 1, Issue 8, 1995, Pages 505-520

Stereoselective Homologation–Amination of Aldehydes by Addition of Their Nitrones to C‐2 Metalated Thiazoles—A General Entry to α‐Amino Aldehydes and Amino Sugars

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EID: 84989528916     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.19950010804     Document Type: Article
Times cited : (111)

References (186)
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    • Treatment of N‐benzyl nitrones derived from benzaldehyde and i‐butyraldehyde with 1a in ether at room temperature or under reflux failed to give the desired product. Instead unchanged starting material was recovered.
  • 109
    • 84989527696 scopus 로고    scopus 로고
    • Due to the limited solubility of the nitrone 2 in diethyl ether (about 20 mgmL −1), a mixture of diethyl ether/tetrahydrofuran in a 1:1 ratio was employed as solvent in multigram‐scale reactions (more than 2 g of 2).
  • 110
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    • A reversed ratio was quoted in our first report (ref. [14a]). owing to the opposite, but incorrect, structural assignment to the major stereoisomer. For a prompt correction, see ref. [14b].
  • 113
    • 84989590761 scopus 로고    scopus 로고
    • For stereochemical assignements, see the section below.
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    • The reaction of 2‐lithiothiazole (1b) with esters is well established. See: (a), J. Chem. Soc. Chem. Commun.
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    • Dondoni, A.1    Perrone, D.2    Merino, P.3
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    • Although 2‐lithiothiazole (1b) is represented for simplicity as a monomet having the metal covalently linked to C‐2, recent X‐ray crystallographic studies on a lithiated thiazole have shown a dimeric structure with the lithium positioned halfway between C‐2 and nitrogen. See
    • (1995) Angew. Chem. Int. Ed. , vol.34 , pp. 487-489
    • Boche, G.1    Hilf, C.2    Harms, K.3    Marsch, M.4    Lohrenz, M.J.C.W.5
  • 130
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    • The same conformation has been assumed to explain the stereoselection of cycloaddition reactions. See also ref. [16g].
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    • This selectivity has been observed in cycloaddition reactions as well. See:, J. Chem. Soc. Perkin Trans I
    • (1985) , pp. 2753-2761
    • Fray, M.J.1    Jones, R.H.2    Thomas, E.J.3
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    • 13C NMR spectra.
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    • 3‐based methodology to N‐benzyl hydroxylamines beating a 2‐furyl group afforded benzaldimines, which were hydrolyzed to amines on treatment with wet silica gel. In no instances was the formation of the isomeric ketimine observed, arising from the removal of the proton α to the furyl group (, Synthesis). Whether the same reaction pathway is also operative for reaction with 2‐thiazolyl‐substituted hydroxylamines is a subject under investigation in our laboratories
    • (1994) , pp. 1450-1456
    • Dondoni, A.1    Junquera, F.2    Merchan, F.L.3    Merino, P.4    Tejero, T.5
  • 143
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    • It is worth pointing out here that the stability of the thiazole ring under various reaction conditions provides another substantial advantage, which amply justifies the use of this heterocycle as a masked formyl group in this methodology. In contrast, the use of the 1,3‐dithiane ring appeared to be quite problematical. For instance, we have been unable to convert the N‐benzylhydroxylamine shown below to amine under the conditions employed for the thiazole analogue. (Formula Presented.)
  • 144
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    • For enquires regarding the X‐ray structure analysis, contact Professor V. Bertolasi at the address indicated.
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    • cis8.0 Hz; see ref. [13c].
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    • For a review on the synthesis and reactivity of Neu5Ac, see:, Synthesis
    • (1991) , pp. 583-593
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    • (1990)


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.