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Volumn 125, Issue 51, 2003, Pages 15878-15892

Intramolecular Hydroamination/Cyclization of Conjugated Aminodienes Catalyzed by Organolanthanide Complexes. Scope, Diastereo- and Enantioselectivity, and Reaction Mechanism

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Indexed keywords

LIGATION EFFECTS;

EID: 0346994917     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja036266y     Document Type: Article
Times cited : (194)

References (123)
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    • note
    • (b) Reference 7a.
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    • note
    • Hydroamination of 1,1-disubstituted alkenes has been reported by Molander;8i however, hydroamination of 1,2-disubstituted alkenes with the same catalyst was not successful.
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    • note
    • For example, the scope of enantioselective intramolecular hydroamination/cyclization by chiral organolanthanide was previously limited to monosubstituted alkenes, affording only methyl substituted chiral azacycles.
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    • note
    • 2)) is estimated to be - 12 kcal/mol (±0.6).
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    • note
    • Presumably, two possible conformers (pseudoequatorial or pseudoaxial propenyl) exist which interconvert slowly on the NMR time scale; therefore, some peaks appear as a pair.
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    • note
    • See the Supporting Information for aminodiene substrate synthesis.
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    • note
    • Hydroamination/cylization of monosubstituted allenylamines affords mixtures of endo- and exo-cyclization regioisomers, whereas 1,3-disubstituted allenylamines exclusively yield the exo-cyclization product. See ref 11b.
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    • Representative eight-coordinate effective ionic radii: La(III), 1.160 Å: Nd(III), 1.109 Å; Sm(III), 1.079 Å; Y(III), 1.019 Å; Yb(III), 0.985 Å; Lu(III), 0.977 Å. See: Shannon, R. D. Acta Crystallogr., Sect. A 1976, A32, 751-767.
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    • note
    • Relative stereochemistry confirmed by NOESY experiments and derivatization.
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    • and references therein for other recent syntheses
    • For the catalytic asymmetric synthesis of coniine via imine hydrosilylation, see: Reding, M. T.; Buchwald, S. L. J. Org. Chem. 1998, 63, 6344-6347 and references therein for other recent syntheses.
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    • Organolanthanide-catalyzed hydrophosphinations exhibit similar but more pronounced kinetic inhibition effects, depending upon the steric bulk of the product. See: Douglass, M. R.; Stern, C. L.; Marks. T. J. J. Am. Chem. Soc. 2001, 123, 10221-10238.
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    • note
    • Parameters in parentheses represent 3σ values derived from the least-squares fit.
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    • note
    • Methyl substitution leads to a destabilization of the proposed transition state C relative to R = H or Ph; however, a reversed H versus Ph substituent effect for two different lanthanide catalysts appears to imply competing steric effects as well.
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    • note
    • 1H NMR,9b and epimerization of chiral lanthanocene catalysts in the presence of amines.9a-c For other related examples, see footnote 38 in ref 10a.
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    • note
    • 2SiCp″(CpR*)Ln catalysts (Ln = Nd, Sm) reveal that the product resonances are often broadened after ∼1 half-life, which implies that the product heterocycles are significantly involved in coordination to/amine exchange with the chiral paramagnetic lanthanide amine-amido complexes.9b
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    • note
    • 3+ for aminoallene cyclizations.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.