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Volumn 44, Issue 41, 2005, Pages 6700-6704

Enantioselective thiourea-catalyzed acyl-Mannich reactions of isoquinolines

Author keywords

Asymmetric catalysis; Heterocycles; Hydrogen bonds; Mannich reaction; Urea derivatives

Indexed keywords

CATALYSIS; COMPLEXATION; NITROGEN COMPOUNDS; UREA ELECTRODES;

EID: 27444443731     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200502277     Document Type: Article
Times cited : (260)

References (65)
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    • see reference [3c], references cited therein
    • For representative examples, see reference [3c], references cited therein,
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    • see reference [3f]
    • b) for a diastereoselective variant that employs a chiral acyl chloride, see reference [3f].
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    • see reference [2b]
    • For enantioselective reactions catalyzed by chiral urea or thiourea compounds, see reference [2b]
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    • For representative examples of other classes of chiral hydrogen-bond-donor catalysts, see: a) E. J. Corey, M. J. Grogan, Org. Lett. 1999, 1, 157-160;
    • (1999) Org. Lett. , vol.1 , pp. 157-160
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    • and references therein
    • a) K. W. Bentley, Nat. Prod. Rep. 2004, 21, 395-424, and references therein;
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    • b) for a review of methods for the preparation of enantioenriched tetrahydroisoquinolines, see: M. Chrzanowska, M. D. Rozwadowska, Chem. Rev. 2004, 104, 3341-3370.
    • (2004) Chem. Rev. , vol.104 , pp. 3341-3370
    • Chrzanowska, M.1    Rozwadowska, M.D.2
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    • note
    • A preliminary survey of ketone enolates did not yield satisfactory results; for example, 2-(trimethylsilyloxy)propene underwent addition to isoquinoline in the presence of TrocCl and 1 to yield the corresponding dihydroisoquinoline in 14% ee (unoptimized).
  • 58
    • 27444447317 scopus 로고    scopus 로고
    • note
    • A list of solvents and other catalysts tested may be found in the Supporting Information.
  • 59
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    • University of Göttingen, Germany
    • 2 (SHELXL-97); all non-hydrogen atoms were refined anisotropically; the positions of hydrogen atoms were found by difference Fourier methods and refined isotropically. CCD-275454 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
    • (1997) SHELXL-97, Program for the Solution of Crystal Structures
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  • 60
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    • A neutral chloroamide structure, rather than an ion pair, may represent a more accurate depiction of the bonding interactions in N-acyliminium chlorides in nonpolar organic solvents (for an NMR spectroscopic study that supports this assertion, see: A. K. Bose, G. Spiegelman, M. S. Manhas, Tetrahedron Lett. 1971, 3167-3170). Calculations that use the density-functional theory (Chemical Equation Presented) (B3LYP/6-31G + + (d,p)) predict substantial chloroamide character for N-acylisoquinolinium chloride
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    • Bose, A.K.1    Spiegelman, G.2    Manhas, M.S.3
  • 61
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    • unpublished results
    • (M. S. Taylor, E. N. Jacobsen, unpublished results), and the strong dependence of enantioselectivity upon solvent polarity observed in both acyl-Mannich and acyl-Pictet-Spengler reactions may be a reflection of the importance of the pairing of the N-acyliminium ions in these processes. These reactions are also subject to dramatic leaving-group effects upon reactivity and enantioselectivity, a phenomenon that seems difficult to reconcile with a fully ionized N-acyliminium ion as the reactive species. The possibility that 1 activates intermediate chloroamides toward substitution reactions by hydrogen-bonding interactions with the carbonyl group represents an intriguing, albeit speculative, mechanistic hypothesis that is consistent with these observations.
    • Taylor, M.S.1    Jacobsen, E.N.2
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    • For a discussion of the crystallization and cocrystallization of urea compounds directed by bifurcated hydrogen-bond interactions, see: a) M. C. Etter, T. W. Panunto, J. Am. Chem. Soc. 1988, 110, 5896-5897;
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    • note
    • Transesterification of the resulting product permitted the absolute configuration to be assigned (see the Supporting Information for details).


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.