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Volumn 75, Issue 7, 2010, Pages 2357-2368

Asymmetric synthesis of 1,3-diamines by diastereoselective reduction of enantiopure n-tert-butanesulfinylketimines: unusual directing effects of the ortho-substituent

Author keywords

[No Author keywords available]

Indexed keywords

ASYMMETRIC SYNTHESIS; CYCLIC TRANSITIONS; DIASTEREOSELECTIVE REDUCTION; ENANTIOPURE; FACIAL SELECTIVITY; KETIMINES;

EID: 77950325888     PISSN: 00223263     EISSN: 15206904     Source Type: Journal    
DOI: 10.1021/jo100173f     Document Type: Article
Times cited : (30)

References (70)
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    • Supporting Information
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    • Stabilization of the E-isomer in β by the intramolecular hydrogen bond between the β-hydroxy group and the oxygen of sulfinyl imine has been suggested; see ref 8c.
    • Stabilization of the E-isomer in β by the intramolecular hydrogen bond between the β-hydroxy group and the oxygen of sulfinyl imine has been suggested; see ref 8c.
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    • 3-d at -15 °C, the amount of major diastereomer of 4a was 96.8%.
    • 3-d at -15 °C, the amount of major diastereomer of 4a was 96.8%.
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    • A protons in Z-isomers were constantly shifted downfield Δδ =
    • A by the phenyl ring. See the Supporting Information (Table S1, page S11) for details.
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    • Related diaryl sulfinylketimines were obtained as a rapidly interconverting mixtures of Z- and E-isomers; see ref 8b.
    • Related diaryl sulfinylketimines were obtained as a rapidly interconverting mixtures of Z- and E-isomers; see ref 8b.
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    • 3-d has been determined for structurally related p-toluenesulfinylketimines. (a) Di-(p-tolyl)methylenep- toluenesulfinamide, 15 kcal/mol (62.8 kJ/mol)
    • 3-d has been determined for structurally related p-toluenesulfinylketimines. (a) Di-(p-tolyl)methylenep- toluenesulfinamide, 15 kcal/mol (62.8 kJ/mol): Annunziata, R.; Cinquini, M.; Cozzi, F. J. Chem. Soc., Perkin Trans. 11982, 339.
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    • Diphenylmethylene benzenesulfinamide, 14.1 kcal/mol (59.0 kJ/mol)
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    • c = 2.22Δv and the Eyring equation(k = 1); see ref 20b.
    • c = 2.22Δv and the Eyring equation(k = 1); see ref 20b.
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    • 8 at -15 °C (see Table 3).
    • 8 at -15 °C (see Table 3).
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    • Cyclic six-membered transition state has been proposed in the reduction of sulfinylketimines with DIBAL: (a)
    • Cyclic six-membered transition state has been proposed in the reduction of sulfinylketimines with DIBAL: (a) Hose, D. R. J.; Mahon, M. F.; Molloy, K. C.; Raynham, T.; Wills, M. J. Chem. Soc., Perkin Trans. 1 1996, 691.
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    • Ref 12.
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    • Atomic charge calculations have demonstrated considerable negative charge on oxygen in sulfinylimines
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    • note
    • 3 or DIBAL to the anion to afford an amidometallohydride prior to the H transfer is conceivable. The observed correlation with E/Z ratio of starting (E)-4a suggests an increased barrier for E/Z interconversion for the anion, which slows down the rate of equilibration on the reduction time scale.
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    • 4 (reft 8g and 8i)
    • 4 (reft 8g and 8i).


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.