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Volumn 17, Issue 23, 2011, Pages 6334-6337

Enantiocontrolled synthesis of β-branched α-amino acids by using CuI-catalyzed 1,4-addition of glycine imines to β-substituted gem-diactivated olefins

Author keywords

amino acids; asymmetric catalysis; conjugate addition; copper; glycinate imines

Indexed keywords

1 ,4-ADDITION; ASYMMETRIC CATALYSIS; ASYMMETRIC CONJUGATE ADDITION; CONJUGATE ADDITION; ELECTRON WITHDRAWING GROUP; ENANTIOCONTROL; GLYCINATE; MICHAEL ACCEPTORS; SCHIFF BASIS;

EID: 79958217048     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.201100374     Document Type: Article
Times cited : (26)

References (47)
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    • For general reviews on this strategy, see
    • For general reviews on this strategy, see
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    • For recent examples, see
    • For recent examples, see
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    • for the asymmetric Michael reaction of glycinate imines to β-substituted conjugated nitroalkenes, see
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    • For the synthesis of β-branched α-amino acids by asymmetric alkylation of glycinate imines with kinetic resolution of racemic secondary alkyl bromides, see
    • For the synthesis of β-branched α-amino acids by asymmetric alkylation of glycinate imines with kinetic resolution of racemic secondary alkyl bromides, see:, T. Ooi, D. Kato, K. Inamura, K. Ohmatsu, K. Maruoka, Org. Lett. 2007, 9, 3945.
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    • 3CN (see the Supporting Information)
    • 3CN (see the Supporting Information).
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    • The use of a very strong base such as KtBuO (2 equiv) resulted in complete conversion after 4 h at RT, although with poor diastereoselectivity (syn/anti=76:24) and no asymmetric induction
    • The use of a very strong base such as KtBuO (2 equiv) resulted in complete conversion after 4 h at RT, although with poor diastereoselectivity (syn/anti=76:24) and no asymmetric induction.
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    • Electric conductivities of various inorganic and organic bases, directly related to their ionization ability, has been measured in organic solvents to explain their different performance in metal-catalyzed cross-coupling reactions
    • Electric conductivities of various inorganic and organic bases, directly related to their ionization ability, has been measured in organic solvents to explain their different performance in metal-catalyzed cross-coupling reactions:, C.-T. Yang, Y. Fu, Y.-B. Huang, J. Yi, Q.-X. Guo, L. Liu, Angew. Chem. 2009, 121, 7534
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    • I loading from 5 mol % to 2.5 mol % (0.5 mmol scale) led to a slower reaction (12 h, RT) but still good yield (71 %), as well as good diastereo- (syn/anti=94:6) and enantiocontrol (91 % ee)
    • I loading from 5 mol % to 2.5 mol % (0.5 mmol scale) led to a slower reaction (12 h, RT) but still good yield (71 %), as well as good diastereo- (syn/anti=94:6) and enantiocontrol (91 % ee).
  • 37
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    • Screening of a number of other metal-chiral ligand combinations led to much poorer reactivity and/or diastero- and enantiocontrol, whereas tuning the steric and electronic properties of the glycinate pronucleophile by modification of the ester and imine moieties did not improve the results obtained with substrate 2 (see the Supporting Information for these studies). For the beneficial effect of altering the steric or electronic properties of the glycinate component in the reactivity and stereoselectivity, see
    • Screening of a number of other metal-chiral ligand combinations led to much poorer reactivity and/or diastero- and enantiocontrol, whereas tuning the steric and electronic properties of the glycinate pronucleophile by modification of the ester and imine moieties did not improve the results obtained with substrate 2 (see the Supporting Information for these studies). For the beneficial effect of altering the steric or electronic properties of the glycinate component in the reactivity and stereoselectivity, see
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    • See also reference [10 b]
    • Angew. Chem. Int. Ed. 2008, 47, 5613. See also reference [10 b].
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    • I-enolate complex as active nucleophile catalysts (see the Supporting Information for a tentative stereochemical model). For computational studies on this type of intermediate, see ref. [9 b]
    • I-enolate complex as active nucleophile catalysts (see the Supporting Information for a tentative stereochemical model). For computational studies on this type of intermediate, see ref. [9 b].
  • 42
    • 79958238156 scopus 로고    scopus 로고
    • 1: a=10.4954(3), b=13.5389(4), c=18.2447(5) Å) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via
    • 1: a=10.4954(3), b=13.5389(4), c=18.2447(5) Å) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via.
  • 43
    • 79958212106 scopus 로고    scopus 로고
    • 1: a=9.9427(3), b=16.9270(4), c=18.6029(5) Å) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via
    • 1: a=9.9427(3), b=16.9270(4), c=18.6029(5) Å) contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via.
  • 44
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    • The stereochemistry of the products of type 7 was established by NMR spectroscopy and by correlation with a known derivative (see the Supporting Information)
    • The stereochemistry of the products of type 7 was established by NMR spectroscopy and by correlation with a known derivative (see the Supporting Information).
  • 45
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    • This methodology has been recently described from racemic substrates
    • This methodology has been recently described from racemic substrates
  • 46
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    • For its application to the preparation of the indole framework of ambiguine G, see
    • R. Viswanathan, C. R. Smith, E. N. Prabhakaran, J. N. Johnston, J. Org. Chem. 2008, 73, 3040. For its application to the preparation of the indole framework of ambiguine G, see
    • (2008) J. Org. Chem. , vol.73 , pp. 3040
    • Viswanathan, R.1    Smith, C.R.2    Prabhakaran, E.N.3    Johnston, J.N.4


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