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Volumn 13, Issue 6, 2011, Pages 1306-1309

Highly diastereo- and enantioselective aldol reaction of methyl α-isocyanoacetate: A cooperative catalysis approach

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EID: 79952602444     PISSN: 15237060     EISSN: 15237052     Source Type: Journal    
DOI: 10.1021/ol103104y     Document Type: Article
Times cited : (126)

References (67)
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    • For Au(I) catalysis, see:, For a Ag(I) catalysis, see: Tetrahedron Lett. 1991, 32, 2799 For a comprehensive review, see: ref 13.
    • For Au(I) catalysis, see: Ito, Y.; Sawamura, M.; Hayashi, T. J. Am. Chem. Soc. 1986, 108, 6405 For a Ag(I) catalysis, see: Hayashi, T.; Uozumi, Y.; Yamazaki, A. Tetrahedron Lett. 1991, 32, 2799 For a comprehensive review, see: ref 13.
    • (1986) J. Am. Chem. Soc. , vol.108 , pp. 6405
    • Ito, Y.1    Sawamura, M.2    Hayashi, T.3    Hayashi, T.4    Uozumi, Y.5    Yamazaki, A.6
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    • See the Supporting Information for more details.
    • See the Supporting Information for more details.
  • 58
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    • 2) resulted in catalysts with low enantioselectivities.
    • 2) resulted in catalysts with low enantioselectivities.
  • 59
    • 0003998388 scopus 로고    scopus 로고
    • Typical ionic radius for Cu(I) with a coordination number of 4 is 0.60 Å, whereas that of Co(II) is around 0.56 Å see:, 87 th ed.; CRC: Boca Raton, FL
    • Typical ionic radius for Cu(I) with a coordination number of 4 is 0.60 Å, whereas that of Co(II) is around 0.56 Å see: Handbook of Chemistry and Physics, 87 th ed.; CRC: Boca Raton, FL, 2006; pp 12 - 11.
    • (2006) Handbook of Chemistry and Physics , pp. 12-11
  • 60
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    • 2NEt), but metal iodides require amidine bases (i.e., DBU); see: Ref 19. A cooperative role of amidine bases in the asymmetric Co(II) catalysis has been recently reported; see: Kalow, J. A.; Doyle, A. G. J. Am. Chem. Soc. 2010, 132, 3268
    • (2010) J. Am. Chem. Soc. , vol.132 , pp. 3268
    • Kalow, J.A.1    Doyle, A.G.2
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    • Use of other metal salts and modified thiourea derivatives is currently under investigation.
    • Use of other metal salts and modified thiourea derivatives is currently under investigation.
  • 63
    • 79952578533 scopus 로고    scopus 로고
    • The anion-binding of thioureas to isocyanides under our cooperative catalysis could not be confirmed by NMR or IR due to the line-broadening caused by the multifunctional nature of our chiral metal complexes. However, our control experiments (Table 1, entries 14-17) clearly indicate the cooperative role of thiourea derivatives on enantioselectivity.
    • The anion-binding of thioureas to isocyanides under our cooperative catalysis could not be confirmed by NMR or IR due to the line-broadening caused by the multifunctional nature of our chiral metal complexes. However, our control experiments (Table 1, entries 14-17) clearly indicate the cooperative role of thiourea derivatives on enantioselectivity.
  • 64
    • 0001361008 scopus 로고
    • Tetrahedral Co(II) complexes are known to be blue, and octahedral Co(II) complexes are usually pink; see: Norwood, V. M., III; Morse, K. W. Inorg. Chem. 1987, 26, 284
    • (1987) Inorg. Chem. , vol.26 , pp. 284
    • Norwood III, V.M.1    Morse, K.W.2
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    • Oxazolines were isolated in <10% yields after 48 h (>20:1 dr and 5% ee).
    • Oxazolines were isolated in <10% yields after 48 h (>20:1 dr and 5% ee).
  • 67
    • 79952582637 scopus 로고    scopus 로고
    • -) provided racemic anti- 3a in 71% yield and 10:1 dr.
    • -) provided racemic anti- 3a in 71% yield and 10:1 dr.


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