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Volumn 349, Issue 4-5, 2007, Pages 567-582

Enantioselective ring opening of epoxides with silicon tetrachloride in the presence of a chiral lewis base: Mechanism studies

Author keywords

Asymmetric catalysis; C C bond formation; Cross coupling; Enzyme catalysis; Homogeneous catalysis

Indexed keywords


EID: 34547311382     PISSN: 16154150     EISSN: 15213897     Source Type: Journal    
DOI: 10.1002/adsc.200600551     Document Type: Article
Times cited : (60)

References (94)
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    • For leading references of enantioselective ring opening of epoxides, see: a
    • For leading references of enantioselective ring opening of epoxides, see: a) L. E. Martinez, J. L. Leighton, D. H. Carsten, E. N. Jacobsen, J. Am. Chem. Soc. 1995, 117, 5897;
    • (1995) J. Am. Chem. Soc , vol.117 , pp. 5897
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    • For a lanthanide-catalyzed addition of anilines to meso epoxides see
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    • The utility of this transformation, however, pales in comparison to the impact of the hydrolytic kinetic reso-lution of racemic epoxides which uses the cobalt salen catalyst or oligomeric/polymeric versions thereof in conjunction with water; a M. Tokunaga, J. F. Larrow, F. Kakiuchi, E. N. Jacobsen, Science 1997, 277, 936;
    • The utility of this transformation, however, pales in comparison to the impact of the hydrolytic kinetic reso-lution of racemic epoxides which uses the cobalt salen catalyst or oligomeric/polymeric versions thereof in conjunction with water; a) M. Tokunaga, J. F. Larrow, F. Kakiuchi, E. N. Jacobsen, Science 1997, 277, 936;
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    • Silicon tetrafluoride has been used together with Hünig base to open epoxides: M. Shimizu, H. Yoshioka Tetrahedron Lett. 1988, 29, 4101.
    • Silicon tetrafluoride has been used together with Hünig base to open epoxides: M. Shimizu, H. Yoshioka Tetrahedron Lett. 1988, 29, 4101.
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    • for a correction of several erroneous reports in the literature, see;
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    • Background reactions were performed with freshly distilled chlorosilanes and only when<5% conversion was detected at room temperature was the chlorosilane used for catalyzed reactions
    • Background reactions were performed with freshly distilled chlorosilanes and only when<5% conversion was detected at room temperature was the chlorosilane used for catalyzed reactions.
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    • Unfortunately, all attempts to study the kinetic behavior of the epoxide opening reaction of 2 in the presence of the chiral catalyst (R)-1 were thwarted by irreproducibility, most likely from the extreme water sensitivity of the reaction.
    • Unfortunately, all attempts to study the kinetic behavior of the epoxide opening reaction of 2 in the presence of the chiral catalyst (R)-1 were thwarted by irreproducibility, most likely from the extreme water sensitivity of the reaction.
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    • For discussion of non-linear effects, the use of enantiomeric excess (ee) is preferred. For a discussion of the relative merits of er vs. ee, see: a) H. B. Kagan, Recl. Trav. Chem. Pays-Bas 1995, 114, 203;
    • For discussion of non-linear effects, the use of enantiomeric excess (ee) is preferred. For a discussion of the relative merits of er vs. ee, see: a) H. B. Kagan, Recl. Trav. Chem. Pays-Bas 1995, 114, 203;
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    • This hypothesis finds analogy in the dual role played by the chromium-salen complexes in Jacobsen's epoxide ring opening reactions, Ref, 15
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