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Volumn 71, Issue 4, 2006, Pages 1523-1536

Chiral phosphoramide-catalyzed enantioselective addition of allylic trichlorosilanes to aldehydes. Preparative studies with bidentate phosphorus-based amides

Author keywords

[No Author keywords available]

Indexed keywords

ALLYLATION; BIDENTATE PHOSPHORAMIDES; QUATERNARY CENTERS;

EID: 33644532245     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo052203h     Document Type: Article
Times cited : (121)

References (76)
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    • Denmark, S.E.1    Su, X.2
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    • Mahrwald, R., Ed.; Wiley-VCH: Weinheim, Chapter 7
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    • (2004) Modern Aldol Reactions , vol.2
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    • Monophosphoramides derived from 14 and 15 have provided excellent enantioselectivities in reactions with other chlorosilane species such as the aldol reaction of enoxytrichlorosilanes and epoxide-opening reactions (silicon tetrachloride). For aldol reaction, see: (a) Denmark, S. E.; Stavenger, R. A. Acc. Chem. Res. 2000, 33, 432-440.
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    • Denmark, S.E.1    Stavenger, R.A.2
  • 32
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    • These bisphosphoramides have been employed with good success in aldol addition reactions of enoxytrichlorosilanes (14) and Mukaiyama-type aldol addition with silicon tetrachloride (15). See: (a) Denmark, S. E.; Pham, S. M. J. Org. Chem. 2003, 68, 5045-5055.
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  • 34
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    • For a recent X-ray crystal structure of a bis-N-oxide complex of silicon tetrachloride, see: Denmark, S. E.; Fan, Y.; Eastgate, M. D. J. Org. Chem. 2005, 70, 5235-5248.
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    • (2005) Adv. Synth. Catal. , vol.347 , pp. 1473-1482
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    • note
    • The crystallographic coordinates of 36 have been deposited with the Cambridge Crystallographic Data Centre; deposition no. CCDC 165491. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, U.K.; fax: (+44) 1223-336-033; or deposit@ccdc.cam.ac.uk).
  • 74
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    • note
    • This analysis is different from that presented in our previous account (ref 16) wherein the aldehyde was suggested to be coordinated trans to a chloride in an axial position. Our calculations strongly suggest that this is not a bound species and would also be deactivated for addition to the aldehyde group.
  • 75
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    • For an in-depth mechanistic discussion of the addition of enoxytrichlorosilyl species to aldehydes, see: Denmark, S. E.; Bui, T. J. Org. Chem. 2005, 70, 10393-10399.
    • (2005) J. Org. Chem. , vol.70 , pp. 10393-10399
    • Denmark, S.E.1    Bui, T.2


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