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Volumn 121, Issue 19, 1999, Pages 4545-4554

Regio- and enantioselective allylic alkylation of an unsymmetrical substrate: A working model

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE; ALLYL COMPOUND; BENZOIC ACID DERIVATIVE; DIAMINE; LIGAND; PALLADIUM; SOLVENT;

EID: 0033583714     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja9828713     Document Type: Article
Times cited : (312)

References (53)
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    • For lead references dealing with regioselectivity, see: Mo: Trost, B. M.; Lautens, M. J. Am. Chem. Soc. 1987, 109, 1469. W: Trost, B. M.; Tometzki, G. B.; Hung, M.-H. J. Am. Chem. Soc. 1987, 109, 2176. Ir: Takeuchi, R.; Kashio, M. Angew. Chem., Int. Ed. Engl. 1997, 36, 263. Rh: Evans, P. A.; Nelson, J. D. J. Am. Chem. Soc. 1998, 120, 5581.
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    • For lead references dealing with regioselectivity, see: Mo: Trost, B. M.; Lautens, M. J. Am. Chem. Soc. 1987, 109, 1469. W: Trost, B. M.; Tometzki, G. B.; Hung, M.-H. J. Am. Chem. Soc. 1987, 109, 2176. Ir: Takeuchi, R.; Kashio, M. Angew. Chem., Int. Ed. Engl. 1997, 36, 263. Rh: Evans, P. A.; Nelson, J. D. J. Am. Chem. Soc. 1998, 120, 5581.
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  • 7
    • 0030940143 scopus 로고    scopus 로고
    • For lead references dealing with regioselectivity, see: Mo: Trost, B. M.; Lautens, M. J. Am. Chem. Soc. 1987, 109, 1469. W: Trost, B. M.; Tometzki, G. B.; Hung, M.-H. J. Am. Chem. Soc. 1987, 109, 2176. Ir: Takeuchi, R.; Kashio, M. Angew. Chem., Int. Ed. Engl. 1997, 36, 263. Rh: Evans, P. A.; Nelson, J. D. J. Am. Chem. Soc. 1998, 120, 5581.
    • (1997) Angew. Chem., Int. Ed. Engl. , vol.36 , pp. 263
    • Takeuchi, R.1    Kashio, M.2
  • 8
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    • For lead references dealing with regioselectivity, see: Mo: Trost, B. M.; Lautens, M. J. Am. Chem. Soc. 1987, 109, 1469. W: Trost, B. M.; Tometzki, G. B.; Hung, M.-H. J. Am. Chem. Soc. 1987, 109, 2176. Ir: Takeuchi, R.; Kashio, M. Angew. Chem., Int. Ed. Engl. 1997, 36, 263. Rh: Evans, P. A.; Nelson, J. D. J. Am. Chem. Soc. 1998, 120, 5581.
    • (1998) J. Am. Chem. Soc. , vol.120 , pp. 5581
    • Evans, P.A.1    Nelson, J.D.2
  • 9
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    • For enantioselective allylic alkylations, see: Mo: Trost, B. M.; Hachiya, I. J. Am. Chem. Soc. 1998, 120, 1104. W: Lloyd-Jones, G. C.; Pfaltz, A. Angew. Chem., Int. Ed. Engl. 1995, 34, 462. Ir: Janssen, J. P.; Helmchen, G. Tetrahedron Lett. 1997, 38, 8025.
    • (1998) J. Am. Chem. Soc. , vol.120 , pp. 1104
    • Trost, B.M.1    Hachiya, I.2
  • 10
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    • For enantioselective allylic alkylations, see: Mo: Trost, B. M.; Hachiya, I. J. Am. Chem. Soc. 1998, 120, 1104. W: Lloyd-Jones, G. C.; Pfaltz, A. Angew. Chem., Int. Ed. Engl. 1995, 34, 462. Ir: Janssen, J. P.; Helmchen, G. Tetrahedron Lett. 1997, 38, 8025.
    • (1995) Angew. Chem., Int. Ed. Engl. , vol.34 , pp. 462
    • Lloyd-Jones, G.C.1    Pfaltz, A.2
  • 11
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    • For enantioselective allylic alkylations, see: Mo: Trost, B. M.; Hachiya, I. J. Am. Chem. Soc. 1998, 120, 1104. W: Lloyd-Jones, G. C.; Pfaltz, A. Angew. Chem., Int. Ed. Engl. 1995, 34, 462. Ir: Janssen, J. P.; Helmchen, G. Tetrahedron Lett. 1997, 38, 8025.
    • (1997) Tetrahedron Lett. , vol.38 , pp. 8025
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    • VCH: Weinheim
    • Karapet'yants, M. Kh.; Karapet'yants, M. L. Thermodynamic Constants of Inorganic and Organic Compounds; Humphrey Science Publishers: Ann Arbor, MI, 1970; p 208. Barin, I. Thermochemical Data of Pure Substances, 3rd ed; VCH: Weinheim, 1995; p 1312.
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    • Trost, B. M.; Bunt, R. C. J. Am. Chem. Soc. 1994, 116, 4089. Trost, B. M.; Bunt, R. C.; Zambrano, J. J. Am. Chem. Soc. 1996, 118, 6520.
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    • We enlisted the aid of Professor A. Togni, but his group was also thwarted
    • We enlisted the aid of Professor A. Togni, but his group was also thwarted.
  • 39
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    • For several X-ray structures, see: Chapman and Hall: New York, NY
    • For several X-ray structures, see: Dictionary of Organometallic Coumpounds; Macintyre, J. E., Ed.; Chapman and Hall: New York, NY, 1995; Vois 1-5.
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    • Macintyre, J.E.1
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    • note
    • 11,20 NMR experiments have been used to determine which complex, syn,syn or syn,anti, is kinetically formed. However, all attempts to utilize this approach with our ligand have proven to be unsuccessful.
  • 42
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    • This paper concludes, as we have for our ligands, that the steric interactions associated with the synchronous events of nucleophilic attack and rotation due to the change of hapticity are responsible for the chiral recognition
    • In work published after submission of this manuscript, the possibility that the product derives from regioselective attack on a syn,anti complex has been discussed, see: Ramdeehul, S.; Dierkes, P.; Aquado, R.; Kamer, P. C.; van Leewen, P. W. N. M.; Osborn, J. A. Angew. Chem., Int. Ed. 1998, 37, 3118. This paper concludes, as we have for our ligands, that the steric interactions associated with the synchronous events of nucleophilic attack and rotation due to the change of hapticity are responsible for the chiral recognition.
    • (1998) Angew. Chem., Int. Ed. , vol.37 , pp. 3118
    • Ramdeehul, S.1    Dierkes, P.2    Aquado, R.3    Kamer, P.C.4    Van Leewen, P.W.N.M.5    Osborn, J.A.6
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    • unpublished results in these laboratories
    • Hagelin, H., unpublished results in these laboratories.
    • Hagelin, H.1
  • 51
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    • note
    • The results obtained herein provide impetus to reexamine the conclusions for the intermolecular reactions reported in ref 6e and will be reported in due course.


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