Rate acceleration in nucleophilic alkylation of carbonyl compounds with a new template containing two metallic centers

Angewandte Chemie - International Edition

Volumn 37, Issue 6, 1998, Pages 835-837

  Ooi, Takashi ^a   Takahashi, Makoto ^a   Maruoka, Keiji ^a  

^a HOKKAIDO UNIVERSITY   (Japan)

Author keywords

Alkylations; Aluminum; Synthetic methods; Template synthesis; Transition states

Indexed keywords

EID: 0031922298     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3773(19980403)37:6<835::AID-ANIE835>3.0.CO;2-Z     Document Type: Article

References (17)

1. Review: E. C. Ashby, Chem. Rev. 1975, 75, 521.
2. a) E. C. Ashby, R. B. Duke, H. M. Neuman, J. Am. Chem. Soc. 1967, 89, 1964;
3. b) E. C. Ashby, Pure Appl. Chem. 1980, 52, 545.
4. For asymmetric two-center catalysis, see H. Steinhagen, G. Helmchen, Angew Chem. 1996, 108, 2489; Angew. Chem. Int. Ed. Engl. 1996, 35, 2339.
5. For asymmetric two-center catalysis, see H. Steinhagen, G. Helmchen, Angew Chem. 1996, 108, 2489; Angew. Chem. Int. Ed. Engl. 1996, 35, 2339.
6. Reviews of organoaluminum chemistry: a) T. Mole, E. A. Jeffery, Organoaluminum Compounds, Elsevier, Amsterdam, 1972; b) K. Maruoka, H. Yamamoto, Angew. Chem. 1985, 97, 670; Angew. Chem. Int. Ed. Engl. 1985, 24, 668; c) K. Maruoka in Synthesis of Organometallic Compounds - A Practical Guide (Ed.: S. Komiya), Wiley, New York, 1997, Chap. 16, p. 364.
7. Reviews of organoaluminum chemistry: a) T. Mole, E. A. Jeffery, Organoaluminum Compounds, Elsevier, Amsterdam, 1972; b) K. Maruoka, H. Yamamoto, Angew. Chem. 1985, 97, 670; Angew. Chem. Int. Ed. Engl. 1985, 24, 668; c) K. Maruoka in Synthesis of Organometallic Compounds - A Practical Guide (Ed.: S. Komiya), Wiley, New York, 1997, Chap. 16, p. 364.
8. Reviews of organoaluminum chemistry: a) T. Mole, E. A. Jeffery, Organoaluminum Compounds, Elsevier, Amsterdam, 1972; b) K. Maruoka, H. Yamamoto, Angew. Chem. 1985, 97, 670; Angew. Chem. Int. Ed. Engl. 1985, 24, 668; c) K. Maruoka in Synthesis of Organometallic Compounds - A Practical Guide (Ed.: S. Komiya), Wiley, New York, 1997, Chap. 16, p. 364.
9. Reviews of organoaluminum chemistry: a) T. Mole, E. A. Jeffery, Organoaluminum Compounds, Elsevier, Amsterdam, 1972; b) K. Maruoka, H. Yamamoto, Angew. Chem. 1985, 97, 670; Angew. Chem. Int. Ed. Engl. 1985, 24, 668; c) K. Maruoka in Synthesis of Organometallic Compounds - A Practical Guide (Ed.: S. Komiya), Wiley, New York, 1997, Chap. 16, p. 364.
10. a) E. C. Ashby, J. Laemmle, H. M. Neumann, J. Am. Chem. Soc. 1968, 90, 5179;
11. b) T. Mole, J. R. Surtees, Aust. J. Chem. 1964, 17, 961.
12. 3-like conformation of aluminum, so transfer of an R group from aluminum to the carbonyl center through an unfavorable four-membered transition state seems quite unlikely. See: T. Ooi, M. Takahashi, K. Maruoka, J. Am. Chem. Soc. 1996, 118, 11307; T. Ooi, E. Tayama, M. Takahashi, K. Maruoka, Tetahedron Lett. 1997, 38, 7403. Other examples of bidentate Lewis acids: V. Sharma, M. Simard, J. D. Wuest, J. Am. Chem. Soc. 1992, 114, 7931; M. Reilly, T. Oh, Tetrahedron Lett. 1995, 36, 217; ibid. 1995, 36, 221.
13. 3-like conformation of aluminum, so transfer of an R group from aluminum to the carbonyl center through an unfavorable four-membered transition state seems quite unlikely. See: T. Ooi, M. Takahashi, K. Maruoka, J. Am. Chem. Soc. 1996, 118, 11307; T. Ooi, E. Tayama, M. Takahashi, K. Maruoka, Tetahedron Lett. 1997, 38, 7403. Other examples of bidentate Lewis acids: V. Sharma, M. Simard, J. D. Wuest, J. Am. Chem. Soc. 1992, 114, 7931; M. Reilly, T. Oh, Tetrahedron Lett. 1995, 36, 217; ibid. 1995, 36, 221.
14. 3-like conformation of aluminum, so transfer of an R group from aluminum to the carbonyl center through an unfavorable four-membered transition state seems quite unlikely. See: T. Ooi, M. Takahashi, K. Maruoka, J. Am. Chem. Soc. 1996, 118, 11307; T. Ooi, E. Tayama, M. Takahashi, K. Maruoka, Tetahedron Lett. 1997, 38, 7403. Other examples of bidentate Lewis acids: V. Sharma, M. Simard, J. D. Wuest, J. Am. Chem. Soc. 1992, 114, 7931; M. Reilly, T. Oh, Tetrahedron Lett. 1995, 36, 217; ibid. 1995, 36, 221.
15. 3-like conformation of aluminum, so transfer of an R group from aluminum to the carbonyl center through an unfavorable four-membered transition state seems quite unlikely. See: T. Ooi, M. Takahashi, K. Maruoka, J. Am. Chem. Soc. 1996, 118, 11307; T. Ooi, E. Tayama, M. Takahashi, K. Maruoka, Tetahedron Lett. 1997, 38, 7403. Other examples of bidentate Lewis acids: V. Sharma, M. Simard, J. D. Wuest, J. Am. Chem. Soc. 1992, 114, 7931; M. Reilly, T. Oh, Tetrahedron Lett. 1995, 36, 217; ibid. 1995, 36, 221.
16. 3-like conformation of aluminum, so transfer of an R group from aluminum to the carbonyl center through an unfavorable four-membered transition state seems quite unlikely. See: T. Ooi, M. Takahashi, K. Maruoka, J. Am. Chem. Soc. 1996, 118, 11307; T. Ooi, E. Tayama, M. Takahashi, K. Maruoka, Tetahedron Lett. 1997, 38, 7403. Other examples of bidentate Lewis acids: V. Sharma, M. Simard, J. D. Wuest, J. Am. Chem. Soc. 1992, 114, 7931; M. Reilly, T. Oh, Tetrahedron Lett. 1995, 36, 217; ibid. 1995, 36, 221.
17. If the proposed mechanism is truly operative, it must be assumed that dilution would not affect the rate of alkylation with 1, but would further retard reaction with 2.