Dehydrogenative silylation of amines and hydrosilylation of imines catalyzed by ytterbium-imine complexes

Journal of Organic Chemistry

Volumn 64, Issue 11, 1999, Pages 3891-3895

  Takaki, Ken ^a   Kamata, Tohru ^a   Miura, Yoshimi ^a   Shishido, Tetsuya ^a   Takehira, Katsuomi ^a  

^a HIROSHIMA UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

AMINE; IMINE; YTTERBIUM;

ARTICLE; CARBON NUCLEAR MAGNETIC RESONANCE; CATALYSIS; CATALYST; CHEMICAL REACTION; COMPLEX FORMATION; MOLECULAR RECOGNITION; PROTON NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS; SYNTHESIS;

EID: 0033612395     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo982154r     Document Type: Article

References (26)

1. (a) Edelmann, F. T. In Topics in Current Chemistry 179; Herrmann, W. A., Ed.; Springer-Verlag: Berlin, 1996; pp 247-276.
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8. (d) Giardello, M. A.; Conticello, V. P., Brard, L.; Gagne, M. R.; Marks, T. J. J. Am. Chem. Soc. 1994, 116, 10241-10254.
9. (e) Haar, C. M.; Stern, C. L.; Marks, T. J. Organometallics 1996, 15, 1765-1784.
10. (a) Sakakura, T.; Lautenschlager, H.-J.; Tanaka, M. J. Chem. Soc., Chem. Commun. 1991, 40-41.
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15. Obora, Y.; Ohta, T.; Stern, C. L.; Marks, T. J. J. Am. Chem. Soc. 1997, 119, 3745-3755.
16. Radu, N. S.; Buchwald, S. L.; Scott, B.; Burns, C. J. Organometallics 1996, 15, 3913-3915.
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20. Opposite transposition (Ln-N + Si-H - Ln-Si + N-H) was proposed to account for the role of phenylsilane accelerator in lanthanocene-catalyzed imine hydrogenation by Marks et al. Simultaneously, they documented the formation of a small amount of hydrosilylation product (<10%); see: ref 4.
21. Dehydrogenative silylation of amines catalyzed by lithium amides has been well-known; see: Kraus, C. A.; Nelson, W. K. J. Am. Chem. Soc. 1934, 56, 195-202.
22. Although the accurate number of the coordinated HMPA is unknown, equivalents of this additive used for generation of 1 are tentatively shown as a coordination number. The product 3a was formed in very low yields (<5%) in the absence of HMPA.
23. No aminosilanes derived from the imine ligands were detected in any reactions.
24. N = 1.1) was isolated in 29% yield by aqueous workup, followed by short-column chromatography on silica gel using hexanes-ethyl acetate (1/1).
25. Forsyth, C. M.; Nolan, S. P.; Marks, T. J. Organometallics 1991, 10, 2543-2645.
26. Oligomerization and hydrogen evolution were not observed on treatment of the two silanes with 1.