Reactions of imines with azazirconacyclobutenes and generation of electron-deficient imidozirconocene complexes

Organometallics

Volumn 23, Issue 10, 2004, Pages 2231-2233

  Ruck, Rebecca T ^a   Bergman, Robert G ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

COMPLEXES; ELECTRON DEFICIENCY; REACTIVITY;

ADDITION REACTIONS; CARBON; CHEMICAL BONDS; COMPLEXATION; NITROGEN; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; UNSATURATED COMPOUNDS; ZIRCONIUM;

BUTENES;

EID: 2542419036     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om0497994     Document Type: Article

References (18)

1. Walsh, P. J.; Hollander, F. J.; Bergman, R. G. Organometallics 1993, 12, 3705.
2. Standard condensation methods for the preparation of α,β- unsaturated imines have not been shown to be successful in the syntheses of these highly arylated α,β-disubstituted derivatives.
3. Hanna, T. A.; Baranger, A. M.; Bergman, R. G. J. Org. Chem. 1996, 61, 4532.
4. Love, B. E.; Raje, P. S.; Williams, T. C., II. Synlett 1994, 493.
5. There are no examples of early-transition metal-N-tosyl imido complexes in the literature. Mid-to-late-transition-metal-N-tosyl imido complexes have been shown to participate in group transfer chemistry. For more information, see: (a) Liang, J.-L.; Huang, J.-S.; Yu, X.-Q.; Zhu, N.; Che, C.-M. Chem. Eur. J. 2002, 8, 1563. (b) Smieja, J. A.; Shirzad, K.; Roy, M.; Kittilstved, K.; Twamley, B. Inorg. Chim. Acta 2002, 335, 141. (c) Au, S.-M.; Huang, J.-S.; Yu, W.-Y.; Fung, W.-H.; Che, C.-M. J. Am. Chem. Soc. 1999, 121, 9120. (d) Au, S.-M.; Fung, W.-H.; Huang, J.-S.; Cheung, K.-K.; Che, C.-M. Inorg. Chem. 1998, 37, 6564. (e) Li, Z.; Quan, R. W.; Jacobsen, E. N. J. Am. Chem. Soc. 1995, 117, 5889. (f) Harlan, E. W.; Holm, R. H. J. Am. Chem. Soc. 1990, 112, 186.
6. There are no examples of early-transition metal-N-tosyl imido complexes in the literature. Mid-to-late-transition-metal-N-tosyl imido complexes have been shown to participate in group transfer chemistry. For more information, see: (a) Liang, J.-L.; Huang, J.-S.; Yu, X.-Q.; Zhu, N.; Che, C.-M. Chem. Eur. J. 2002, 8, 1563. (b) Smieja, J. A.; Shirzad, K.; Roy, M.; Kittilstved, K.; Twamley, B. Inorg. Chim. Acta 2002, 335, 141. (c) Au, S.-M.; Huang, J.-S.; Yu, W.-Y.; Fung, W.-H.; Che, C.-M. J. Am. Chem. Soc. 1999, 121, 9120. (d) Au, S.-M.; Fung, W.-H.; Huang, J.-S.; Cheung, K.-K.; Che, C.-M. Inorg. Chem. 1998, 37, 6564. (e) Li, Z.; Quan, R. W.; Jacobsen, E. N. J. Am. Chem. Soc. 1995, 117, 5889. (f) Harlan, E. W.; Holm, R. H. J. Am. Chem. Soc. 1990, 112, 186.
7. There are no examples of early-transition metal-N-tosyl imido complexes in the literature. Mid-to-late-transition-metal-N-tosyl imido complexes have been shown to participate in group transfer chemistry. For more information, see: (a) Liang, J.-L.; Huang, J.-S.; Yu, X.-Q.; Zhu, N.; Che, C.-M. Chem. Eur. J. 2002, 8, 1563. (b) Smieja, J. A.; Shirzad, K.; Roy, M.; Kittilstved, K.; Twamley, B. Inorg. Chim. Acta 2002, 335, 141. (c) Au, S.-M.; Huang, J.-S.; Yu, W.-Y.; Fung, W.-H.; Che, C.-M. J. Am. Chem. Soc. 1999, 121, 9120. (d) Au, S.-M.; Fung, W.-H.; Huang, J.-S.; Cheung, K.-K.; Che, C.-M. Inorg. Chem. 1998, 37, 6564. (e) Li, Z.; Quan, R. W.; Jacobsen, E. N. J. Am. Chem. Soc. 1995, 117, 5889. (f) Harlan, E. W.; Holm, R. H. J. Am. Chem. Soc. 1990, 112, 186.
8. There are no examples of early-transition metal-N-tosyl imido complexes in the literature. Mid-to-late-transition-metal-N-tosyl imido complexes have been shown to participate in group transfer chemistry. For more information, see: (a) Liang, J.-L.; Huang, J.-S.; Yu, X.-Q.; Zhu, N.; Che, C.-M. Chem. Eur. J. 2002, 8, 1563. (b) Smieja, J. A.; Shirzad, K.; Roy, M.; Kittilstved, K.; Twamley, B. Inorg. Chim. Acta 2002, 335, 141. (c) Au, S.-M.; Huang, J.-S.; Yu, W.-Y.; Fung, W.-H.; Che, C.-M. J. Am. Chem. Soc. 1999, 121, 9120. (d) Au, S.-M.; Fung, W.-H.; Huang, J.-S.; Cheung, K.-K.; Che, C.-M. Inorg. Chem. 1998, 37, 6564. (e) Li, Z.; Quan, R. W.; Jacobsen, E. N. J. Am. Chem. Soc. 1995, 117, 5889. (f) Harlan, E. W.; Holm, R. H. J. Am. Chem. Soc. 1990, 112, 186.
9. There are no examples of early-transition metal-N-tosyl imido complexes in the literature. Mid-to-late-transition-metal-N-tosyl imido complexes have been shown to participate in group transfer chemistry. For more information, see: (a) Liang, J.-L.; Huang, J.-S.; Yu, X.-Q.; Zhu, N.; Che, C.-M. Chem. Eur. J. 2002, 8, 1563. (b) Smieja, J. A.; Shirzad, K.; Roy, M.; Kittilstved, K.; Twamley, B. Inorg. Chim. Acta 2002, 335, 141. (c) Au, S.-M.; Huang, J.-S.; Yu, W.-Y.; Fung, W.-H.; Che, C.-M. J. Am. Chem. Soc. 1999, 121, 9120. (d) Au, S.-M.; Fung, W.-H.; Huang, J.-S.; Cheung, K.-K.; Che, C.-M. Inorg. Chem. 1998, 37, 6564. (e) Li, Z.; Quan, R. W.; Jacobsen, E. N. J. Am. Chem. Soc. 1995, 117, 5889. (f) Harlan, E. W.; Holm, R. H. J. Am. Chem. Soc. 1990, 112, 186.
10. There are no examples of early-transition metal-N-tosyl imido complexes in the literature. Mid-to-late-transition-metal-N-tosyl imido complexes have been shown to participate in group transfer chemistry. For more information, see: (a) Liang, J.-L.; Huang, J.-S.; Yu, X.-Q.; Zhu, N.; Che, C.-M. Chem. Eur. J. 2002, 8, 1563. (b) Smieja, J. A.; Shirzad, K.; Roy, M.; Kittilstved, K.; Twamley, B. Inorg. Chim. Acta 2002, 335, 141. (c) Au, S.-M.; Huang, J.-S.; Yu, W.-Y.; Fung, W.-H.; Che, C.-M. J. Am. Chem. Soc. 1999, 121, 9120. (d) Au, S.-M.; Fung, W.-H.; Huang, J.-S.; Cheung, K.-K.; Che, C.-M. Inorg. Chem. 1998, 37, 6564. (e) Li, Z.; Quan, R. W.; Jacobsen, E. N. J. Am. Chem. Soc. 1995, 117, 5889. (f) Harlan, E. W.; Holm, R. H. J. Am. Chem. Soc. 1990, 112, 186.
11. Alper, P. B.; Meyers, C.; Lerchner, A.; Siegel, D. R.; Carriera, E. M. Angew. Chem., Int. Ed. Engl. 1999, 38, 3186.
12. An analogous structure was determined on the precipitate in the tosyl reaction; however, the crystal for this species decomposed on the diffractomer, and only a partial data set was collected.
13. Liu, G.; Cogan, D. A.; Ellman, J. A. J. Am. Chem. Soc. 1997, 119, 9913.
14. Decomposition was not limited to N-tert-butylsulfinylbenzaldimine; N-(p-toluenesulfinyl)benzaldimine began to decompose at 90°C.
15. Yamada, K.; Harwood, S. J.; Gröger, H.; Shibasaki, M. Angew. Chem., Int. Ed. Engl. 1999, 38, 3504.
16. We have also generated the N-phosphinyl imidozirconocene complex 16 by an alternative method. All spectral data for 18 generated in this manner correlate with those observed by the methodology above. Chemical equation presented
17. 1c.
18. We propose three possible roles for the oxygen substituent: (1) in withdrawing electron density from the imine C=N bond, the oxygen substituent may facilitate insertion by making the imine more electrophilic and, thus, higher in energy and more reactive; (2) the oxygen substituent may be required to coordinate to zirconium and, therefore, direct the insertion; (3) the protecting group on nitrogen may increase the distance between the imine and the bulk of the protecting group, thus facilitating insertion.