Kinetic isotope effects in the intramolecular insertion of a metal carbene into a C-H bond adjacent to nitrogen

Tetrahedron Letters

Volumn 40, Issue 46, 1999, Pages 8035-8038

  Sulikowski, Gary A ^a   Lee, Sangku ^a  

^a TEXAS A AND M UNIVERSITY   (United States)

Author keywords

Carbene C H insertion; Deuterium kinetic isotope effect; Stereoelectronic effect

Indexed keywords

COPPER DERIVATIVE; DEUTERIUM; ESTER; NITROGEN; RHODIUM DERIVATIVE;

ARTICLE; CATALYST; CHEMICAL BOND; CIS TRANS ISOMERISM; CYCLIZATION; KINETICS; STEREOCHEMISTRY;

EID: 0033550253     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4039(99)01686-X     Document Type: Article

References (16)

1. (a) Doyle, M. P.; McKervey, M. A.; Ye, T. In Modern Catalytic Methods for Organic Synthesis with Diazo Compounds; John Wiley & Sons: New York, 1998.
2. (b) Sulikowski, G. A.; Cha, K. L.; Sulikowski, M. M. Tetrahedron: Asymmetry 1998, 9, 3145-3169.
3. (a) Lee, S.; Lim, H.-J.; Cha, K. L.; Sulikowski, G. A. Tetrahedron 1997, 53, 16521-16532
4. (a) Clark, J. S.; Dossetter, A. G.; Russell, C. A.; Whittingham, W. G. J. Org. Chem. 1997, 62, 4910-4911.
5. (b) Doyle, M. P.; Dyatkin, A. B.; Autry, C. L. J. Chem. Soc., Perkin Trans. 1 1995, 619-621.
6. Lee, Y.; Huang, H.; Sayre, L. M. J. Am. Chem. Soc. 1996, 18, 7241-7242.
7. (a) Demonceau, A.; Noels, A. F.; Costa, J.-L. J. Mol. Cat. 1990, 58, 21-26.
8. (b) Wang, P.; Adams, J. J. Am. Chem. Soc. 1994, 116, 3296-3305.
9. Baer, T. A.; Gutsche, C. D. J. Am. Chem. Soc. 1971, 93, 5180-5186.
10. Landais, Y.; Parra-Rapado, L.; Planchenault, D.; Weber, V. Tetrahedron Lett. 1997, 38, 229-232.
11. Padwa, A.; Austin, D. J.; Price, A. T.; Semones, M. A.; Doyle, M. P.; Protopopova, M. N.; Winchester, W. R.; Tran, A. J. Am. Chem. Soc. 1993, 115, 8669-8680.
12. Doyle, M. P.; Westrum, L. J.; Wolthuis, W. N. E.; See, M. M.; Boone, W. P.; Bagheri, V.; Pearson, M. M. J. Am. Chem. Soc. 1993, 115, 958-964.
13. Pirrung, M. C.; Morehead, A. T. J. Am. Chem. Soc. 1994, 116, 8991-9000.
14. (a) Taber, D. F.; You, K. K.; Rheingold, A. L. J. Am. Chem. Soc. 1996, 118, 547-556.
15. (b) Taber, D. F.; Malcolm, S. C. J. Org. Chem. 1998, 63, 3717-3721.
16. The analysis shown in Fig. 1 would suggest high trans stereoselectivity for the metal carbene mediated cyclization of 6. However, this is not the case (cf. Table 1). Our only explaination at this time is that a combination of other unfavorable interactions offsets the favorable stereoelectronic effect shown in 12 leading to an overall non-stereoselective cyclization.