Concurrent cyclopropanation by carbenes and carbanions

Journal of the American Chemical Society

Volumn 127, Issue 25, 2005, Pages 8960-8961

  Moss, Robert A ^a   Tian, Jingzhi ^a  

^a RUTGERS UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ACETONITRILE; ACRYLONITRILE; ANION; BROMINE DERIVATIVE; CARBANION; CARBENOID; CHLOROFORM; CYCLOPROPANE; ETHYLENE DERIVATIVE; PHENYLBROMODIAZIRINE; TRIMETHYLETHYLENE; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; CYCLOPROPANATION; HYDROLYSIS; MATHEMATICAL ANALYSIS; PHASE TRANSITION; PHOTOCHEMISTRY; PHOTOLYSIS;

ALKENES; ANIONS; CARBON; CYCLIZATION; CYCLOPROPANES; HALOGENS; HYDROCARBONS; METHANE; MOLECULAR STRUCTURE;

EID: 21244472957     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja052426p     Document Type: Article

References (29)

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11. Experimental details appear in the Supporting Information.
12. Moss, R. A. in Carbenes; Jones, M., Jr., Moss, R. A., Eds.; Wiley-Interscience: New York, 1973; Vol. 1, pp 153f.
13. MeCN (1.5 M) was added to help solubilize salts; see below.
14. (a) Moss, R. A. Acc. Chem. Res. 1980, 13, 58.
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16. (c) Soundararajan, N.; Platz, M. S.; Jackson, J. E.; Doyle, M. P.; Oon, S.-M.; Liu, M. T. H.; Anand, S. M. J. Am. Chem. Soc. 1988, 110, 7143.
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18. 13
19. Tabular results for all products appear in the Supporting Information.
20. 13
21. - adducts generally cyclize. See: Fedorynski, M. Chem. Rev. 2003, 103, 1099.
22. Control experiments showed that TBABr or TBACl did not significantly interconvert diazirines 1-Br or 1-Cl.
23. -.
24. For a description of our LFP system, see: Moss, R. A.; Johnson, L. A.; Merrer, D. C.; Lee, G. E., Jr. J. Am. Chem. Soc. 1999, 121, 5940. The 1000 W Xe monitoring lamp has been replaced by a 150 W pulsed Xe lamp.
25. Gould, I. R.; Turro, N. J.; Butcher, J., Jr.; Doubleday, C., Jr.; Hacker, N. P.; Lehr, G. F.; Moss, R. A.; Cox, D. P.; Guo, W.; Munjal, R. C.; Perez, L. A.; Fedorynski, M. Tetrahedron 1985, 41, 1587.
26. +) benzyl anion absorbs at 342 nm in THF: Bockrath, B.; Dorfman, L. M. J. Am. Chem. Soc. 1975, 97, 3307.
27. For previous kinetics studies of carbene/halide quenching, see: Moss, R. A.; Fan, H.; Gurumurthy, R.; Ho, G.-J. J. Am. Chem. Soc. 1991, 113, 1435.
28. rel = 0.042, determined above.
29. Details of the kinetics studies will appear in a separate publication.