Latent nucleophilicity of dichlorocarbene

Organic Letters

Volumn 11, Issue 9, 2009, Pages 1947-1950

  Moss, Robert A ^a   Zhang, Min ^a   Krogh Jespersen, Karsten ^a  

^a RUTGERS UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 66149099715     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol900381r     Document Type: Article

References (31)

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22. 3, and 50% aq NaOH by phase-transfer catalysis. The cyclopropanes were purified by preparative GC (SF-96). 1H and 13C NMR spectra of the adducts appear in the Supporting Information.
23. Moss, R. A. In Carbenes; Jones, M., Jr., Moss, R. A., Eds.; Wiley: New York, 1973; Vol. 1, p 153f.
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25. Moss, R. A.; Fedorynski, M.; Shieh, W.-C. J. Am Chem. Soc. 1979, 101, 4736.
26. 2-alkene addition is provided by: Keating, A. E.; Merrigan, S. R.; Singleton, D. A.; Houk, K. N. J. Am. Chem. Soc. 1999, 121, 3933.
27. For a purely electrophilic attack of a carbene, the tilt angle would be 0°. Large tilt angle values (>45°) signify substantial nucleophilic character;6 e.g., at the B3LYP/6-311+G(d) level, the value of the tilt angle is only 42° in the CCl2- propene TS, a distinctly electrophilic attack by the carbene.
28. Mulliken, R. S. J. Chem. Phys. 1955, 23, 1833.
29. In contrast, the TS for CCl2 adding to propene shows a net charge transfer of 0.07e in the opposite direction (B3LYP/6-311+G(d)).
30. 2-ACN, respectively; Krogh-Jespersen, K. Unpublished results.)
31. 23 and also that the approximate variational transition state for CCl2- ClACN obtained at the B3LYP/6-311+G(d) level does not differ significantly from the conventional TS presented in Figure 3 and Table S-4 (Supporting Information).