Innermolecular reactions of fluorophenylcarbene inside a hemicarcerand

Organic Letters

Volumn 11, Issue 17, 2009, Pages 3866-3869

  Lu, Zhifeng ^a   Moss, Robert A ^a   Sauers, Ronald R ^a   Warmuth, Ralf ^a  

^a RUTGERS UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 69449099686     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol901474u     Document Type: Article

References (28)

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20. See Supporting Information for experimental details and spectra.
21. max = 550 nm at 13 K in a nitrogen matrix) have been reported: Zuev, P. S.; Sheridan, R. S. J. Am. Chem. Soc. 1994, 116, 9381.
22. Calculations at the B3LYP/6-31G(d) level indicate that the addition of PhCF to 1, 2, 3-trimethoxybenzene (a model for hemicarcerand 2) at the C(1)-C(2) double bond requires 14.7 kcal/mol of activation energy and affords the corresponding norcaradiene with an exothermicity of 27.6 kcal/ mol. Further reactions of the norcaradiene afford a tropone with an additional exothermicity of 16.1 kcal/mol. A reaction/enthalpy scheme appears in Supporting Information.
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26. Not surprisingly, the even less stabilized phenylcarbene (PhCH) also attacks the hemicarcerand; cf. ref 4.
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