The stereospecific cyclopropanation of diarylcarbene cation radicals

Tetrahedron Letters

Volumn 37, Issue 28, 1996, Pages 4927-4930

  Stoub, Darren G ^a   Cheng, Kung Lung ^a   Goodman, Joshua L ^a  

^a UNIVERSITY OF ROCHESTER   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE DERIVATIVE; ANTIMONY DERIVATIVE; CATION; CYCLOPROPANE DERIVATIVE; DIAZOMETHANE; RADICAL;

ABSORPTION SPECTROSCOPY; ARTICLE; CHEMICAL REACTION; OXIDATION; STEREOISOMERISM; STEREOSPECIFICITY;

EID: 0030575376     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/0040-4039(96)00988-4     Document Type: Article

References (31)

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16. +̇, which suggests that oxidation of 1 is required.
17. 1H NMR indicate that the ratio of cyclopropane stereoisomers is ≥ 99%, with the major product having the same relative stereochemistry as the alkene used.
18. 5. Attempts to use electron-poor alkenes were unsuccessful because of competing thermal neutral reactions of the alkenes with 1, presumably 1,3 dipolar cycloaddition reactions.
19. +̇ were significantly slower, in part because of the higher oxidation potentials of the diazo compounds. We are currently investigating these reactions.
20. +̇ was obtained by photoinduced electron transfer, see Todd et al. J. Amer. Chem. Soc. 1991, 113, 3601.
21. 2b
22. (c) The kinetics also rules out the possibility of a cation radical mediated 3+2 dipolar cycloadditon of the diazo compound with cyclohexene to form the heterocyclic cation radical which can subsequently lose nitrogen.
23. 8. (a) Adam, W.; Sahin, C.; Sendelbach, J.; Walter, H.; Chen, G-F.; Williams, F. J. Amer. Chem. Soc. 1994, 116, 2576, and references therein.
24. (b) Adam, W.; Walter, H.; Chen, G-F.; Williams, F. J. Amer. Chem. Soc. 1992, 114, 3007.
25. 4 alkene was used for these experiments.
26. 1 For mono and 1,2 alkyl substituted alkenes, the enthalpy for 1,2 hydrogen rearrangement is calculated to be significantly less exothermic. Alternatively, these reactions may be concerted and not proceed via 1,3 cation radicals.
27. 11. For example, see Baron, W. J.; Hendrick, M. E. J. Amer. Chem. Soc. 1973, 95, 6286.
28. 12. (a) Dix, E. J.; Goodman, J. L. J. Amer. Chem. Soc. 1973, 95, 6286.
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31. 13. In fact, the the thermodynamics of ring closure of 1,3 cation radicals has received considerable attention in the literature. See Borden et. al. Chem. Phys. Lett. 1986, 123, 337.