Evidence for a Stepwise Addition of Carbenes to Strained Double Bonds: Reactions of Dihalocarbenes with Cyclopropenes

Angewandte Chemie (International Edition in English)

Volumn 36, Issue 15, 1997, Pages 1623-1626

  Weber, Jürgen ^b   Brinker, Udo H ^a  

^a Inst fur Org Chem der Univ   (Austria)

^b BINGHAMTON UNIVERSITY   (United States)

Author keywords

Carbenes; Cyclopropenes; Rearrangements; Strained molecules

Indexed keywords

EID: 0030763185     PISSN: 05700833     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.199716231     Document Type: Article

References (36)

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29. We thank Professor R. Boese, Universität Essen, Germany, for the X-ray structure determinination of 8. Crystallographic data (excluding structure factors) for the structures reported in this paper have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication no. CCDC-179-179. Copies of the data can be obtained free of charge on application to The Director, CCDC, 12 Union Road, Cambridge CB21EZ, UK (fax: int. code +(1223)336-033; e-mail: deposit@chemcrys.cam.ac.uk).
30. Tetrahalocyclopropane 8 was synthesized from commercially available chlorodifluoroacetic acid: Treatment with sodium hydroxide gave the corresponding sodium salt, which reacted with phenylmagnesium bromide to afford chlorodifluoromethyl ketone [18] in 87% yield. Wittig reaction with methylenetriphenylphosphonium bromide produced α-(chlorodifluoromethyl)styrene (yield 71%). Addition of bromophenylcarbene, generated from treatment of benzal bromide with potassium tert-butoxide, afforded 8 and its trans isomer in very low yields. The isomers were purified in multiple steps and finally separated by HPLC.
31. T. Ando, F. Namigata, M. Kataoka, K. Yachida, W. Funasaka, Bull. Chem. Soc. 1967, 40, 1275.
32. The ratio of aryl-substituted butadienes to cyclobutenes was also found to be approximately 20:80, which is in good agreement with the previously determined ratio of 2 to 5.
33. Dipolar resonance structures have been proposed as intermediates in dihalocarbene additions to alkenes: P. S. Skell, A. Y. Garner, J. Am. Chem. Soc. 1956, 78, 5430; W. von E. Doering, W. A. Henderson, Jr., J. Am. Chem. Soc. 1958, 80, 5274.
34. Dipolar resonance structures have been proposed as intermediates in dihalocarbene additions to alkenes: P. S. Skell, A. Y. Garner, J. Am. Chem. Soc. 1956, 78, 5430; W. von E. Doering, W. A. Henderson, Jr., J. Am. Chem. Soc. 1958, 80, 5274.
35. The strain energy probably has a major influence on the reaction of a dihalocarbene with cyclopropene 1. Due to release of olefinic strain, an intermediate zwitterion should be lower in energy than 1. Stabilization of the transition state can be achieved through ring opening and complete release of strain in the cyclopropane ring with concomitant formation of conjugated double bonds. On the other hand, ring closure of 7 to a geminal dichlorobicyclobutane leads to an initial increase in strain energy. However, once the bicyclic compound 3 has been formed, the CCA rearrangement inevitably proceeds, thereby releasing substantial amounts of strain energy.
36. In addition to cyclobutene 5, the coupling products meso- and (R,S)-2,2′-dichloro-1,1′,3,3′-tetraphenylbi[cyclobut-1-en-3- yl] were isolated.