[3 + 2] Methylenecyclopentane Annulations of Unactivated and Electron-Rich Olefins with 2-(Phenylsulfonyl)-l-methylenecyclopropanes

Journal of Organic Chemistry

Volumn 55, Issue 16, 1990, Pages 4780-4782

  Singleton, Daniel A ^a   Church, Kevin M ^a  

^a TEXAS A AND M UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0001191542     PISSN: 00223263     EISSN: 15206904     Source Type: Journal    
DOI: 10.1021/jo00303a002     Document Type: Article

References (38)

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2. Binger, P.; Germer, A. Chem. Ber. 1981, 114, 3325 and references therein.
3. The special case of (diphenyl-methylene)cyclopropane works with unhindered unactivated olefins: Binger, P.; Bentz, P. Angew. Chem., Int. Ed. Engl. 1982, 18, 622.
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17. Radical mediated annulations of electron-poor olefins: Curran, D. P.; Chen, M.-H. J. Am. Chem. Soc. 1987, 109, 6558.
18. In a two-step reaction, Curran has applied his atom-transfer cycloaddition to an excess of unactivated olefin (1-hexene) using an iodopropargylmalonate: Curran, D. P.; Chen, M.-H.; Spletzer, E.; Seong, C. M.; Chang, C.-T. J. Am. Chem. Soc., in press.
19. We thank Professor Curran for a preprint of his work: Cekovic, Z.; Saicic, R. Tetrahedron Lett. 1986, 27, 5893.
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24. We thank Professor Feldman for a preprint of his work. For related reactions, see: Feldman, K. S.; Fisher, T. E. Tetrahedron 1989,45, 2969.
25. Feldman, K. S.; Simpson, R. E. Tetrahedron Lett. 1989, 30, 6985.
26. Miura, K.; Fugami, K.; Oshima, K.; Utimoto, K. Tetrahedron Lett. 1988, 29, 5135. These reactions utilize 50 eauiv of the reacting olefin.
27. For recent reviews of free-radical reactions in organic synthesis, see: Curran, D. P. Synthesis 1988, 417.
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30. Satisfactory elemental analyses and/or exact mass molecular weights have been obtained on all new compounds. In all cases, 1H and 13C NMR and IR spectral data were consistent with the assigned structures.
31. The stereochemistry of the major isomers of 4 and 14 were assigned from dNOE studies, where the appropriate 1,3-enhancement was observed in each case. No NOE was observed in the minor isomer. The stereochemistry of the major isomer of 16 was assigned by potassium fert-butoxide catalyzed equilibration, in which the kinetically minor product was found to be thermodynamically predominant (>4:1). The trans isomer is predicted by molecular mechanics calculations (MM2, Macromodel) to be ca. 1 kcal more stable. The validity of the calculations is supported by the observation of the same result in 14. The trans isomer is more stable because it can best avoid allylic strain from the isopropylidene group. See: Allinger, N. L.; Hirsch, J. A.; Miller, M. A.; Tyminski, I. J. J. Am. Chem. Soc. 1968,90, 5773.
32. Johnson, F. Chem. Rev. 1968, 68, 375. The stereochemistry of the major isomer of 13 was tentatively assigned from a strong similarity of chemical shifts and coupling patterns with the major isomers of 14 and 16. Comparisons of actual and modeled coupling constants for 4 and 14 also tentatively indicated the assigned structures.
33. Dialkyl disulfides show a tailing absorption which extends pass 300 nm (e~~10): Calvert, J. G.; Pitts, J. N. Photochemistry; Wiley: New York, 1961: p 490.
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37. For a discussion of ideality in free-radical chain reactions, see ref 4a, p 499.
38. We have observed that the parent 2-(phenylsulfonyl)-l-methylenecyclopropane also annulates olefins in good yield. These studies will be reported in due course.