Intramolecular Carbon-Hydrogen Insertions of Alkyiidenecarbenes. 1. Selectivity

Journal of Organic Chemistry

Volumn 48, Issue 26, 1983, Pages 5251-5256

  Gilbert, John C ^a   Giamalva, David H ^a   Weerasooriya1, Upali ^a  

^a UNIVERSITY OF TEXAS AT AUSTIN   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000500403     PISSN: 00223263     EISSN: 15206904     Source Type: Journal    
DOI: 10.1021/jo00174a019     Document Type: Article

References (29)

1. This work taken in part from the dissertations of U.W. and D.H.G., submitted in partial fulfillment of requirements for the Ph. D. degree, University of Texas at Austin, 1980 and 1981.
2. Reviews: (a) Hartzler, H.D. In “Carbenes”; Moss, R.A., Jones, M., Jr., Eds.; Wiley-Interscience: New York, 1975; Vol 2, Chapter 2. (b) Stang, P.J. Chem. Rev. 1978, 78, 383. (c) Stang, P.J. Acc. Chem. Res. 1982, 15, 348.
3. Reviews: (a) Gilcrist, T.L.; Rees, C.W. “Carbenes, Nitrenes and Arynes”; Appleton-Century Crofts, Inc.: New York, 1969. (b) Kirmse, W. “Carbene Chemistry”, 2nd ed.; Academic Press: New York, 1971. (c) Jones, M., Jr.; Moss, R.A., Eds. “Carbenes”; Wiley-Interscience: New York, 1973; Vol. I. (d) Barton, D.H.R.; Ollis, W.D. “Comprehensive Organic Chemistry”; Pergamon Press: New York, 1979; Vol. 2.
4. Intermolecular: (a) Sakakibara, T.; Odaira, Y.; Tsutsumi, S. Tetrahedron Lett. 1968, 503. (b) Newman, M.S.; Okorodudu, A.O.M.J. Org. Chem. 1969, 34, 1220. (c) Newman, M.S.; Beard, C.D.J. Am. Chem. Soc. 1970, 92, 4309. (d) Newman, M.S.; Patrick, T.B.J. Org. Chem. 1970, 92, 4312. (e) Gilbert, J.C.; Butler, J.R.J. Org. Chem. 1970, 92, 7607. (f) Stang, P.J.; Mangum, M.G.; Fox, D.P.; Haak, P.J. Org. Chem. 1974, 96, 4562. (g) Gilbert, J.C.; Weerasooriya, U. Tetrahedron Lett. 1980, 21, 2041. (h) Gilbert, J.C.; Weerasooriya, U.; Wiechman, B.; Ho, L. Tetrahedron Lett. 1980, 21, 5003. (i) Stang, P.J.; Christensen, S.B.J. Org. Chem. 1981, 46, 823. (j) Gilbert, J.C.; Weerasooriya, U. Tetrahedron Lett. 1983, 48, 448.
5. Intramolecular: (a) Erickson, K.L.; Wolinsky, J. J. Am. Chem. Soc. 1965, 87, 1143. (b) Walsh, R.A.; Bottini, A.T.J. Org. Chem. 1970, 35, 1086. (c) Fisher, R.H.; Baumann, M.; Koebrich, G. Tetrahedron Lett. 1974, 1207. (d) Brown, F.C.; Eastwood, R.W.; Harrington, K.J.; McMullen, G.L. Aust. J. Chem. 1974, 27, 2393. (e) Wolinsky, J.; Clark, G.W.; Thorstenson, P.C.J. Org. Chem. 1976, 41, 745. (f) Brown, R.F.C.; Eastwood, F.W.; Jackman, G.P. Aust. J. Chem. 1977, 30, 1757. (g) Karpf, M.; Dreiding, A.S. Helv. Chim. Acta 1979, 62, 852. (h) Gilbert, J.C.; Weerasooriya, U.; Giamalva, D. Tetrahedron Lett. 1979, 4619. (i) Karpf, M.; Dreiding, A.S. Helv. Chim. Acta 1981, 64, 1123. (j) Karpf, M.; Huguet, J.; Dreiding, A.S. Helv. Chim. Acta 1982, 65, 13. (k) Hauske, J.R.; Guadliana, M.; Desai, K.J. Org. Chem. 1982, 47, 5019.
6. The methylenecyclopropanes are believed 5e to be formed by an addition-isomerization sequence rather than by insertion into the C-H bond at C-3.
7. Ab initio techniques predict a heat of reaction of 40 kcal/mol, whereas an SCF approach (MINDO/3) predicts 46 kcal/mol (Gilbert, J.C., unpublished results).
8. Dykstra, C.E.; Schaefer, H.F. III.J. Am. Chem. Soc. 1978, 100, 1378.
9. Gilbert, J.C.; Weerasooriya, U. J. Org. Chem. 1982, 42, 1837.
10. Su, D.T.T.; Thornton, E.R. J. Am. Chem. Soc. 1978, 100, 1872.
11. The migratory aptitudes of aryl and hydrogen appear to be comparable in cases where the alkylidenecarbene is generated by flash vacuum pyrolysis. f However, preliminary data obtained in our laboratories show hydrogen to migrate exclusively, relative to either phenyl or p-anisyl, when the carbene is generated at-78 °C (Baze, M.E., unpublished results).
12. “The Sadtler Standard Spectra”; Sadtler Research Laboratories: Philadelphia, PA, 1980; 1H NMR, Spectrum No. 8185.
13. Budzikiewicz, H.; Brauman, J.I.; Djerassi, C. Tetrahedron 1965, 21, 1855.
14. Cox, J.D.; Pilcher, G. “Thermochemistry of Organic and Organometallic Compounds”; Academic Press: New York, 1970.
15. Silverstein, R.M.; Bassler, G.C.; Morrill, T.C. “Spectrometric Identification of Organic Compounds”, 4th ed.; Wiley: New York, 1981.
16. An isomer of the major product had a mass spectrum that closely matched that of 4-nonyne; this material constituted only 0.6% of the product mixture.
17. Lord, R.C.; Walker, R.W. J. Am. Chem. Soc. 1954, 76, 2518.
18. Calculations have indicated that electron-withdrawing substituents should stabilize alkylidenecarbenes.19 Such stabilization should lead to greater selectivities for the carbenes derived from ynones, in analogy to the relationship between selectivity and stability noted for saturated carbenes.3 On the basis of the limited data given in Table II, this appears to be the case, although the trend is hardly dramatic, if indeed it is real.
19. Apeloig, Y.; Schreiber, R. Tetrahedron Lett. 1978, 4555.
20. It is of interest that these carbenes appear to have a selectivity comparable to that of dicarbomethoxycarbene [(CH3OCO)2C:J generated photochemically from the corresponding diazo compound.21
21. Doering, W.E.; Knox, L.H. J. Am. Chem. Soc. 1961, 83, 1989. Jones, M., Jr.; Ando, W.; Hendrick, M.E.; Kulczycki, A., Jr.; Howley, P.M.; Hummel, K.F.; Malament, D.S.J. Am. Chem. Soc. 1972, 94, 7499.
22. One fascinating example involving use of the diazoethene method to achieve insertion into the C-H bond of a methoxy group has recently been reported.
23. We thank K and K Laboratories for providing the authentic sample.
24. Guyon, R.; Villa, P. Bull. Soc. Chim. Fr. 1972, 137S.
25. “Tables for Identification of Organic Compounds”; CRC Press: Cleveland, OH, 1960.
26. This value is suspected to be in error, as the frequency is far higher than would be expected for a dialkyl ketone.
27. Seyferth, D.; Marmar, R.M.; Hilbert, P.H. J. Org. Chem. 1971, 36, 1379.
28. Plate, A.F.; Mel'nikov, A.A. Zh. Obschch. Khim. 1959, 29, 1379.
29. Pehk, T.; Rang, S.; Eisen, O.; Lippman, O. Eesti NSV Tead. Akad. Toim. Keem. Geol. 1968, 17, 296.