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Volumn 50, Issue 25, 1985, Pages 5223-5230

Intramolecular N-H, O-H, and S-H Insertion Reactions. Synthesis of Heterocycles from α-Diazo β-Keto Esters

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EID: 0001060227     PISSN: 00223263     EISSN: 15206904     Source Type: Journal    
DOI: 10.1021/jo00225a047     Document Type: Article
Times cited : (175)

References (37)
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    • A general review on carbenoid reactions is presented in: Wulfman, D. S.; Poling, B. “Reactive Intermediates”; Abramovitch, R. A., Ed.; Plenum Press: New York, 1980, Vol. 1, p 321.
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    • Recent studies on carbenoid C-H insertion are given in (b) Taber, D. F.; Petty, E. H. J. Org. Chem. 1982, 47, 4808. (c) Taber, D. F.; Raman, K. J. Am. Chem. Soc. 1983, 105, 5935. (d) Taber, D. F.; Petty, E. H.; Raman, K. J. Am. Chem. Soc. 1985, 107, 196. (e) Demonceau, A.; Noels, A. F.; Hubert, A. J.; Teyssie, P. J. Chem. Soc., Chem. Commun. 1981, 688. (f) Taber, D. F.; Ruckle, R. E.; Jr. Tetrahedron Lett. 1985, 26, 3059
    • Recent studies on carbenoid C-H insertion are given in: (a) Cane, D. E.; Thomas, P. J. J. Am. Chem. Soc. 1984, 106, 5295. (b) Taber, D. F.; Petty, E. H. J. Org. Chem. 1982, 47, 4808. (c) Taber, D. F.; Raman, K. J. Am. Chem. Soc. 1983, 105, 5935. (d) Taber, D. F.; Petty, E. H.; Raman, K. J. Am. Chem. Soc. 1985, 107, 196. (e) Demonceau, A.; Noels, A. F.; Hubert, A. J.; Teyssie, P. J. Chem. Soc., Chem. Commun. 1981, 688. (f) Taber, D. F.; Ruckle, R. E.; Jr. Tetrahedron Lett. 1985, 26, 3059.
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    • Recent studies on carbenoid cyclopropanation are found in (b) Doyle, M. P.; van Leusen, D.; Tamblyn, W. H. Synthesis 1981, 787. (c) Anciaux, A. J.; Hubert, A. J.; Noels, A. F.; Petiniot, N.; Teyssie, P. J. Org. Chem. 1980, 45, 695
    • Recent studies on carbenoid cyclopropanation are found in: (a) Doyle, M. P.; Dorow, R. L.; Buhro, W. E.; Griffin, J. H.; Tamblyn, W. H.; Trudell, M. L. Organometallics 1984, 3, 44. (b) Doyle, M. P.; van Leusen, D.; Tamblyn, W. H. Synthesis 1981, 787. (c) Anciaux, A. J.; Hubert, A. J.; Noels, A. F.; Petiniot, N.; Teyssie, P. J. Org. Chem. 1980, 45, 695.
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    • Carbenoids have been used for intramolecular X-H insertion (b) Ratcliffe, R. W.; Salzmann, T. N.; Christensen, B. G. Tetrahedron Lett. 1980, 21, 31. (c) Salzmann, T. N.; Ratcliffe, R. W.; Christensen, B. G. Tetrahedron Lett. 1980, 21, 1193. (d) Melillo, D. G.; Shinkai, I.; Liu, T.; Ryan, K.; Sletzinger, M. Tetrahedron Lett. 1980, 21, 2783. (e) Salzmann, T. N.; Ratcliffe, R. W.; Christensen, B. G. Bouffard, F. A. J. Am. Chem. Soc. 1980, 102, 6163. (f) Yamamoto, S.; Itani, H.; Takahashi, H.; Tsuji, T.; Nagata, W. Tetrahedron Lett. 1984, 25, 4545. (g) Campbell, M. M.; Jasys, V. J. Heterocycles 1981, 16, 1487. (h) Moody, C. J.; Pearson, C. J.; Lawton, G. Tetrahedron Lett. 1985, 26, 3171
    • Carbenoids have been used for intramolecular X-H insertion: (a) Cama, L. D.; Christensen, B. G. Tetrahedron Lett. 1978, 4233. (b) Ratcliffe, R. W.; Salzmann, T. N.; Christensen, B. G. Tetrahedron Lett. 1980, 21, 31. (c) Salzmann, T. N.; Ratcliffe, R. W.; Christensen, B. G. Tetrahedron Lett. 1980, 21, 1193. (d) Melillo, D. G.; Shinkai, I.; Liu, T.; Ryan, K.; Sletzinger, M. Tetrahedron Lett. 1980, 21, 2783. (e) Salzmann, T. N.; Ratcliffe, R. W.; Christensen, B. G. Bouffard, F. A. J. Am. Chem. Soc. 1980, 102, 6163. (f) Yamamoto, S.; Itani, H.; Takahashi, H.; Tsuji, T.; Nagata, W. Tetrahedron Lett. 1984, 25, 4545. (g) Campbell, M. M.; Jasys, V. J. Heterocycles 1981, 16, 1487. (h) Moody, C. J.; Pearson, C. J.; Lawton, G. Tetrahedron Lett. 1985, 26, 3171.
    • (1978) Tetrahedron Lett. , pp. 4233
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    • An attempt to accomplish an intramolecular N-H insertion on 2-substituted 1,2-diazetidin-3-ones is described by
    • An attempt to accomplish an intramolecular N-H insertion on 2-substituted 1,2-diazetidin-3-ones is described by: Taylor, E. C.; Davies, H. M. L. J. Org. Chem. 1984, 49, 113.
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    • (a) Cox, M. T.; Jackson, A. H.; Kenner, G. W.; McCombie, S. W.; Smith, K. M. J. Chem. Soc. Perkin Trans. 1 1974, 516. (b) Bram, G.; Vilkas, M. Bull. Soc. Chim. Fr. 1964, 945. (c) Bates, H. A.; Rapoport, H. J. Am. Chem. Soc. 1979, 101, 1259.
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    • (a) Pinnick, H. W.; Chang, Y.-H. J. Org. Chem. 1978, 43, 4662. (b) Luly, J. R.; Rapoport, H. J. Am. Chem. Soc. 1983, 105, 2859.
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    • Synthesis
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    • An interesting synthesis of 2-alkyl-3-oxotetrahydrothiophene from 4-(alkylthio)-1-diazobutan-2-one is the only example of a carbenoid reaction used to synthesize any of the heterocycles we have made. This reaction proceeds via intramolecular carbenoid addition to sulfur to give an intermediate cyclic sulfur ylide that then rearranges to the product either via a [2, 3] sigmatropic shift or a Stevens rearrangement, depending upon the alkylthio group
    • An interesting synthesis of 2-alkyl-3-oxotetrahydrothiophene from 4-(alkylthio)-1-diazobutan-2-one is the only example of a carbenoid reaction used to synthesize any of the heterocycles we have made. This reaction proceeds via intramolecular carbenoid addition to sulfur to give an intermediate cyclic sulfur ylide that then rearranges to the product either via a [2,3] sigmatropic shift or a Stevens rearrangement, depending upon the alkylthio group. Kondo, K.; Ojima, I. J. Chem. Soc., Chem. Commun. 1972, 860.
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    • Another route outlined below employed the Blaise reaction for synthesizing 37; however, we found it less satisfactory than the scheme described in the text. (formula omited)
    • Another route (Bellassoued, M.; Gaudemar, M. J. Organomet. Chem. 1974, 81, 139) outlined below employed the Blaise reaction for synthesizing 37; however, we found it less satisfactory than the scheme described in the text. (formula omited)
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    • A similar procedure to that used to protect cysteine was employed by
    • A similar procedure to that used to protect cysteine was employed by: Erickson, B. W.; Merrifield, R. B. J. Am. Chem. Soc. 1973, 95, 3750.
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    • 4; however, hydrogen sulfide did not react
    • 4; however, hydrogen sulfide did not react. Johnson, S. A.; Hunt, H. R.; Neumann, H. M. Inorg. Chem. 1963, 2, 960.
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    • 6a: Greenstein, J. P.; Winitz, M. “Chemistry of the Amino Acids”; Wiley: New York, 1961; Vol. II, p 891. 6b: Sifferd, R. H.; Du Vigneaud, V. J. Biol. Chem. 1935, 108, 753. 6c: Fosker, A. P.; Law, H. D. J. Chem. Soc. 1965, 7305. 6d: Reitz, M. S.; Rodwell, V. W. Methods Enzymol. 1971, 17 (Part B), 159.
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