Conclusions
-
1.
In contrast to the case of cyanoacetylene, the nucleophilic addition to methyl propiolate takes place with the preferential or exclusive formation of trans products, if steri cally hindered N-nucleophiles and N-, P-, S-nucleophiles with a weakened +M-effect of the central heteroatom are used.
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2.
For the qualitative evaluation of the stereochemical result of the nucleophilic addition reaction to activated acetylenes, it was proposed to use the σR constant of the activating substituent.
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R. G. Kostyanovskii and Yu. I. El'natanov, Izv. Akad. Nauk SSSR, Ser. Khim., 2581 (1983).
R. G. Kostyanovskii, O. A. Yuzhakova, and V. F. Bystrov, Zh. Vses. Khim. Ova.,10, 229 (1965).
J. I. Dickstein and S. I. Miller, “The Chemistry of the Carbon-Carbon Triple Bond, part 2, S. Patai (ed.), Intersci. Publ., Chichester-New York-Brisbane-Toronto (1978), p. 813.
P. T. Trapentsier, I. Ya. Kalvin'sh, É. É. Liepin'sh, and E. Ya. Lukevich, Khim. Geterotsikl. Soedin., 481 (1983).
H. W. Heine, T. R. Hoye, P. G. Willand, and R. C. Hoye, J. Org. Chem.,38, 2984 (1973); R. G. Kostyanovsky, K. S. Zakharov, M. Zaripova, and V. F. Rudtchenko, Tetrahedron Lett., 4207 (1974); R. G. (Kostyanovsky, K. S. Zakharov, M. Zaripova, and V. F. Rudtchenko (Rudchenko), Izv. Akad. Nauk SSSR, Ser. Khim., 875 (1975).
R. Huisgen, K. Herbig, A. Sieql, and H. Huber, Chem. Ber.,99, 2526 (1966).
R. G. Kostyanovskii (Kostyanovsky), Yu. I. Él'natanov, and V. G. Plekhanov, Izv. Akad. Nauk SSSR, Ser. Khim., 2355 (1971); R. G. Kostyanovsky, V. G. Plekhanov, Kh. Khafizov, et al., Org. Mass Spectrum.,7, 1113 (1973).
N. E. Waite, J. C. Tebby, R. S. Ward, and D. H. Williams, J. Chem. Soc. (C), 1100 (1969).
R. Osman and Y. Shvo, Tetrahedron,34, 2321 (1978); Y. Shvo and H. Shanan-Atidi, J. Am. Chem. Soc,91, 6689 (1969).
P. Caramella and K. N. Houk, Tetrahedron Lett.,22, 819 (1981).
I. I. Chervin, M. D. Isobaev, Yu. I. Él'natanov, et al., Izv. Akad. Nauk SSSR, Ser. Khim., 1769 (1981).
R. W. Taft, J. Am. Chem. Soc.,79, 1045 (1957); O. A. Yuzhakova, V. F. Bystrov, and R. G. Kostyanovskii, Izv. Akad. Nauk SSSR, Ser. Khim., 240 (1966); E. N. Tsvetkov and M. I. Kabachnik, Usp. Khim.,40, 177 (1971); M. Charton, Progress in Physical Organic Chemistry, Vol. 13, R. W. Taft (ed.), Wiley, New York (1981), p. 119.
R. N. Haszeldine, J. Chem. Soc, 3490 (1952); W. R. Cullen, D. S. Dawson, and G. E. Styan, Can. J. Chem.,43, 3392 (1965); E. L. Stogryan and S. J. Brois, J. Am. Chem. Soc,89, 605 (1967).
A. N. Pudovik, N. G. Khusainova, and A. B. Ageeva, Zh. Org. Khim.,34, 3938 (1964).
M. M. Kats, É- F. Lavretskaya, I. I. Chervin, et al., Khim.-Farm. Zh., 675 (1987).
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Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 382–391, Februar, 1988.
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Él'natanov, Y.I., Kostyanovskii, R.G. Reactions of N-, P-, and S-nucleophiles with methyl propiolate. Russ Chem Bull 37, 302–311 (1988). https://doi.org/10.1007/BF00957431
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DOI: https://doi.org/10.1007/BF00957431