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Volumn 124, Issue 38, 2002, Pages 11358-11367

Structure and stereodynamics of N,N-bis(silyloxy)enamines

Author keywords

[No Author keywords available]

Indexed keywords

STEREODYNAMICS;

EID: 0037174451     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja026548i     Document Type: Article
Times cited : (26)

References (63)
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    • (d) Ioffe, S. L.; Lyapkalo, I. M.; Makarenkova, L. M. J. Org. Chem. Russ. 1998, 34, 1141 (in Russian); Russ. J. Org. Chem. 1998, 34, 1085 (English translation).
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    • note
    • 3N in the absence of the silylating reagent (see ref 1b).
  • 11
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    • note
    • The angle between the lone pair and the π-system increases along with an increase of the nitrogen's pyramid heights.
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    • The structure of enamines is discussed in the following review: Hickmott, P. W. Tetrahedron 1982, 38, 1975.
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  • 13
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    • The structure of saturated N,N-bis(alkoxy)amines is discussed in the following review: Rudchenko, V. F. Chem. Rev. 1993, 93, 725.
    • (1993) Chem. Rev. , vol.93 , pp. 725
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    • note
    • 29Si NMR at low temperature. A further broadening of the split lines down to 180 K has not been observed.
  • 21
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    • note
    • One has to be careful in comparing the values of activation energy presented in this paper for different processes. Most of the literature data were obtained using different methods and procedures that may strongly affect certain values.
  • 26
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    • Rudchenko, V. F.; Ignatov, S. M.; Chervin, I. I.; Nosova, V. S.; Kostyanovskii, R. G. Izv. Acad. Nauk. SSSR, Ser. Khim. 1986, 1153; Chem. Abstr. 1987, 106, 175847r.
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    • P. W. Hickmott in 1980 formulated the opposite point of view: Ahmed, M. G.; Ahmed, S. A.; Hickmott, P. W. J. Chem. Soc., Perkin Trans. 1 1980, 2383. He suggested that the introduction of a σ-electronegative group (e.g., OAlk) to the nitrogen atom has to increase the efficiency of n-π-conjugation due to the decrease of the electrostatic repulsion of the lone pairs. However, the stereoelectronic effects in the studied structure (substituted N-vinylhydroxylamine) prevented the conjugation of the nitrogen lone pair and C,C double bond. Thus, opposite the expected increase of nucleophilicity, he observed a low activity of the substituted N-vinylhydroxylamine toward some strong electrophiles.
    • (1980) J. Chem. Soc., Perkin Trans. 1 , pp. 2382
    • Ahmed, M.G.1    Ahmed, S.A.2    Hickmott, P.W.3
  • 29
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    • All calculations that are discussed throughout the text were performed using the quantum chemical program PRIRODA: Laikov, D. N. Chem. Phys. Lett. 1997, 281, 151.
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    • The CN rotation potential curve as well as the inversion transition state for ethylenamine (2) have been previously computed by both ab initio and DFT methods: Pugh, J. K.; Streitwieser, A. J. Org. Chem. 2001, 66, 1334. Our results are consistent with these data.
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    • Pugh, J.K.1    Streitwieser, A.2
  • 31
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    • note
    • The presented CN rotation curves for N,N-bis(oxy)enamines 4 and 5 were obtained by scanning the PES (36 points). The CN rotation curves for 2 and 1a were plotted using the saddle points that were computed taking into account the zero-point vibration energy (Table 1). The shape of the CN rotation curve for 2 is known from the literature (ref 19), while that for 1a is supposed to be similar to the shape of the CN rotation curve for 5. For the model enamine 3 only one conformation (minimum A*) has been computed taking into account the zero-point vibration energy (Table 1).
  • 32
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    • note
    • The AM1-calculated potential energy curve for CN rotation in N.N-bis-(hydroxy)enamine 4 has no minimum B.
  • 33
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    • (a) The decomposition of the rotation potential into a number of functions that describe the different interactions has been previously applied: Radom, L.; Hehre W. J.; Pople J. A. J. Am. Chem. Soc. 1972, 94, 2371. For details see the Supporting Information.
    • (1972) J. Am. Chem. Soc. , vol.94 , pp. 2371
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  • 34
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    • note
    • (b) The plots of steric and conjugative constituents of the CN rotation potential for compounds 2, 4, and 1a are presented in Supporting Information.
  • 35
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    • note
    • We equated the value of the steric energy function to zero in the point of conformation B, since this procedure enables us to evaluate the steric and conjugative energies in the other points.
  • 36
    • 2142771969 scopus 로고    scopus 로고
    • note
    • This phenomenon will be a subject of our special studies.
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    • note
    • In the literature we failed to find the crystal structures of the enamines that would be the close structural analogues of BENAs 1k and 1o studied herein. The enamines 9 and 10, presented in Table 4, were selected from the number of described structures, since they contain the most planar and the most pyramidal nitrogen atoms, respectively.
  • 39
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    • English translation
    • Antipin, M. Yu.; Struchkov, Yu. T.; Shishkov, I. F.; Golubinsky. A. V.; El'fimova, T. L.; Vilkov, L. V.; Bredikhin, A. A.; Vereshchagin, A. N.; Ignatov, S. M.; Rudchenko, V. F.; Kostyanovsky, R. G. Izv. Acad. Nauk. SSSR, Ser. Khim. 1986, 2235 (in Russian); Bull. Acad. Sci. USSR Div. Chem. Sci. 1986, 2040 (English translation).
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    • note
    • The typical dependence of the spectra of BENAs on temperature is presented in the Supporting Information.
  • 45
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    • English translation
    • 2 is evidence that the dynamic process in BENAs is also hindered N inversion.
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    • The introduction of π-electron-withdrawing groups to the nitrogen atom significantly decreases the activation barrier for N inversion in the series of aziridines: Kessler, V. H. Angew. Chem. 1970, 227.
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    • For example, see ref 7b
    • For example, see ref 7b.
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    • note
    • max = 256 nm [log ε = 3.8].
  • 50
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    • note
    • N2′-type mechanism has been formerly postulated for the reaction of BENAs with amines (ref 1a).
  • 51
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    • note
    • For the results of the investigations into the mechanism of the reaction of BENAs with N-centered nucleophiles, see: Lesiv, A. V.; Ioffe, S. L.; Strelenko, Y. A.; Tartakovsky, V. A. Helv. Chim. Acta. in press.
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    • note
    • 3 = Me. Scheme 3).
  • 58
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    • in Russian
    • Zalukajevs, L.; Vanags, E. J. Gen. Chem. USSR 1956, 26, 3115 (in Russian); 1956, 26, 3469 (English translation); Chem. Abstr. 1957, 51, 8668b.
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    • English translation
    • Zalukajevs, L.; Vanags, E. J. Gen. Chem. USSR 1956, 26, 3115 (in Russian); 1956, 26, 3469 (English translation); Chem. Abstr. 1957, 51, 8668b.
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    • The DYNNMR program has been used for iteration: Shastin, A. V.; Godovikova, T. I.; Golova, S. P.; Povorin, M. V.; Dmitriev, D. E.; Dekaprilevich, M. O.; Strelenko, Yu. A.; Struchkov, Yu. T.; Khmelnytsky, L. I.; Korsunsky, B. L. Khim. Geter. Soed. 1995, 5, 679 (in Russian); Chem. Abstr. 1996, 124, 145027c.
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.