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Volumn 81, Issue 6, 2008, Pages 740-753

"Syn effect" in nucleophilic addition of amines to 1,3-dienyl sulfone and ethyl (E)-2,4-pentadienoate

Author keywords

[No Author keywords available]

Indexed keywords

AROMATICITY; DIETHYLAMINE; ESTER GROUPS; HIGH TEMPERATURES; LOW CONCENTRATIONS; NUCLEOPHILIC ADDITIONS;

EID: 58149307921     PISSN: 00092673     EISSN: 13480634     Source Type: Journal    
DOI: 10.1246/bcsj.81.740     Document Type: Article
Times cited : (11)

References (47)
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    • The syn effect is herein defined as an effect which stabilizes the syn conformation against the steric hindrance at the transition state
    • The "syn effect" is herein defined as an effect which stabilizes the syn conformation against the steric hindrance at the transition state.
  • 5
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    • Related studies on the syn effect:a A. Shibayama, T. Nakamura, T. Asada, T. Shintani, Y. Ukaji, H. Kinoshita, K. Inomata, Bull. Chem. Soc. Jpn. 1997, 70, 381.
    • Related studies on the "syn effect":a) A. Shibayama, T. Nakamura, T. Asada, T. Shintani, Y. Ukaji, H. Kinoshita, K. Inomata, Bull. Chem. Soc. Jpn. 1997, 70, 381.
  • 15
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    • A conjugate addition reaction of piperidine to an α-substituted dienyl sulfone, (2E)-2-tosyl-2,4-pentadiene, produced the corresponding (E)-allylic sulfones stereoselectively: T. Cuvigny, C. Herve du Penhoat, M. Julia, Tetrahedron 1986, 42, 5321.
    • A conjugate addition reaction of piperidine to an α-substituted dienyl sulfone, (2E)-2-tosyl-2,4-pentadiene, produced the corresponding (E)-allylic sulfones stereoselectively: T. Cuvigny, C. Herve du Penhoat, M. Julia, Tetrahedron 1986, 42, 5321.
  • 16
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    • Preliminary results have been reported: M. Yamazaki, S. K. Guha, Y. Ukaji, K. Inomata, Chem. Lett. 2006, 35, 514.
    • Preliminary results have been reported: M. Yamazaki, S. K. Guha, Y. Ukaji, K. Inomata, Chem. Lett. 2006, 35, 514.
  • 17
    • 58149292598 scopus 로고    scopus 로고
    • 2NH (2d) (150mM) to 1 at 25 °C, Z/E ratios of 3d were found to be almost constant (between 75/25 and 73/27) in a period of 92 h.
    • 2NH (2d) (150mM) to 1 at 25 °C, Z/E ratios of 3d were found to be almost constant (between 75/25 and 73/27) in a period of 92 h.
  • 22
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    • G. de la Herrán, C. Murcia, A. G. Csáky7die;, Org. Lett. 2005, 7, 5629.
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    • In the cases of 5c-5e and 5g-5j, the Z/E ratios were determined by the spectra measured in CDCI3 containing CF 3CO2D to separate 1H NMR peaks, and no isomerization was observed for 24 h. Specific chemical shifts used for determination of Z/E ratios, which were measured in CDCI3 containing CF3CO2D, are shown in Experimental Section
    • 2D, are shown in Experimental Section.
  • 24
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    • Reaction conditions: 4 (lOOmM, Et2NH (300 mM, proton source (150mM, I HI, 25 °C, 24h. Without proton source (4% yield; Z/E, 83/17, CF3C03H (pK3, 0;25a 42, 7/93),2 HCO2H (3.7;25a 14, 12/88, 2,4,6-tri(f-butyl)phenol (12.19;25c 10, 66/34, EtOH (17;25a 6, 73/27, i-PrOH (18;225b 5, 82/18, f-BuOH 19;25a5, 83/17
    • 25a5%; 83/17).
  • 25
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    • Radical mechanism could be ruled out because the presence of TEMPO, N-hydroxyphthalimide, or galvinoxyl free radical did not affect the Z/E ratios
    • Radical mechanism could be ruled out because the presence of TEMPO, N-hydroxyphthalimide, or galvinoxyl free radical did not affect the Z/E ratios.
  • 26
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    • Crystal structure of an (E)-l,3-butadienyl sulfone revealed the conformation of its diene moiety to be s-trans: M. Zeller, A. D. Hunter, P. Sampson, N. Chumachenko, Acta Crystallogr., Sect. E 2006, 62, ol369; An X-ray analysis of (E)-2,4-pentan- dienoic acid also proved to be s-trans conformation: F. A. Cotton, J. P. Donahue, C. A. Murillo, J. Am. Chem. Soc. 2003, 125, 5436;
    • Crystal structure of an (E)-l,3-butadienyl sulfone revealed the conformation of its diene moiety to be s-trans: M. Zeller, A. D. Hunter, P. Sampson, N. Chumachenko, Acta Crystallogr., Sect. E 2006, 62, ol369; An X-ray analysis of (E)-2,4-pentan- dienoic acid also proved to be s-trans conformation: F. A. Cotton, J. P. Donahue, C. A. Murillo, J. Am. Chem. Soc. 2003, 125, 5436;
  • 27
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    • Furthermore, methyl (£)-2,4-pentadienoate was reported to be predominantly in the planar s-trans conformation in solution: T. Fueno, K. Yamaguchi, J. Am. Chem. Soc. 1972, 94, 1119.
    • Furthermore, methyl (£)-2,4-pentadienoate was reported to be predominantly in the planar s-trans conformation in solution: T. Fueno, K. Yamaguchi, J. Am. Chem. Soc. 1972, 94, 1119.
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  • 35
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    • An effective n→* interaction cannot occur in the conformation E
    • An effective n→* interaction cannot occur in the conformation E.
  • 36
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    • The order of hyperconjugative electron-donating ability of bonds to carbon has been reported to be C-H > C-C > C-F. See: P. R. Rablen, R. W. Hoffmann, D. A. Hrovat, W. T. Borden, J. Chem. Soc, Perkin Trans. 2 1999, 1719
    • The order of hyperconjugative electron-donating ability of bonds to carbon has been reported to be C-H > C-C > C-F. See: P. R. Rablen, R. W. Hoffmann, D. A. Hrovat, W. T. Borden, J. Chem. Soc, Perkin Trans. 2 1999, 1719.
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    • Both linear and cyclic structures were discussed as to amine dimers: a O. Banjoko, C. Ezeani, J. Chem. Soc, Perkin Trans. 2 1986, 531.
    • Both linear and cyclic structures were discussed as to amine dimers: a) O. Banjoko, C. Ezeani, J. Chem. Soc, Perkin Trans. 2 1986, 531.
  • 39
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    • related MO study on conjugate addition of amines: E. J. Land, C. A. Ramsden, P. A. Riley, Tetrahedron 2006, 62, 4884.
    • related MO study on conjugate addition of amines: E. J. Land, C. A. Ramsden, P. A. Riley, Tetrahedron 2006, 62, 4884.
  • 40
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    • 5c,5e
    • 5c,5e
  • 41
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    • h-f through a double bond in Z isomer was larger than that of E isomer which shows that H and F on a double bond have a trans configuration in Z isomer: T. S. Everett, in Chemistry of Organic Fluorine Compounds II, ed. by M. Hudlicky, A. E. Pavlath, American Chemical Society, Washington, DC, 1995, p. 1042; A recent example of assignment of the stereochemistry of vinyl fluorides: S. Hara, T. Guan, M. Yoshida, Org. Lett. 2006, 8, 2639.
    • h-f through a double bond in Z isomer was larger than that of E isomer which shows that H and F on a double bond have a trans configuration in Z isomer: T. S. Everett, in Chemistry of Organic Fluorine Compounds II, ed. by M. Hudlicky, A. E. Pavlath, American Chemical Society, Washington, DC, 1995, p. 1042; A recent example of assignment of the stereochemistry of vinyl fluorides: S. Hara, T. Guan, M. Yoshida, Org. Lett. 2006, 8, 2639.
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    • 2nd ed, W. A. Benjamin, Inc, Menlo Park, California
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    • House, H.O.1


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.