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Volumn 74, Issue 9, 2009, Pages 3551-3553

Cyclohexanecarbonitriles: Assigning configurations at quaternary centers from 13C NMR CN chemical shifts

Author keywords

[No Author keywords available]

Indexed keywords

DIASTEREOMERS; NMR CHEMICAL SHIFTS; QUATERNARY CENTERS; STEREOCENTER;

EID: 66449126273     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo900286f     Document Type: Article
Times cited : (19)

References (63)
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    • Taken in part from the Ph.D. Thesis of G. Wei, Duquesne University, 2007.
    • Taken in part from the Ph.D. Thesis of G. Wei, Duquesne University, 2007.
  • 3
    • 66449101689 scopus 로고    scopus 로고
    • North, M. Nitriles: General Methods and Aliphatic Nitriles. In ComprehensiVe Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: Oxford, UK, 1991; 3, pp 611-640.
    • (b) North, M. Nitriles: General Methods and Aliphatic Nitriles. In ComprehensiVe Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon: Oxford, UK, 1991; Vol. 3, pp 611-640.
  • 5
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    • Preparation and Synthetic Applications of Cyano Compounds
    • Patai, S, Ed, Wiley: New York
    • (b) Fatiadi, A. J. Preparation and Synthetic Applications of Cyano Compounds. In The Chemistry of Functional Groups. Supplement C; Patai, S., Ed.: Wiley: New York, 1983; pp 1157-1190.
    • (1983) The Chemistry of Functional Groups. Supplement C , pp. 1157-1190
    • Fatiadi, A.J.1
  • 7
    • 0002913007 scopus 로고
    • Terpenoids
    • Mann, J, Davidson, R. S, Hobbs, J. B, Banthorpe, D. V, Harborne, J. B, Eds, Addison Wesley Longman Ltd, Reading, MA, Chapter 5
    • Banthorpe, D. V. Terpenoids. In Natural Products: Their Chemistry and Biological Significance; Mann, J., Davidson, R. S., Hobbs, J. B., Banthorpe, D. V., Harborne, J. B., Eds.; Addison Wesley Longman Ltd.: Reading, MA, 1994; Chapter 5.
    • (1994) Natural Products: Their Chemistry and Biological Significance
    • Banthorpe, D.V.1
  • 9
    • 34848916346 scopus 로고    scopus 로고
    • For a recent example see: Fleming, F. F.; Liu, W.; Ghosh, S.; Steward, O. W. Angew. Chem., Int. Ed. 2007, 46, 7098. For a review of cyclic nitrile alkylations see: Fleming, F. F.; Shook, B. C. Tetrahedron 2002, 58, 1.
    • For a recent example see: Fleming, F. F.; Liu, W.; Ghosh, S.; Steward, O. W. Angew. Chem., Int. Ed. 2007, 46, 7098. For a review of cyclic nitrile alkylations see: Fleming, F. F.; Shook, B. C. Tetrahedron 2002, 58, 1.
  • 10
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    • Podlech, J
    • Podlech, J.
  • 11
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    • Introduction of the Cyano Group by Conjugate Addition, Houben-Weyl, Murahashi, S.-i, Ed, Georg Thieme: Stuttgart, Germany
    • (a) Introduction of the Cyano Group by Conjugate Addition. In Science of Synthesis (Houben-Weyl); Murahashi, S.-i., Ed.; Georg Thieme: Stuttgart, Germany, 2004; Vol. 19, pp 311-324.
    • (2004) Science of Synthesis , vol.19 , pp. 311-324
  • 15
    • 66449095496 scopus 로고
    • For an example where NMR was unable to resolve the stereochemistry of a nitrile-bearing carbon see
    • For an example where NMR was unable to resolve the stereochemistry of a nitrile-bearing carbon see: Smith, P. H.; Fine, S. M.; Del Paggio, A. A. Acta Crystallogr., Sect. C: Cryst. Struct. Commun. 1985, C41, 581.
    • (1985) Acta Crystallogr., Sect. C: Cryst. Struct. Commun , vol.C41 , pp. 581
    • Smith, P.H.1    Fine, S.M.2    Del Paggio, A.A.3
  • 17
    • 84868947106 scopus 로고    scopus 로고
    • Nagata, W.; Yoshioka, M.; Narisada, M.; Watanabe, H. Tetrahedron Lett. 1964, 3133. No citations of these references were located using SciFinder Scholar (02/06/09). Whereas an empirical correlation exists between the band intensity and configuration, the stretching frequency, at least for cyclohexanecarbonitrile, is the same for both diastereomers: Horntvedt, H. T.; Klæboe, P. Acta Chem. Scand. 1975, 29, 528.
    • (b) Nagata, W.; Yoshioka, M.; Narisada, M.; Watanabe, H. Tetrahedron Lett. 1964, 3133. No citations of these references were located using SciFinder Scholar (02/06/09). Whereas an empirical correlation exists between the band intensity and configuration, the stretching frequency, at least for cyclohexanecarbonitrile, is the same for both diastereomers: Horntvedt, H. T.; Klæboe, P. Acta Chem. Scand. 1975, 29, 528.
  • 18
    • 49149136294 scopus 로고    scopus 로고
    • Kinetic hydrocyanation of decalones installs axial nitriles whereas both isomers can form under thermodynamic conditions: Agami, C, Fadlallah, M, Levisalles, J. Tetrahedron 1981, 37, 903
    • Kinetic hydrocyanation of decalones installs axial nitriles whereas both isomers can form under thermodynamic conditions: Agami, C.; Fadlallah, M.; Levisalles, J. Tetrahedron 1981, 37, 903.
  • 22
    • 66449128054 scopus 로고    scopus 로고
    • Searches conducted on December 17, 2008 using SciFinder Scholar.
    • Searches conducted on December 17, 2008 using SciFinder Scholar.
  • 23
    • 66449114763 scopus 로고    scopus 로고
    • Insufficient data prevented the analysis from being extended to 5- and 7-membered cyclic nitriles. Exploratory comparisons of the 13C NMR chemical shifts for 2-cyanopiperidines show minimal differences for the nitrile carbon in axial and equatorial diastereomers: Wolckenhauser, S. A.; Rychnovsky, S. D. Tetrahedron 2005, 61, 3371.
    • Insufficient data prevented the analysis from being extended to 5- and 7-membered cyclic nitriles. Exploratory comparisons of the 13C NMR chemical shifts for 2-cyanopiperidines show minimal differences for the nitrile carbon in axial and equatorial diastereomers: Wolckenhauser, S. A.; Rychnovsky, S. D. Tetrahedron 2005, 61, 3371.
  • 24
    • 4944263814 scopus 로고    scopus 로고
    • Heteroatom substituents on the nitrile-bearing carbon induce different anisotropy effects. From the limited available chemical shifts of cyclohexanone cyanohydrins, equatorially oriented nitriles resonate further downfield than their axial counterparts in the 13C NMR: Kobler, C.; Bohrer, A.; Effenberger, F. Tetrahedron 2004, 60, 10397.
    • Heteroatom substituents on the nitrile-bearing carbon induce different anisotropy effects. From the limited available chemical shifts of cyclohexanone cyanohydrins, equatorially oriented nitriles resonate further downfield than their axial counterparts in the 13C NMR: Kobler, C.; Bohrer, A.; Effenberger, F. Tetrahedron 2004, 60, 10397.
  • 25
    • 66449121187 scopus 로고    scopus 로고
    • Many of the configurational assignments were based on crystallographic analyses or made by chemical correlation. Configurational assignments were often evident from diagnostic coupling constants at other ring positions and in other cases were made by assuming that the small nitrile adopts the more sterically demanding axial orientation
    • Many of the configurational assignments were based on crystallographic analyses or made by chemical correlation. Configurational assignments were often evident from diagnostic coupling constants at other ring positions and in other cases were made by assuming that the small nitrile adopts the more sterically demanding axial orientation.
  • 26
    • 66449117481 scopus 로고    scopus 로고
    • The structures, the 13C NMR shifts, and the references are collated in tables provided in the Supporting Information.
    • The structures, the 13C NMR shifts, and the references are collated in tables provided in the Supporting Information.
  • 27
    • 66449110402 scopus 로고    scopus 로고
    • Long chain nitriles resonate from d119-122 (refs 20a and 20b) while alkylsubstituted benzonitriles resonate from d117-121 (ref 20c).
    • Long chain nitriles resonate from d119-122 (refs 20a and 20b) while alkylsubstituted benzonitriles resonate from d117-121 (ref 20c).
  • 31
    • 66449105651 scopus 로고    scopus 로고
    • Aromatic methine signals occasionally extend into the nitrile region but are readily differentiated from the quaternary nitrile signals by DEPT NMR
    • Aromatic methine signals occasionally extend into the nitrile region but are readily differentiated from the quaternary nitrile signals by DEPT NMR.
  • 56
    • 0005558568 scopus 로고    scopus 로고
    • For interaction of the carbonyl p-system with the nitrile see: (a) Agami, C.; Kazakos, A.; Levisalles, J.; Sevin, A. Tetrahedron 1980, 36, 2977.
    • For interaction of the carbonyl p-system with the nitrile see: (a) Agami, C.; Kazakos, A.; Levisalles, J.; Sevin, A. Tetrahedron 1980, 36, 2977.
  • 58
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    • Cross, A. D.; Harrison, I. T. J. Am. Chem. Soc. 1963, 85, 3223. The effect of adjacent carbonyl groups is evident in nitriles i and ii where the quaternary nitriles resonate in the normal region while the tertirary nitriles resonate abnormally upfield. The assignment of the nitrile carbon resonances is made by analogy to the chemical shifts of similar -oxonitiles (ref 32a) which differs from the assignment in the original report (ref 32b).
    • Cross, A. D.; Harrison, I. T. J. Am. Chem. Soc. 1963, 85, 3223. The effect of adjacent carbonyl groups is evident in nitriles i and ii where the quaternary nitriles resonate in the "normal" region while the tertirary nitriles resonate abnormally upfield. The assignment of the nitrile carbon resonances is made by analogy to the chemical shifts of similar -oxonitiles (ref 32a) which differs from the assignment in the original report (ref 32b).
  • 62
    • 66449104780 scopus 로고    scopus 로고
    • The conformational mobility of the cis-decalin (8′aS)-methyl-6′-oxo-octahydro-spiro[[1,3]dioxolane-2, 2′-naphthalene, 4′aR)-carbonitrile (ref 34a) averages the anisotropy induced by the adjacent bonds: Johan Winne, personal communication
    • The conformational mobility of the cis-decalin (8′aS)-methyl-6′-oxo-octahydro-spiro[[1,3]dioxolane-2, 2′-naphthalene]-(4′aR)-carbonitrile (ref 34a) averages the anisotropy induced by the adjacent bonds: Johan Winne, personal communication.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.