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Volumn 72, Issue 4, 2007, Pages 1431-1436

Metalated nitriles: Chelation-controlled cyclizations to cis and trans hydrindanes and decalins

Author keywords

[No Author keywords available]

Indexed keywords

DECALINS; HYDRINDANES; LITHIUM ALKOXIDE;

EID: 33846965282     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo062270r     Document Type: Article
Times cited : (20)

References (89)
  • 6
    • 33846967312 scopus 로고    scopus 로고
    • -1: Eliel, Ernest L.; Wilen, Samuel H.; Mander, Lewis N. In Stereochemistry of Organic Compounds; Wiley: New York, 1994; pp 696-7.
    • -1: Eliel, Ernest L.; Wilen, Samuel H.; Mander, Lewis N. In Stereochemistry of Organic Compounds; Wiley: New York, 1994; pp 696-7.
  • 7
    • 0004088819 scopus 로고
    • Rappoport. Z, Ed, Interscience Publishers: New York, Chapter 5
    • Sheppard, W. A. In The Chemistry of the Cyano Group; Rappoport. Z., Ed.; Interscience Publishers: New York, 1970; Chapter 5.
    • (1970) The Chemistry of the Cyano Group
    • Sheppard, W.A.1
  • 37
    • 2542514849 scopus 로고    scopus 로고
    • Fluxional mixtures of N- and C-metalated nitriles are observed in some instances: Sott, R.; Granander, J.; Hilmersson, G. J. Am. Chem. Soc. 2004, 126, 6798.
    • Fluxional mixtures of N- and C-metalated nitriles are observed in some instances: Sott, R.; Granander, J.; Hilmersson, G. J. Am. Chem. Soc. 2004, 126, 6798.
  • 38
    • 0000556636 scopus 로고    scopus 로고
    • N-C-X angle where X is the midpoint between the two substituents at the anionic carbon: Wiberg, K. B.; Castejon, H. J. Org. Chem. 1995, 60, 6327.
    • N-C-X angle where X is the midpoint between the two substituents at the anionic carbon: Wiberg, K. B.; Castejon, H. J. Org. Chem. 1995, 60, 6327.
  • 39
    • 0037263577 scopus 로고    scopus 로고
    • For a discussion of the inversion barrier and mechanism see
    • For a discussion of the inversion barrier and mechanism see: Carlier, P. R. Chirality 2003, 15, 340.
    • (2003) Chirality , vol.15 , pp. 340
    • Carlier, P.R.1
  • 43
    • 0033550167 scopus 로고    scopus 로고
    • Chelation of nitriles by lithium cations is directly analagous to the chelation of organolithiums with proximal alkenes and aromatic π systems: (a) Harris, C. R, Danishefsky, S. J. J. Org. Chem. 1999, 64, 8434
    • Chelation of nitriles by lithium cations is directly analagous to the chelation of organolithiums with proximal alkenes and aromatic π systems: (a) Harris, C. R.; Danishefsky, S. J. J. Org. Chem. 1999, 64, 8434.
  • 54
    • 0035930002 scopus 로고    scopus 로고
    • For a related interaction between fluorine and the nitrile π-electrons see
    • For a related interaction between fluorine and the nitrile π-electrons see: Nishide, K.; Hagimoto, Y.; Hasegawa, H.; Shiro, M.; Node, M. Chem. Commun. 2001, 2394.
    • (2001) Chem. Commun , pp. 2394
    • Nishide, K.1    Hagimoto, Y.2    Hasegawa, H.3    Shiro, M.4    Node, M.5
  • 55
    • 33846959670 scopus 로고    scopus 로고
    • 6 that preferentially cyclizes to the cis-decalin 9 for geometric reasons (cf. 4 → 5a′ → 6. Scheme 1).
    • 6 that preferentially cyclizes to the cis-decalin 9 for geometric reasons (cf. 4 → 5a′ → 6. Scheme 1).
  • 58
    • 0001018933 scopus 로고    scopus 로고
    • 2 leads directly to N-metalated nitriles: Koch, R.; Wiedel, B.; Anders, E. J. Org. Chein. 1996, 61, 2523.
    • 2 leads directly to N-metalated nitriles: Koch, R.; Wiedel, B.; Anders, E. J. Org. Chein. 1996, 61, 2523.
  • 59
    • 33846989643 scopus 로고    scopus 로고
    • Chelation in THF is favored because the lithium is maintained in close proximity by the strong oxygen-lithium bond whereas the weaker Lewis acid interaction observed in 11 requires the less coordinating solvent benzene to be effective
    • Chelation in THF is favored because the lithium is maintained in close proximity by the strong oxygen-lithium bond whereas the weaker Lewis acid interaction observed in 11 requires the less coordinating solvent benzene to be effective.
  • 62
    • 33845550632 scopus 로고    scopus 로고
    • d (a) Olah, G. A.; Husain, A.; Singh, B. P.; Mehrotra, A. K. J. Org. Chem. 1983, 48, 3667.
    • d (a) Olah, G. A.; Husain, A.; Singh, B. P.; Mehrotra, A. K. J. Org. Chem. 1983, 48, 3667.
  • 68
    • 33645396229 scopus 로고    scopus 로고
    • Although the axial β-hydroxynitriles are the minor components in this sequence, several strategies exist for selectively reducing the oxonitrile precursor into either diastereomer: Fleming, F. F, Iyer, P. S. Synthesis 2006, 893
    • Although the axial β-hydroxynitriles are the minor components in this sequence, several strategies exist for selectively reducing the oxonitrile precursor into either diastereomer: Fleming, F. F.; Iyer, P. S. Synthesis 2006, 893.
  • 69
    • 0001732026 scopus 로고    scopus 로고
    • The two syn axial interactions with the forming methylene carbon are probably less than the assigned 0.85 kcal mol-1 since the transition state for nitrile anion alkylations is early: Bare, T. H, Hershey, N. D, House, H. O, Swain, C. G. J. Org. Chem. 1972, 37, 997
    • -1 since the transition state for nitrile anion alkylations is early: Bare, T. H.; Hershey, N. D.; House, H. O.; Swain, C. G. J. Org. Chem. 1972, 37, 997.
  • 70
    • 33846983775 scopus 로고    scopus 로고
    • Stereoelectronic effects are purported to be more influential in the transition state and particularly in nonpolar solvents vide infra, Chandrasekhar, S. ARKIVOC 2005, 13, 37
    • Stereoelectronic effects are purported to be more influential in the transition state and particularly in nonpolar solvents (vide infra): Chandrasekhar, S. ARKIVOC 2005, 13, 37.
  • 71
    • 33846990311 scopus 로고    scopus 로고
    • The syn-axial interactions of the nitrile and alkoxide groups in 21b and 21c are identical in this comparative analysis.
    • The syn-axial interactions of the nitrile and alkoxide groups in 21b and 21c are identical in this comparative analysis.
  • 72
    • 0037204694 scopus 로고    scopus 로고
    • 2 (1 equiv) and NaH (1 equiv) or MeMgCl (2.1 equiv) causes elimination to the cyclic alkenenitrile: (a) Fleming, F. F.; Shook, B. C. J. Org. Chem. 2002, 67, 3668.
    • 2 (1 equiv) and NaH (1 equiv) or MeMgCl (2.1 equiv) causes elimination to the cyclic alkenenitrile: (a) Fleming, F. F.; Shook, B. C. J. Org. Chem. 2002, 67, 3668.
  • 74
    • 33846977244 scopus 로고    scopus 로고
    • 20a
    • 20a
  • 75
    • 33846972864 scopus 로고    scopus 로고
    • Nitrile 20a cyclizes exclusively to the cis-decalin 25 regardless of the stereochemistry of the nitrile bearing carbon.
    • Nitrile 20a cyclizes exclusively to the cis-decalin 25 regardless of the stereochemistry of the nitrile bearing carbon.
  • 76
    • 33846981008 scopus 로고    scopus 로고
    • 20b
    • 20b
  • 77
    • 33846984116 scopus 로고    scopus 로고
    • The range in yield reflects differences in reaction efficiencies from diastereomeric nitrile precursors
    • The range in yield reflects differences in reaction efficiencies from diastereomeric nitrile precursors.
  • 78
    • 33846971471 scopus 로고    scopus 로고
    • Jones oxidation of 34 and 33 afforded two diastereomeric hydrindanones ix and x with the former being identical with that obtained by Jones oxidation of 30.
    • Jones oxidation of 34 and 33 afforded two diastereomeric hydrindanones ix and x with the former being identical with that obtained by Jones oxidation of 30.
  • 79
    • 33846960606 scopus 로고    scopus 로고
    • 3
    • 3
  • 81
    • 33846941775 scopus 로고    scopus 로고
    • The stereochemistry was determined by conversion to the corresponding p-nitrobezoate xii whose stereochemistry was determined by X-ray crystallography. The authors have deposited the crystallographic data for xii with the Cambridge Crystallographic Data Center (CCDC 626356). The data can be obtained, on request, from the Director, Cambridge Crystallographic Data Center, 12 Union Road, Cambridge, CB2 1EZ, UK.
    • The stereochemistry was determined by conversion to the corresponding p-nitrobezoate xii whose stereochemistry was determined by X-ray crystallography. The authors have deposited the crystallographic data for xii with the Cambridge Crystallographic Data Center (CCDC 626356). The data can be obtained, on request, from the Director, Cambridge Crystallographic Data Center, 12 Union Road, Cambridge, CB2 1EZ, UK.
  • 82
    • 0037144679 scopus 로고    scopus 로고
    • 13C NMR shifts: Dehli. J. R.; Gotor, V. J. Org. Chem. 2002, 67, 6816.
    • 13C NMR shifts: Dehli. J. R.; Gotor, V. J. Org. Chem. 2002, 67, 6816.
  • 83
    • 33846953789 scopus 로고    scopus 로고
    • The ring junction stereochemistry was determined by conversion to the corresponding p-nitrobezoate xiii whose stereochemistry was determined by X-ray crystallography. The authors have deposited the crystallographic data for xiii with the Cambridge Crystallographic Data Center (CCDC 626357). The data can be obtained, on request, from the Director. Cambridge Crystallographic Data Center, 12 Union Road, Cambridge, CB2 1EZ, UK.
    • The ring junction stereochemistry was determined by conversion to the corresponding p-nitrobezoate xiii whose stereochemistry was determined by X-ray crystallography. The authors have deposited the crystallographic data for xiii with the Cambridge Crystallographic Data Center (CCDC 626357). The data can be obtained, on request, from the Director. Cambridge Crystallographic Data Center, 12 Union Road, Cambridge, CB2 1EZ, UK.
  • 84
    • 33846974938 scopus 로고    scopus 로고
    • 2Cl in 41 and 42 are minimal in this 5-membered ring: Eliel, E. L.; Wilen, S. H.; Mander, L. N. In Stereochemistry of Organic Compounds; Wiley: New York, 1994; pp 758-762.
    • 2Cl in 41 and 42 are minimal in this 5-membered ring: Eliel, E. L.; Wilen, S. H.; Mander, L. N. In Stereochemistry of Organic Compounds; Wiley: New York, 1994; pp 758-762.
  • 85
    • 33846975659 scopus 로고    scopus 로고
    • The relative stabilities of cis and trans hydrindanes depends on temperature and substitution pattern, with angularly substituted cis-hydrindanes generally being more stable than their trans-hydrindane counterparts: Eliel, E. L, Wilen, S. H, Mander, L. N. In Stereochemistry of Organic Compounds; Wiley: New York, 1994; pp 774-775
    • The relative stabilities of cis and trans hydrindanes depends on temperature and substitution pattern, with angularly substituted cis-hydrindanes generally being more stable than their trans-hydrindane counterparts: Eliel, E. L.; Wilen, S. H.; Mander, L. N. In Stereochemistry of Organic Compounds; Wiley: New York, 1994; pp 774-775.
  • 86
    • 13644267675 scopus 로고    scopus 로고
    • Metalated nitriles are more electron rich than their neutral parent nitriles: (a) Wu, F.; Foley, S. R.; Burns, C. T.; Jordan, R. F. J. Am. Chem. Soc. 2005, 127, 1841.
    • Metalated nitriles are more electron rich than their neutral parent nitriles: (a) Wu, F.; Foley, S. R.; Burns, C. T.; Jordan, R. F. J. Am. Chem. Soc. 2005, 127, 1841.
  • 88
    • 33846964025 scopus 로고    scopus 로고
    • 2 in THF without HMPA leads to full recovery of 43 indicating that the cyclization is kinetically controlled.
    • 2 in THF without HMPA leads to full recovery of 43 indicating that the cyclization is kinetically controlled.


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