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Volumn 60, Issue 7, 2004, Pages 1453-1462

Selectivities in the 1,3-dipolar cycloaddition of nitrile oxides to dicyclopentadiene and its derivatives

Author keywords

1,3 Dipolar cycloaddition; Dicyclopentadiene; Nitrile oxide; Thiele's ester

Indexed keywords

ALDOXIME; DICARBOXYLIC ACID DERIVATIVE; DICYCLOPENTADIENE; DIMETHYLDICYCLOPENTADIENE DICARBOXYLATE; NITRILE; NITRILE OXIDE; NITROALKANE; ORGANIC COMPOUND; SOLVENT; UNCLASSIFIED DRUG;

EID: 0742324458     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tet.2003.12.026     Document Type: Article
Times cited : (33)

References (116)
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    • For recent reviews on π-facial selectivity: (a) Chem. Rev. 1999, 99(5):
    • For recent reviews on π-facial selectivity: (a) Chem. Rev. 1999, 99(5):.
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    • Addition of trifluoroacetonitrile oxide to dicyclopentadiene has been found to give a mixture of isomers, but no attempts have been made to characterize the isomers; the endo cyclopentenyl double bond was hydrogenated making the two regioisomers indistinguishable: see Ref. 18
    • Addition of trifluoroacetonitrile oxide to dicyclopentadiene has been found to give a mixture of isomers, but no attempts have been made to characterize the isomers; the endo cyclopentenyl double bond was hydrogenated making the two regioisomers indistinguishable: see Ref. 18.
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    • For instance, the relative addition constants k for norbornene and cyclopentene in their cycloadditions with benzonitrile oxide are 15.3 and 0.21, respectively. Ethylene (k=1) was taken as the standard dipolarophile, see:
    • For instance, the relative addition constants k for norbornene and cyclopentene in their cycloadditions with benzonitrile oxide are 15.3 and 0.21, respectively. Ethylene (k=1) was taken as the standard dipolarophile, see: Bast K., Christl M., Huisgen R., Mack W. Chem. Ber. 106:1973;3312.
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    • See also Ref. 2b for recent references
    • See also Ref. 2b for recent references.
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    • note
    • While the isomer 7b was isolated in pure form from 7b / 8b mixture by fractional crystallization from ethanol, attempts to separate isomers 7a and 8a were not successful (see Section 5).
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    • note
    • Selective formation of one of the several possible thermally allowed pericyclic reaction products was called periselectivity: see Ref. 7c.
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    • note
    • Presence of excess nitrile oxide precursors (up to 4 equiv. of oxime or nitroalkane) and/or excess reagents did not alter the isomer ratios. In presence of excess dipolarophile, on the other hand, the reaction remained incomplete, but the isomer ratio remained unchanged. However, best yields were obtained when nitrile oxides 1 were generated in presence of the dipolarophile.
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    • For e.g. the bicycloheptenyl double bond in Thiele's ester
    • For e.g. the bicycloheptenyl double bond in Thiele's ester 6b undergoes hydrogenation much faster compared to the cyclopentenyl double bond: see Alder K., Stein G. Annales. 485:1931;223.
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    • For e.g. both the double bonds in dicyclopentadiene
    • For e.g. both the double bonds in dicyclopentadiene 6a are epoxidised at the same rate: see Turner R.B., Meador W.R., Winkler R.E. J. Am. Chem. Soc. 79:1957;4116.
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    • The torsional effects and steric hindrance exerted by the 5-endo H's were blamed for the exo preference: see Ref. 11
    • The torsional effects and steric hindrance exerted by the 5-endo H's were blamed for the exo preference: see Ref. 11.
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    • note
    • w=0.0890. Complete crystallographic data (excluding structure factors) for this structure have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication number CCDC 211238. Copies of the data can be obtained, free of charge, on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (fax:+44-1223-336033 or e-mail: deposit@ccdc.cam.ac.uk).
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.