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Volumn 65, Issue 50, 2009, Pages 10495-10505

Endo-selective Diels-Alder reaction of methacrylonitrile: application to the synthesis of Georgywood

Author keywords

[No Author keywords available]

Indexed keywords

1,2 DIMETHYL 4 (4 METHYLPENT 3 ENYL)CYCLOHEX 3 ENE CARBONITRILE; 1,2 DIMETHYL 4 (4 METHYLPENT 3 ENYL)CYCLOHEX 3 ENECARBONITRILE; 1,2,8,8 TETRAMETHYL 1,2,3,4,5,6,7,8 OCTAHYDRONAPHTHALENE 2 CARBONITRILE; 1,3 DIMETHYL 4 (PROP 1 EN 2 YL)CYCLOHEX 1 ENE; 1,3 DIMETHYL 4 (PROPAN 2 YLIDENE)CYCLOHEX 1 ENE; 2 METHYL 4 (4 METHYLPENT 3 ENYL)CYCLOHEX 3 ENECARBONITRILE; ALUMINUM; BORON; GALLIUM; HALIDE; METHACRYLONITRILE; UNCLASSIFIED DRUG;

EID: 70350703391     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tet.2009.09.089     Document Type: Article
Times cited : (8)

References (78)
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    • Tetracyclone (a), methyl coumalate (b) and furan (c) were not considered for comparison with Homomyrcene 2 due to additional carbonyl, phenyl or oxygen substituents in conjugation with the diene. Endo-selective DA reactions from these dienes and (meth)acrylonitrile have been reported:
    • Tetracyclone (a), methyl coumalate (b) and furan (c) were not considered for comparison with Homomyrcene 2 due to additional carbonyl, phenyl or oxygen substituents in conjugation with the diene. Endo-selective DA reactions from these dienes and (meth)acrylonitrile have been reported:
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    • note
    • All four carbon atoms of an endocyclic conjugated diene are part of a cyclic structure, not to be confused with the endo/exo descriptors of the Diels-Alder transition states. The endo/exo description of the obtained Diels-Alder adducts is identical with the cis/trans description of the diastereomers a and b, respectively.
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    • note
    • Ion resins or acid clays gave no conversion. See Ref. 8 for the use of Zeolites in the DA reaction of cyclopentadiene and methacrylonitrile.
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    • 3 has been reported to catalyze DA reactions of butadiene or isoprene with (meth)acrylonitriles, but no data about endo/exo selectivities were given:
    • 3 has been reported to catalyze DA reactions of butadiene or isoprene with (meth)acrylonitriles, but no data about endo/exo selectivities were given:. Efendiev E.Kh., Rasulbekova T.I., and Akhmedov R.M. Azerbaidzhanskii Khimicheskii Zhurnal (1979) 43-46
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    • Probably due to competing complexation/inactivation of the Lewis acid as experienced in other LA-promoted reactions, see for example Ref. 4b
    • Probably due to competing complexation/inactivation of the Lewis acid as experienced in other LA-promoted reactions, see for example Ref. 4b.
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    • Acidic ion resins or clays gave no conversion up to 80 °C. MANDA reaction of 2a in ethanol showed no effect.
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    • note
    • Equations have been generated by using all the available molecular descriptors and genetic function approximation of Molecular Operating Environment (MOE), version 2007.09, Chemical Computing Group Inc. Montreal, Canada, 2007. The root mean square error of prediction could be probably improved with more accurate experimental data.
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    • Geometry optimizations and Gibbs free energy values in toluene have been computed by applying the COSMO-RS solvent modeling approach (From Quantum Chemistry to Fluid Phase Thermodynamics and Drug Design, Andreas Klamt, Elsevier Science Ltd., Amsterdam, The Netherlands 2005, ISBN: 0-444-51994-7) based on ab inito wavefunctions (HF:svp_ahlrichs/DFT: B97-2//tzvp_alrichs/MP2-SCS) by using Parallel Quantum Solutions (2013 Green Acres Road Suite A, Fayetteville, Arkansas, 72703, U.S.A.) software (version 3.3) at our Quantum Cube parallel computer (8 AMD 2.4 GHz CPUs). For transition state search, TS option was used with a subsequent frequency analysis.
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    • For the thermal DA reaction of an 1,1,2-trialkylsubstituted diene see:
    • For the thermal DA reaction of an 1,1,2-trialkylsubstituted diene see:. Nazarov I.N., and Mavrov M.V. Zh. Obshch. Khim. 29 (1959) 1169-1176
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    • The cisoid conformer of E,E-2f is sterically less hindered than the one of the E,Z-isomer. See for example: Chapter B3
    • The cisoid conformer of E,E-2f is sterically less hindered than the one of the E,Z-isomer. See for example:. Sauer J. Angew. Chem. 79 (1967) 76-94 Chapter B3
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    • Ether-free Grignard-addition to sterically hindered nitriles followed by hydrolysis with strong acids, see for example:
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.