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Volumn 20, Issue 10, 1996, Pages 1047-1060

Catalytic asymmetric hydrogenation of ketopantolactone by rhodium(I) aminophosphine-phosphinite complexes. A theoretical analysis by molecular mechanics and extended Hückel calculations

Author keywords

Asymmetric hydrogenation; Chiral bisphosphines; H ckel; Molecular mechanics; Rhodium dihydrides

Indexed keywords


EID: 0006242458     PISSN: 11440546     EISSN: None     Source Type: Journal    
DOI: None     Document Type: Article
Times cited : (7)

References (66)
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    • For recent examples of applications of computational methods to transition-metal intermediates in catalytic pathways, see: (a) Castonguay L. A., Rappé A. K., Casewit C. J., J. Am. Chem. Soc., 1991, 113, 7177.
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    • The use of steric energy resulting from Newtonian mechanics-based molecular modelling techniques is sometimes warranted by the fact that, unlike regioselectivity which can depend on electronic factors, enantioselectivity is almost completely steric. There are however many recent reports which relate on the observation of large electronic effects on the enantioselectivity of catalytic reactions: Schnyder A., Hintermann L., Togni A., Angew. Chem. Int. Ed. Engl., 1995, 34, 931, and references cited therein. In order to keep from the former assumptions, we preferred to base our analyses on total energy which include electronic factors.
    • (1995) Angew. Chem. Int. Ed. Engl. , vol.34 , pp. 931
    • Schnyder, A.1    Hintermann, L.2    Togni, A.3
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    • A combination of molecular mechanics and ab initio methods applicable to the prediction of stereochemistries of Lewis-acid catalyzed reactions of chiral acrylates with dienes has recently been reported: de Pascual-Teresa B., Gonzalez J., Alonsio A., Houk K. N., J. Am. Chem. Soc., 1995, 117, 4347.
    • (1995) J. Am. Chem. Soc. , vol.117 , pp. 4347
    • De Pascual-Teresa, B.1    Gonzalez, J.2    Alonsio, A.3    Houk, K.N.4
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    • CAChe Scientific Inc., 18700 N.W. Walker Road, Building 92-01, Beaverton, OR 97006
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    • note
    • Numerous alternative conformations of the seven-membered metallacycle have been evaluated. In particular, minimizations conducted on a twist-boat conformation with the nitrogen atom in the P(N)-Rh-P(O) plane often led to the distorted chair conformation 2. Therefore, the latter conformation was systematically investigated.
  • 63
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    • The nucleophilic attack of the H atom to the carbonyl C atom yielding an alkoxy rhodium species is commonly accepted for the hydride migration step (see reference 11). The formation of an hydroxyalkyl rhodium species has been suggested to occur in the presence of amines as promotors; see: Chan A. S. C., Landis C. R., J. Mol. Catal., 1989, 49, 165.
    • (1989) J. Mol. Catal. , vol.49 , pp. 165
    • Chan, A.S.C.1    Landis, C.R.2
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    • note
    • 2.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.