Catalyst-substrate helical character matching determines enantiomeric excess

Tetrahedron

Volumn 61, Issue 30, 2005, Pages 7134-7143

  Wang, David Zhigang ^a  

^a Och Spine at New York Presbyterian Hospitals   (United States)

Author keywords

Asymmetric catalysis; Chirality; Helicity; Homohelical interaction; Polarizability

Indexed keywords

ARTICLE; CHEMICAL INTERACTION; CHIRALITY; ELECTRON; ENANTIOSELECTIVITY; ENERGY TRANSFER; MOLECULAR DYNAMICS; POLARIZATION; PRIORITY JOURNAL; RIGIDITY; THEORETICAL STUDY;

EID: 20544466200     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tet.2005.05.059     Document Type: Article

References (81)

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2. D.Z. Wang Chirality 17 2005 S177 The paper also examines the relationships between helical electronic effects and steric and other effects in stereochemical controls in the general context of asymmetric catalysis
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10. An alternative statement of this principle would be that in a reaction a catalyst that effects a high ee towards a substrate would effect lower ees towards other substrates that have either higher or lower helical characters. Illustrations are given in the text. This principle helps guide the selection of more promising substrates for a catalyst. It is important to note that similarities in substrate helix characters often do not translate into similarities in their structural or steric characters. In asymmetric catalysis this gives a catalyst both specificity (highest ee towards one substrate) and versatility (comparable ees towards many other, helically resemble substrates). See Refs. 1,2,4 for many examples.
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41. 2 bonds are now restricted, rendering such phenyl-Rh interactions to be further weakened by the enhanced π-polarizability anisotropy. These effects lead to a net consequence that the effective polarizability of phenyl ring is substantially reduced thus the catalyst ring helical character of 5n is much lower than those of other catalysts of similar aromatic-versus-alkyl P-substituents but in an unstrained electronic environment, such as 4b-d, and may be close to that of the perfect catalyst 5. This, in conjunction with steric effects posed by its rigid structure, might have made it a highly enantioselective catalyst. See: T. Imamoto, K.V.L. Crépy, and K. Katagiri Tetrahedron: Asymmetry 15 2004 2213
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