Conservation of helical asymmetry in chiral interactions

Tetrahedron

Volumn 61, Issue 30, 2005, Pages 7125-7133

  Wang, David Zhigang ^a  

^a Howard Hughes Medical Institute   (United States)

Author keywords

Asymmetric catalysis; Chirality; Helicity; Homohelical interaction; Kinetic resolution; Polarizability

Indexed keywords

ARTICLE; CATALYSIS; CHEMICAL INTERACTION; CHIRALITY; ELECTRONICS; ENANTIOSELECTIVITY; MOLECULAR DYNAMICS; MOLECULAR RECOGNITION; PRIORITY JOURNAL; STEREOCHEMISTRY;

EID: 20544439325     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/j.tet.2005.05.058     Document Type: Article

References (50)

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10. When right-handed helicity dominates, the molecule is dextrorotatory at long wavelengths, and left-handed helicity leads to levorotation. As concluded by Brewster in Ref. 5a, 'as a general rule, that a system in which electrons are constrained to right-handed helical paths will give a positive Cotton effect and dextro-rotation at long wavelength, enters, explicitly or implicitly, into all of the major theoretical models of optical activity'. Such a polarizability-bond structure connection thus provides a new way to assign absolute stereochemistry on the basis of optical rotation. See Ref. 10.
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39. That the stereochemical outcomes here could be correlated to the helical electronic interactions between a catalyst and its substrate in their initial association step, without necessarily engaging in those interactions in the transition states of the derivatization step, is somewhat unusual and may be a characteristic of efficient kinetic resolution systems, in which the reaction profiles depend critically on the chiral discrimination of enantiomers by the chiral catalyst. Disruption of an electronically favorable homohelical catalyst-substrate association in the derivatization step should result in an energy penalty that may contribute to a higher transition state barrier.
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50. Wang, D. Z. Tetrahedron 2005, 61, the following paper in this issue see doi:10.1016/j.tet.2005.05.059.