Theoretical revisit of regioselectivities of diels - Alder reactions: Orbital-based reevaluation of multicentered reactivity in terms of reactive hybrid orbitals

Journal of Physical Chemistry A

Volumn 109, Issue 5, 2005, Pages 816-824

  Hirao, Hajime ^a,b   Ohwada, Tomohiko ^a  

^a UNIVERSITY OF TOKYO   (Japan)

^b NOVARTIS PHARMA AG   (Switzerland)

Author keywords

[No Author keywords available]

Indexed keywords

HYDRIDE POTENTIALS; REACTIVITY INDEX; REACTIVITY MODELS; REGIOSELECTIVITY;

ACTIVATION ENERGY; APPROXIMATION THEORY; CARRIER CONCENTRATION; MATHEMATICAL MODELS; PARAMETER ESTIMATION; PROBABILITY DENSITY FUNCTION; STEREOCHEMISTRY;

CHEMICAL REACTIONS;

ARTICLE; CHEMICAL MODEL; CHEMICAL STRUCTURE; ELECTRON;

ELECTRONS; MODELS, CHEMICAL; MODELS, MOLECULAR; MOLECULAR STRUCTURE;

EID: 13444305313     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp048111y     Document Type: Article

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54. Here we comment on the chloro substitution, because experimental data are available for the Diels-Alder reaction of 2-chlorobutadiene with a dienophile bearing an electron-withdrawing group. Hehre et al. theoretically examined the regioselectivity of this reaction (ref 15), and predicted no selectivity. However, the RHO method assigned para selectivity, which is in agreement with the experiment.
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57. k(X). Note that all the elements in C' corresponding to AOs in atoms other than k are zero. Since the MOs are orthogonal to one another, the quantity in eq R1 is equal to the LCMO coefficient of the frontier orbital.
58. ∝(X)
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