Journal ArticleDOI
Theoretical Studies of the Oxy Anionic Substituent Effect
TLDR
In this article, the authors employed ab initio generalized valence bond and configuration interaction theoretical methods, and calculated C-H bond energies for H3COH, H3CONa, H 3COK, and H3 CO- leading to bond energies (at 0 K) of 90.7 (the experimental value is 9 1.8 f 1.2), 80.6, 79.0, and 74.2 kcal/mol, respectively.Abstract:
Employing ab initio generalized valence bond and configuration interaction theoretical methods, we calculated C-H bond energies for H3COH, H3CONa, H3COK, and H3CO- leading to bond energies (at 0 K) of 90.7 (the experimental value is 9 1.8 f 1.2), 80.6, 79.0, and 74.2 kcal/mol, respectively. This dramatic decrease in the adjacent bond strength due to an oxy substituent helps explain the oxy anionic substituent effect in which very marked rate enhancements have been obtained.read more
Citations
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Protein Radicals in Enzyme Catalysis.
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O–H hydrogen bonding promotes H-atom transfer from α C–H bonds for C-alkylation of alcohols
TL;DR: The studies indicate a particular role of tetra-n-butylammonium phosphate in enhancing the selectivity for α C-H bonds in alcohols in the presence of allylic, benzylic, α-C=O, and α-ether C–H bonds.
Journal ArticleDOI
Critical Analysis of Antibody Catalysis
TL;DR: Development of improved transition-state analogs, refinements in immunization and screening protocols, and elaboration of general strategies for augmenting the efficiency of first-generation catalytic antibodies are identified as evident, but difficult, challenges for this field.
References
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Book
The chemistry of the carbon-nitrogen double bond
TL;DR: Patai's Chemistry of Functional Groups as mentioned in this paper is one of chemistry's landmark book series in organic chemistry and is the most complete reference available in functional group chemistry, covering all aspects of the chemistry of an important functional group in each volume, with the emphasis not only on the functional group but on the whole molecule.
Journal ArticleDOI
Application of ab initio molecular orbital calculations to the structural moieties of carbohydrates. 3
Journal ArticleDOI
Application of ab initio molecular orbital calculations to the structural moieties of carbohydrates. 5. The geometry of the hydrogen bonds
TL;DR: In this article, the authors used RHF/4-31G level molecular orbital calculations and Boltzmann factors to calculate the room temperature probability distribution of the O--H...O hydrogen-bond angle using a model consisting of two methanol molecules.
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