An ab initio study of the rearrangement of carbonyl compounds to oxacarbenes

1977 ◽  
Vol 66 (1) ◽  
pp. 298-302 ◽  
Author(s):  
Julianna A. Altmann ◽  
I. G. Csizmadia ◽  
Keith Yates ◽  
Peter Yates
Keyword(s):  
Ab Initio ◽  
Carbonyl Compounds ◽  
Ab Initio Study

On the conformational preferences of α,β-unsaturated carbonyl compounds. An ab initio study

1996 ◽  
Vol 362 (2) ◽  
pp. 187-197 ◽  
Author(s):  
JoséI. García ◽  
JoséA. Mayoral ◽  
Luis Salvatella ◽  
Xavier Assfeld ◽  
Manuel F. Ruiz-López
Keyword(s):  
Ab Initio ◽  
Carbonyl Compounds ◽  
Ab Initio Study ◽  
Conformational Preferences

The reactions of alkoxide-alkanol negative ions with carbonyl compounds. An ion cyclotron resonance and ab initio study

1982 ◽  
Vol 35 (12) ◽  
pp. 2471 ◽  
Author(s):  
G Klass ◽  
JC Sheldon ◽  
JH Bowie
Keyword(s):  
Ab Initio ◽  
Carbonyl Compounds ◽  
Cyclotron Resonance ◽  
Negative Ions ◽  
Negative Ion ◽  
Reaction Pathways ◽  
Ion Cyclotron Resonance ◽  
Ab Initio Study ◽  
Reaction Sequence ◽  
Stable Product

Simple alkyl aldehydes, ketones and esters containing the unit >: CH-CO-react with alkoxide-alkanol negative ions [RO----HOR] to form stable [M+RO-] negative ions (neutral denoted by M). The initial intermediate in the reaction sequence is produced by the formation of a hydrogen bond between the negatively charged oxygen of [RO----HOR] and the hydrogen of the > >CH-CO- unit. This intermediate decomposes to the stable product ion by two reaction sequences: (i) by direct elimination of ROH, and (ii) by rearrangement to a decomposing 'doubly-solvated' negative ion in which the central hydrogen of [RO----HOR] and the hydrogen of the >CH-CO unit become identical. As both reaction pathways are complex, all intermediates and certain transition states have been properly defined by using ab initio calculations at the 4-31G level.

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