Delineation of the factors governing reactivity and selectivity in epoxide formation from ammonium ylides and aldehydes

Organic and Biomolecular Chemistry

Volumn 4, Issue 4, 2006, Pages 621-623

  Robiette, Raphaël ^a   Conza, Matteo ^a   Aggarwal, Varinder K ^a  

^a UNIVERSITY OF BRISTOL   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

AMINES; AMMONIUM COMPOUNDS; AROMATIC COMPOUNDS; BIOCHEMISTRY; PROBABILITY DENSITY FUNCTION; SUBSTITUTION REACTIONS;

AMMONIUM YLIDES; DELINEATION; DIASTEREOSELECTIVITY; RING CLOSURE;

ALDEHYDES;

EID: 32544457114     PISSN: 14770520     EISSN: None     Source Type: Journal    
DOI: 10.1039/b516926g     Document Type: Article

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23. A set of constrained geometry optimization at successively smaller values of the C-C distance was carried out to check that the interaction between reactants is indeed uniformly attractive The energies reported here are electronic energies, while kinetics depend on the corresponding free energies, so entropic considerations need to be taken into account. For addition of the ylide and epoxidation to occur without reversion to reactants, the elimination TS needs to lie lower in free energy than the variational TS for cleavage into reactants. As a rough estimate, the loose, variational cleavage TS may have a slightly higher entropy (hence more favourable free energy) than the tighter elimination TS, but this should not make the relative free energies drastically different to the relative potential energies. The cleavage TS will have a potential energy very close to, if a bit lower than, that of the reactants. The small difference in potential energy between the two TS shown in Fig. 1 will translate into a small difference in their free energies, so that changes in substitution could quite easily tune the system either into fully reversible behaviour or completely irreversible behaviour - as suggested by experimental evidence It is worth noting, however, that stabilisation of the ylide might lead to the emergence of a barrier to addition
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