Triple shifts and thioether assistance in rearrangements associated with an unusual biomethylation of the sterol side chain.
J Org Chem
; 78(3): 935-41, 2013 Feb 01.
Article
em En
| MEDLINE
| ID: mdl-23270431
ABSTRACT
Quantum chemical calculations (B3LYP and MP2) are described for the formation and rearrangements of carbocations derived from the biological methylation reaction that produces 24-propyl sterols in pelagophyte algae. Previous mechanistic proposals are discussed in light of the results of these calculations. Of particular note is the prediction of a new triple-shift rearrangement that is inherently preferred for the biosynthetically relevant carbocations. Our calculations also reveal how these reactions may be affected by intermolecular interactions with S-adenosylmethionine.
Texto completo:
1
Coleções:
01-internacional
Base de dados:
MEDLINE
Assunto principal:
Esteróis
/
Sulfetos
Tipo de estudo:
Risk_factors_studies
Idioma:
En
Ano de publicação:
2013
Tipo de documento:
Article