Origins of regio- and stereochemistry in type 2 intramolecular N-acylnitroso Diels-Alder reactions: a computational study of tether length and substituent effects.
J Org Chem
; 78(8): 4090-8, 2013 Apr 19.
Article
en En
| MEDLINE
| ID: mdl-23477601
ABSTRACT
Quantum mechanical calculations have been used to investigate type 2 intramolecular N-acylnitroso Diels-Alder reactions. Experimentally observed regioselectivities and diastereoselectivities of these reactions have been reproduced using B3LYP/6-31+G(d) DFT calculations. The factors that govern selectivity (i.e., tether length, tether substitution and diene substitution) were systematically investigated. Tethers less than 6 carbon atoms lead to 1,3-regioisomers due to conformational restrictions. Substituents on the tether lead to diastereoselective outcomes dictated by transannular interactions in the transition states. The modest diastereoselectivity of diene-substituted substrates is rationalized as arising from reduction of eclipsing interactions in the flattened diene transition states. This method should prove valuable for planning syntheses involving type 2 intramolecular Diels-Alder reactions.
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1
Colección:
01-internacional
Banco de datos:
MEDLINE
Asunto principal:
Reacción de Cicloadición
/
Compuestos Nitrosos
Idioma:
En
Revista:
J Org Chem
Año:
2013
Tipo del documento:
Article
País de afiliación:
Estados Unidos