Theoretical Evidence of Pyramidalized Bicyclic Serine Enolates in Highly Diastereoselective Alkylations

A new chiral serine equivalent and its enantiomer have been synthesized from (S)- and (R)-N-Bocserine methyl esters (Boc: tert-butyloxy-carbonyl). The use of these compounds as chiral building blocks has been demonstrated in the synthesis of α-alkyl α-amino acids by diastereoselective po tassium eno...

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Detalles Bibliográficos
Autores: Aydillo, C. [0000-0002-0542-967X], Jiménez-Osés, G. [0000-0003-0105-4337], Busto, J.H. [0000-0003-4403-4790], Peregrina, J.M. [0000-0003-3778-7065], Zurbano, M.M. [0000-0001-6370-3537], Avenoza, A. [0000-0002-5465-3555]
Tipo de recurso: artículo
Estado:Versión publicada
Fecha de publicación:2007
País:España
Institución:Universidad de La Rioja (UR)
Repositorio:RIUR. Repositorio Institucional de la Universidad de La Rioja
OAI Identifier:oai:portal.dialnet.es:doc/5bbc6912b750603269e814a0
Acceso en línea:https://investigacion.unirioja.es/documentos/5bbc6912b750603269e814a0
Access Level:acceso abierto
Palabra clave:Ab initio calculations
Alkylation
Amino acids
Asymmetric synthesis
Carbanions
Descripción
Sumario:A new chiral serine equivalent and its enantiomer have been synthesized from (S)- and (R)-N-Bocserine methyl esters (Boc: tert-butyloxy-carbonyl). The use of these compounds as chiral building blocks has been demonstrated in the synthesis of α-alkyl α-amino acids by diastereoselective po tassium enolate alkylation reactions and subsequent acid hydrolyses. Theoretical studies were performed to eluci date the stereochemical outcome of both the formation of five-membered cyclic N,O-acetals and the subsequent alkylation process, which occurs with total retention of configuration. This feature could be explained in terms of the high degree of pyramidalization of enolate intermediates. © 2007 Wiley-VCH Verlag GmbH & Co. KGaA.