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Theoretical Evidence for Pyramidalized Bicyclic Serine Enolates in Highly Diastereoselective Alkylations
Author(s) -
Aydillo Carlos,
JiménezOsés Gonzalo,
Busto Jesús H.,
Peregrina Jesús M.,
Zurbano María M.,
Avenoza Alberto
Publication year - 2007
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200601746
Subject(s) - alkylation , enantiomer , chemistry , serine , bicyclic molecule , stereochemistry , amino acid , alkyl , potassium , organic chemistry , catalysis , enzyme , biochemistry
A new chiral serine equivalent and its enantiomer have been synthesized from ( S )‐ and ( R )‐ N ‐Boc‐serine methyl esters (Boc: tert ‐butyloxycarbonyl). The use of these compounds as chiral building blocks has been demonstrated in the synthesis of α‐alkyl α‐amino acids by diastereoselective potassium enolate alkylation reactions and subsequent acid hydrolyses. Theoretical studies were performed to elucidate 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.