General Papers ARKIVOC 2011 (ix) 354-366
Page 354
©
ARKAT-USA, Inc.
Addition reaction of benzylbenzylidenenamine to lithium enolates of
1,3-dioxolan-4-one: synthesis of 2-phenylisoserines
Lizbeth Juárez-Guerra, Susana Rojas-Lima,* and Heraclio López-Ruiz
Área Adémica de Química,Universidad Autónoma del Estado de Hidalgo, Carretera Pachuca-
Tulancingo Km. 4.5, Ciudad Universitaria, 42184, Mineral de la Reforma Hidalgo, México
E-mail: lima@uaeh.edu.mx
Abstract
The synthesis of two new 2-phenylisoserines, each bearing a quaternary stereocenter is
described. These compounds, which are analogs of the amino acid side chain found in taxol and
taxotere, were obtained by addition of the lithium enolates of (2S,5S)-2-isopropyl-5-phenyl-1,3-
dioxolan-4-one and (2S,5S)-2-tert -butyl-2-methyl-5-phenyl-1,3-dioxolan-4-one to
benzylbenzylideneamine in the presence of BF3
.
O(Et)2. The diastereomeric mixtures were
separated in each case and the absolute configurations thereof were determined by X-ray
analysis.
Keywords: 2-Phenylisoserines, 1,3-dioxolan-4-one, Mannich reaction, benzylbenzyliden-
enamine
Introduction
The Mannich reaction and transformations involving nucleophilic addition to the C=N of imine
derivatives are of significant importance in organic synthesis.
1
Isoserines (α-hydroxy-β-amino
acids) are key molecules present in important bioactive substances such as the anticancer agents
paclitaxel 1, docetaxel 2 and bestatin 3 (Figure 1).
2
Because of their importance, several efficient methods to synthesize isoserines have been
developed. Catalytic asymmetric synthesis and especially asymmetric aminohydroxylation have
been applied to the synthesis of the analogs of the docetaxel side chain.
3
Recently, Hu reported
an efficient synthesis of α-hydroxy-β-aminoesters containing quaternary stereocenters by
trapping imines and diazo compound with oxonium ylide generated in situ from rhodium
carbenoids and an alcohol.
4
Most notably, certain catalytic Mannich-type reactions have
considerable precedent for the preparation of α -hydroxy-β-amino acids derivatives.
5
Bataglia has
developed syntheses of chiral α-substituted isoserines, using cis/trans mixtures of cyclic 1,3-
dioxolan-4-one that were not enatiomerically pure.
6
In order to widen the scope of the 1,3-