A simple and direct synthesis of erythro-β-amino-α-hydroxy esters from trans-β-phenylglycidic ester

Article abstract of DOI:10.1081/SCC-120038499

trans-β-Phenylglycidic esters undergo ring opening when treated in tertbutyl alcohol with primary amines (R-NH₂, with R = secondary group or tertiary group), which attacks epoxide exclusively at C-3 and avoids aminolysis of the ester group affording the erythro-β-amino-α-hydroxy esters as the sole product.

Full text of DOI:10.1081/SCC-120038499

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A Simple and Direct Synthesis of
Erythro‐β‐amino‐α‐hydroxy Esters from
trans‐β‐Phenylglycidic Ester
Rafâa Besbes a & Mohamed Rached Ennigrou a
a Laboratoire de Synthèse Organique par voie Organométallique, Faculté des Sciences de
Tunis , Campus Universitaire , 1060, Tunis, Tunisia
Published online: 17 Aug 2006.
To cite this article: Rafâa Besbes & Mohamed Rached Ennigrou (2004) A Simple and Direct Synthesis of
Erythro‐β‐amino‐α‐hydroxy Esters from trans‐β‐Phenylglycidic Ester, Synthetic Communications: An International Journal
for Rapid Communication of Synthetic Organic Chemistry, 34:12, 2185-2194, DOI: 10.1081/SCC-120038499
To link to this article: http://dx.doi.org/10.1081/SCC-120038499
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SYNTHETIC COMMUNICATIONSw
Vol. 34, No. 12, pp. 2185–2194, 2004
A Simple and Direct Synthesis of Erythro-b-
amino-a-hydroxy Esters from trans-b-
Phenylglycidic Ester
*
ˆ
Rafaa Besbes and Mohamed Rached Ennigrou
` ´
Laboratoire de Synthese Organique par voie Organometallique,
´
Faculte des Sciences de Tunis, Campus Universitaire,
Tunis, Tunisia
ABSTRACT
trans-b-Phenylglycidic esters undergo ring opening when treated in tert-
butyl alcohol with primary amines (R–NH2, with R ¼ secondary group
or tertiary group), which attacks epoxide exclusively at C-3 and avoids
aminolysis of the ester group affording the erythro-b-amino-a-hydroxy
esters as the sole product.
Key Words: Erythro-b-amino-a-hydroxy esters; tert-Butyl alcohol;
Biological activity; trans-b-Phenylglycidic ester; Ester group.
*
`
Correspondence: Mohamed Rached Ennigrou, Laboratoire de Synthese Organique
´ ´
par voie Organometallique, Faculte des Sciences de Tunis, Campus Universitaire
1060, Tunis, Tunisia; E-mail: MohamedRached.Ennigrou@fst.rnu.tn.
2185
DOI: 10.1081/SCC-120038499
0039-7911 (Print); 1532-2432 (Online)
www.dekker.com
Copyright # 2004 by Marcel Dekker, Inc.

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Besbes and Ennigrou
INTRODUCTION
b-Phenylglycidic esters are important intermediates for the synthesis of
biologically active compounds.[1–4] Here in, we investigate the reactivity of
these epoxides towards nucleophiles. They are known to be attractive building
blocks for the synthesis of b-amino-a-hydroxy esters 2, moiety in the biologi-
cal activity of compounds that show interesting pharmacological properties
such as bestatin, pepstatin,[1] and taxol.[2,3]
The ring opening of b-phenylglycidic esters has been accomplished with a
variety of different nucleophilic agents and has been extensively studied.[2,4]
However, there are few reports concerning nucleophilic ring opening of these
epoxides by amine reagents, which is the frequently used method for the gener-
ation of b-amino-a-hydroxy esters. Early work showed that epoxides could be
opened with ammonia, benzylamine, and hydrazine, allowing in some cases the
obtention of amide[3,5–9] or a mixture[10] of ester and amide. These methods do
not effect the ring opening of epoxide without an aminolysis of ester group.
However, only two examples which use aromatic amines[5,6,11] or sodium
azide[1,12] as nucleophiles, readily gave the ester product. It is worthy to note
that early literature[5,6] gives scant information and some results reported on
the direction of opening of epoxide are somewhat conflicting.
Here, we report a total regio-, chemo-, and stereoselective synthesis of
erythro-b-amino-a-hydroxy esters 2, in one step, from the reaction of trans-
b-phenylglycidic ester as starting materials, easily prepared from Darzens
reaction,[13] with primary amines (R–NH2, with R ¼ secondary or tertiary
group) under refluxing in tert-butyl alcohol (Sch. 1). Note that the traditional
preparation of 2 requires more than one step.[3,4f,14]
The mechanism of formation maybe understood as one in which the alco-
hol acted as a weak acid, protonating[15] the epoxide and participate in its
opening by the nucleophilic attack of amine exclusively to the C-3 leading
to the trans opening product (erythro ester). When reaction is carried out in
a non-protic solvent such as toluene or acetonitrile no product was obtained.
Moreover, we argue that the steric bulk of the substitutent group of both
Scheme 1.

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2187
alcohol and amines might improve the chemoselectivity exhibited for this
reaction, thus minimizing the amount of unwanted amide compounds 3 to
the point that its formation is prevented.
In order to confirm this hypothesis, we have examined more closely the
steric effect exerted by both amine and solvent. During the course of this inves-
tigation, we noticed that no difference was found when the reaction of b-phenyl-
glycidic ester with benzylamine was achieved in ethanol[10] or tert-butyl alcohol
and gave predominantly the erythro ester 2a (entry 1, Table 1). The undesirable
amide product 3a was formed in a low yield. Similarly, the analogous reaction in
ethanol with more encumbered amine like isopropylamine furnished the
products 2b and 3b in modest yields (entry 2, Table 1). Nevertheless, the
same reaction carried out in tert-butyl alcohol was found to proceed slower
and provided the erythro ester 2b as a single product in good yield. These results
suggest that the incursion of the steric effect exerted simultaneously by both
amine and solvent is necessary to avoid formation of amide 3.
To generalize these results, other amines (R ¼ secondary group) were
similarly refluxed in tert-butyl alcohol with epoxide and the products 2b–e
were isolated in 77–90% yields. As seen in Table 1, the completely regio-
and chemoselective C-3 attack of amine, when the substituent at the nitrogen
atom was secondary group, occurred in all cases given the desired product 2 in
high yields. With more bulky amine (R ¼ tertiary group) (entry 7, Table 1),
reaction took a longer time and led to moderate yield (58%) of the desired
product.
Single crystals of the ethyl (erythro)-3-phenyl-3-tertbutylamino-2-hydroxy-
propionate 2f were analyzed by x-ray crystallography. (Fig. 1).
It should be noted that we have extended the present reaction to secondary
amines. Thus, when epoxide was treated with N-methylbenzylamine the same
reaction was observed and afforded the ethyl 3-phenyl-3-N-methylbenzyl-
amino-2-hydroxypropionate 2g in 94% yield as a single erythro-isomer.
This study will be the subject of a future report.
Further conversion and application for the compounds 2, thus obtained, are
now under investigation in our laboratory. They are potentially useful inter-
mediates for the synthesis of b-lactams[16] and aziridines.[10]

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Besbes and Ennigrou
a
b

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2189
Figure 1. Structure of compound 2f as determined by x-ray analysis.
In conclusion, we have shown that b-phenylglycidic ester reacts with
primary amines to afford a totally chemo-, regio-, and stereoselective reactions
with the exclusive formation of the b-amino-a-hydroxy esters by the choice of
the substituent at the nitrogen atoms as well as the nature of the solvent.
EXPERIMENTAL
All reagents were purchased from Acros. Reaction progress was moni-
tored by TLC on silica gel plates (Fluka Kieselgel 60 F254). For column
chromatography, Fluka Kieselgel 70–230 mesh was used. The infrared (IR)
1
spectra were determined on a Perkin–Elmer Paragon 1000 PC. H and 13C
NMR spectra were recorded on Bruker AM 300 spectrometer in CDCl3 as
solvent and TMS as the internal standard. Mass spectra (GC-MS) were
measured on a HP 5890 A mass spectrometer at 70 eV. Microanalyses were
performed by the “Service de Microanalyse de l’Institut National
de Recherche et d‘Analyse Physico-Chimique.”
Preparation of Ethyl (Erythro)-3-phenyl-3-alkylamino-2-
hydroxypropionate 2b–g: General Procedure
To a solution of b-phenylglycidic ester (5 mmol) in alcohol solvent
(10 mL) (tert-butyl alcohol for entry 1, 3–7 and ethanol for entry 2), amine

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Besbes and Ennigrou
(15 mmol) was added. The solution was stirred at reflux for the time indicated
in Table 1. When the epoxide disappearance was completed (monitored by
TLC), the solvent was removed and the residue was purified by flash chroma-
tography using CHCl3/EtOAc (7 : 3) as eluent. Compounds 2b–f and 3b were
crystallized from hexane.
Ethyl (Erythro)-3-phenyl-3-i-propylamino-2-hydroxypropionate (2b). IR
(CHCl3, n, cm21): 3525, 3331, 1731. 1H NMR (300 MHz CDCl3): 7.27
(m, 5H), 4.48 (d, 1H, J ¼ 4.2 Hz), 4.14 (d, 1H, J ¼ 4.2 Hz), 4.03 (q, 2H,
J ¼ 6.9 Hz), 2.90 (br, 2H, OH and NH), 2.68 (m, 1H), 1.12 (t, 3H,
J ¼ 6.9 Hz), 1.06 (d, 3H, J ¼ 6.6 Hz), 1.02 (d, 3H, J ¼ 5.8 Hz). 13C NMR
(75 MHz CDCl3): 172.7 (CO2), 138.1 (Carom), 128.3, 127.8, 127.7 (CHarom
)
73.4 (CHOH), 61.6 and 61.3 (PhCHN and CH2O), 45.1 (CH3CHN), 23.9
and 21.9 (2CH3CHN), 14.0 (CH3CH2O). M.S. m/z (%): 252 (MHþ, 0.5%),
178 (4), 148 (100), 106 (51), 91 (17), 79 (12.5). Anal. calcd. for
C14H21NO3 : C, 66.91; H, 8.42; N, 5.57. Found: C, 66.78; H, 8.50; N, 5.22.
Ethyl (Erythro)-3-phenyl-3-s-butylamino-2-hydroxypropionate (2c). IR
(CHCl3, n, cm21): 3525, 3336, 1731. 1H NMR (300 MHz CDCl3): 7.25
(m, 5H), 4.50 and 4.48 (2d, 1H, J ¼ 4.2 Hz), 4.17 and 4.15 (2d, 1H,
J ¼ 4.2 Hz), 4.02 (m, 2H) 3.60 (br, 2H, OH and NH), 2.53 and 2.41 (2m,
1H), 1.57–1.29 (m, 2H), 1.12 and 1.11 (2t, 3H, J ¼ 6.9 Hz), 1.04 and 0.97
(2d, 3H, J ¼ 6.2 Hz), 0.87 and 0.86 (2t, 3H, J ¼ 7.3 Hz). 13C NMR (75 MHz
CDCl3): 172.5 (CO2), 138.3, and 137.8, (Carom), 128.2, 127.7, 127.6 (CHarom),
73.5 and 72.9 (CHOH), 61.5, 61.3, 61.1, 61.0 (PHCHN and CH2O), 51.0 and
50.7 (CH3CHN), 30.3 and 28.4 (CH3CH2CH), 20.3 and 19.0 (CH3CHN), 13.9
(CH3CH2O), 10.3 and 9.6 (CH3CH2CH). M.S. m/z (%): 266 (MHþ, 1%), 236
(2), 192 (3), 162 (100), 106 (70), 91 (29), 79 (15), 77 (9.5). Anal. calcd. for
C15H23NO3:C, 67.90; H, 8.74; N, 5.28. Found: C, 67.02; H, 8.67; N, 5.27.
Ethyl (Erythro)-3-phenyl-3-(a-methylbenzyl)amino-2-hydroxypropio-
nate (2d). IR (CHCl3, n, cm21): 3520, 3336, 1728. 1H NMR (300MHz
CDCl3): 7.30 (m, 10H), 4.40 (d, 1H, J ¼ 4.2 Hz), 3.97 (m, 2H) 3.76 (d, 1H,
J ¼ 4.2 Hz), 3.55 (q, 1H, J ¼ 6.6 Hz), 3.06 (br, 2H, OH and NH), 1.33 (d, 3H,
J ¼ 6.6 Hz), 1.05 (t, 3H, J ¼ 6.9 Hz). 13C NMR (75 MHz CDCl3): 172.5 (CO2),
144.5, and 137.8, (2Carom), 128.4, 128.3, 128.1, 127.7, 127.0, 126.9 126.6
(CHarom), 73.8 (CHOH), 61.6 and 61.2 (PhCHN and CH2O), 54.6 (CH3CHN),
25.0 (CH3CHN), 13.8 (CH3CH2O). M.S. m/z (%): 209 (93), 208 (43), 194 (77),
165 (13), 105 (100), 91 (12), 89 (24), 79 (30.5), 77 (68.5). Anal. calcd. for
C19H23NO3: C, 72.82; H, 7.40; N, 4.47. Found: C, 72.61; H, 7.32; N, 4.55.
Ethyl (Erythro)-3-phenyl-3-cyclohexylamino-2-hydroxypropionate
1
(2e). IR (CHCl3, n, cm21): 3520, 3328, 1728. H NMR (300 MHz CDCl3):
7.28 (m, 5H), 4.51 (d, 1H, J ¼ 4.2 Hz), 4.22 (d, 1H, J ¼ 4.2 Hz), 4.02
(q, 2H, J ¼ 6.9 Hz), 3.10 (br, 2H, OH and NH), 2.36–1.18 (m, 11H), 1.10
(t, 3H, J ¼ 6.9 Hz). 13C NMR (75 MHz CDCl3): 172.6 (CO2), 138.3 (Carom),

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2191
128.3, 128.1, 127.7, 127.6 (CHarom), 73.4 (CHOH), 61.1 and 61.0 (PhCHN
and CH2O), 53.2 (CH2CHN), 34.2, 32.7, 26.0, 24.9, 24.6 (CH2 cyclohexyl),
14.0 (CH3CH2O). M.S. m/z (%): 292 (MHþ, 0.5%), 218 (4), 188 (100), 106
(52), 91 (25), 79 (9.5). Anal. calcd. for C17H25NO3: C, 70.07; H, 8.65; N,
4.81. Found: C, 69.89; H, 8.61; N, 4.82.
Ethyl (Erythro)-3-phenyl-3-t-butylamino-2-hydroxypropionate (2f). IR
(CHCl3, n, cm21): 3524, 3346, 1732. 1H NMR (300MHz CDCl3): 7.38–7.16
(m, 5H), 4.00 (m, 2H), 3.95 (s, 2H), 3.50 (br s, 1H), 2.50 (s, 1H), 1.13 (t, 3H,
J ¼ 6.9 Hz), 0.88 (s, 9H). 13C NMR (75 MHz CDCl3): 174.5 (CO2), 143.9
(Carom), 128.3, 127.8, 127.4, 126.3 (CHarom), 75.6 (CHOH), 59.5 and 59.3
(PhCHN and CH2O), 50.6 (CH3C), 29.9 (3CH3C), 13.9 (CH3CH2O). M.S.
m/z (%): 266 (MHþ, 0.5%), 250 (3), 192 (3), 162 (58), 106 (100), 91 (25),
79 (14). Anal. calcd. for C15H23NO3: C, 67.90; H, 8.74; N, 5.28. Found: C,
67.51; H, 8.79; N, 5.27.
Ethyl (Erythro)-3-phenyl-3-N-methylbenzylamino-2-hydroxypropionate
1
(2g). IR (CHCl3, n, cm21): 3524, 1732. H NMR (300MHz CDCl3): 7.15
(m, 5H), 4.69 (d, 1H, J ¼ 5.8 Hz), 4.00 (q, 2H, J ¼ 6.9 Hz), 3.73 (d, 1H,
J ¼ 5.8 Hz), 3.50 and 3.21 (AB, 2H, J ¼ 13.4 Hz), 3.03 (s, 1H), 2.10 (s, 3H),
1.05 (t, 3H, J ¼ 6.9Hz). 13C NMR (75 MHz CDCl3): 173.0 (CO2), 138.9 and
135.8 (2Carom), 128.6, 128.5, 128.4, 127.3, 126.9 (CHarom), 71.4 and 70.9
(CHOH) and PhCHN), 61.3 and 59.3 (PhCH2N and CH2O), 38.7 (CH3N),
14.1 (CH3CH2O). M.S. m/z (%): 240 (2), 210 (90), 118 (7), 91 (100), 77 (4).
Anal. calcd. for C19H23NO3 : C, 72.82; H, 7.40; N, 4.47. Found: C, 72.64; H,
7.41; N, 4.51.
(Erythro)-3-phenyl-N,N0-diisopropyl-isoserinamide (3b). IR (CHCl3,
n, cm21): 3680, 3606, 3409, 1661. 1H NMR (300MHz CDCl3): 7.28 (m, 5H),
6.63 (d, 1H, J ¼ 8.4 Hz), 4.44 (d, 1H, J ¼ 4.5 Hz), 4.40 (br s, 1H), 4.22 (d, 1H,
J ¼ 4.5 Hz), 3.80 (m, 1H), 2.71 (m, 1H), 1.09 (d, 3H, J ¼ 6.2 Hz), 1.05 (d, 3H,
J ¼ 6.6 Hz), 1.01 (d, 3H, J ¼ 6.6 Hz), 0.61 (d, 3H, J ¼ 6.2 Hz). 13C NMR
(75 MHz CDCl3): 170.6 (CO2), 137.8 (Carom), 128.1, 128.0, 127.6 (CHarom),
72.8 (CHOH), 60.8 (PhCHN), 45.4 and 40.2 (CHNHCHPh and CHNHCO),
23.4, 22.3, 22.1, 21.5 (4CH3CHN). M.S. m/z (%): 147 (29.5), 132 (100), 105
(58), 104 (31.5), 89 (20), 77 (50.5). Anal. calcd. for C15H24N2O2: C, 68.15;
H, 9.15; N, 10.60. Found: C, 67.34; H, 8.94; N, 10.19.
X-Ray Crystallographic Analysis of Compound (2f)
Crystal data: C15H23NO3; monoclinic, space group P21/n; a ¼ 14.794(3),
3
˚
˚
b ¼ 6.888(2), c ¼ 15.501(4) A, b ¼ 101.08(2)8, V ¼ 1550.1(7) A , Z ¼ 4,
Dc ¼ 1.14g cm23. Intensity data collected with u ꢀ 228 using Mo Ka radiation
˚
(0.71073A) on an Enraf-Nonius CAD4 diffractometer; T ¼ 293 K, 2199

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reflections measured; 1899 reflections observed [I ꢁ 3s(I)]; solution by direct
methods; full matrix least-squares refinement using SHLXL-97 (Sheldrick,
G. M. SHELXL-97. Program for the Refinement for Crystal Structures. University
¨
of Gottingen, Germany, 1997); non-hydrogens anisotropic, all hydrogen atoms
obtained by Fourier-difference and refined isotropically. An ORTEP view of
the molecule (johnson, C. K., ORTEPIII, for Windows-Farrugia, L. J. (1997)
J. Appl. Cryst. 30, 565) is shown in Fig. 1. The molecules in the crystal are
connected by two hydrogen bonds: O1–H2–N [O1–H2 ¼ 0.435(5), H2–N
˚
(1 2 x, 2y, 1 2 z) ¼ 1.938(1) A, O1–H2–N ¼ 165.29(1)8] and N-H1–O2
˚
[N–H1 ¼ 0.844 (3), H1–O2 (x, 21 þ y, z) ¼ 2.488 (1) A, N–H1–
O2 ¼ 162.19(2)8].
ACKNOWLEDGMENT
We thank Pr. Driss A. for providing the x-ray crystal analysis. Thanks are
also due to Pr. Labassi T. for interesting and valuable English discussions.
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Received in Poland August 18, 2003

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