Regio-controlled and stereo-controlled ring expansion of N-substituted-2 benzoylaziridines using Fe(NO3)3

Article abstract of DOI:10.1002/jhet.1773

Several N-acyl-2-benzoylaziridines were previously prepared conveniently and used in the preparation of 5-benzoyl-2,4-diaryl oxazolines in the presence of NaI. In this work, synthesis of some trans-4-benzoyl- 2,5-diaryl oxazolines by a regio-controlled an

Full text of DOI:10.1002/jhet.1773

Month 2014 Regio-controlled and Stereo-controlled Ring Expansion of N-Substituted-2
Benzoylaziridines Using Fe(NO3)3
*
Heshmat A. Samimi and Zahra Shams
Department of Chemistry, Faculty of Sciences, University of Shahrekord, PO Box 115, Shahrekord, Iran
*
E-mail: samimi-h@sci.sku.ac.ir
Received April 8, 2012
DOI 10.1002/jhet.1773
Published online 00 Month 2014 in Wiley Online Library (wileyonlinelibrary.com).
R2
R2
R2
O
H
N
i
O
N
ii
N
O
N
O
R1
O
O
R1
O
R1
R1
not formed
Ph
1
3
Ph
2
Ph
Ph
R1=C6H5, 3-NO2C6H4, 4-ClC6H4, 2,4-Cl2C6H3, 4-OMeC6H4; R2=C6H5, 4-NO2C6H4
i) RCOCl,Et3N,CH2Cl2, rt. ii) Fe(NO3)3,CH3CN,r.t.
Several N-acyl-2-benzoylaziridines were previously prepared conveniently and used in the preparation of
5-benzoyl-2,4-diaryl oxazolines in the presence of NaI. In this work, synthesis of some trans-4-benzoyl-
2,5-diaryl oxazolines by a regio-controlled and stereo-controlled reaction in the presence of Iron (III)
nitrate at room temperature is reported. A plausible mechanism has been proposed for ring expansion
of N-acylaziridines to oxazolines.
J. Heterocyclic Chem., 00, 00 (2014).
INTRODUCTION
RESULTS AND DISCUSSION
Oxazolines have a wide variety of applications such as
chiral auxiliaries [1], pharmaceutical and biological activi-
ties, [2] synthetic intermediates [2], protecting groups [3],
versatile intermediates in P–C bond formation [4], ligands
in the asymmetric catalysis of organic reactions [5], and in
the synthesis of b-substituted serines because of their util-
ity in the synthesis of various antibiotics [4b].
Initially, we prepared trans-2-benzoylaziridines 1
via Gabriel–Cromwell procedure [13]. Then trans-2-
Benzoylaziridines 1 were used for the preparation of
N-acetyl-2-benzoylaziridines 2 in the presence of Et3N in
CH2Cl2 (Scheme 1). Some of N-acetyl-2-benzoylaziridines
(2a,f) were characterized by their spectral data (13C NMR,
1H NMR, and IR) and melting points.
For more than a century, considerable interest has been
devoted to find a new methodology for the synthesis
of oxazoline building blocks [6]. In most cases, they are
prepared from amino alcohols [5b], carboxylic esters [5c],
nitriles, or aldehydes as starting materials [7].
N-Acyl activated aziridines easily afford ring opening and
can be transformed into the corresponding oxazolines through
a ring expansion reaction in the presence of some different
Lewis acids [8–12]. The majority of these ring enlargements
proceed with full stereochemical control [9,10].
Despite few work reported on the reactivity of aziri-
dines, further developments in utilization of aziridines
derivatives as useful synthetic precursors is still required.
In addition, so far, no example has been reported in the
literature describing the synthesis of two regioisomers of
oxazolines from the same N-acyl aziridines [8–12].
In continuation of our recent interest in the synthesis
and using of heterocyclic compounds as well as the ring
expansion of keto aziridines with NaI for the prepara-
tion of some trans-5-benzoyloxazolines [11,13], herein
we report the synthesis of their regioisomers, namely
trans-4-benzoyloxazolines, in the presence of Iron(III) nitrate
at room temperature in moderate to good yields (Scheme 1).
In this study, as a model reaction, the effect of different
catalysts on the efficiency of ring expansion of 1,2-dibenzoyl-
3-phenyl aziridine (2a) was investigated in acetonitrile
(Scheme 2). The results of this study revealed that the ring
expansion reaction in the presence of ZnCl2, ZnO, AlCl3, Zn
(HSO4)2, Co(HSO4)2, and H3BO3 gave a mixture of unknown
products with a small amount of trans-4-benzoyloxazolines
(10–56%) of the desired oxazoline (Scheme 2, Table 1). In the
absence of catalyst, the reaction did not give any of oxazolines
(entry 8). However, the best results for the conversion of
1,2-dibenzoyl-3-phenyl aziridine (2a) to trans-4-benzoyl-
2,5-diphenyl oxazoline (3a) achieved with Fe(NO3)3 in
acetonitrile (81% yield; Table 1, entry 7).
The effects of some solvents such as Et2O, CH2Cl2,
EtOH, CHCl3, and CH3CN on the ring-expansion of
1,2-dibenzoyl-3-phenyl aziridine (2a) in the presence of
Fe(NO3)3 were examined. Only acetonitrile was a suitable
solvent for this isomerization.
However, it is well known that N-acetyl aziridines can
undergo ring expansion in the presence of catalysts such
as BF3.OEt2 or Sc(OTf)3 in CH3CN with the formation
of imidazoles, but it gives oxazolines in solvents such as
CH2Cl2 or CHCl3 [8c–d]. Surprisingly, against that, our
© 2014 HeteroCorporation

H. A. Samimi and Z. Shams
Vol 000
Ph
3a
Scheme 1
Ph
R2
O
N
H
N
H
O
H
O
N
O
O
R2
O
H
N
ii
O
R1
Ph
Ph
i
N
H
O
3
Ph
Ph
Ph
R1
O
R1
4a
Ph
R2
1
2
Ph
H4,H5; 5.5,5.7 ppm ;
J= 6.5 Hz
H4,H5;5.6,6.3 ppm ;
J= 7.2 Hz
iii
N
O
C4,C5:74,87 ppm
Mp. 89-90 C
(reference 11)
C4,C-5: 79, 81 ppm
Mp.115-118 C
O
R1
o
o
i) RCOCl,Et3N,CH2Cl2, rt. ii) Fe(NO3)3,CH3CN,r.t.
iii) NaI, CH3CN, MW
4
Ph
(This work)
Figure 1. Spectral data and melting point of 4a and 3a.
There are three plausible mechanisms for ring expansion
of aziridines to oxazolines (SN2, SN1, or SNi) [10], but the
formation of imidazoles can only occur via SN2 or SN1.
We earlier reported a reaction that proceeds by the two SN2
mechanisms (double inversion) with complete retention of
configuration in a regio-controlled and stereo-controlled
reaction in the presence of NaI as an efficient catalyst under
microwave irradiation (Scheme 1) [11]. In SN1 mechanism,
intermediate would cause racemization via a carbenium
ion and a mixture of the products with S-configurations and
R-configurations would be produced [10]. The last is a front
side attack of the carbonyl oxygen directly on the ring carbon
to break the C–N bond (i.e., the SNi mechanism), where the
configuration of the ring carbon is retained in the products
because the oxygen approaches from the same side as the
leaving group (nitrogen) leaves [10].
Herein, our result would suggest two possible routes for
oxazoline formation in the presence of Lewis acid (Scheme 3).
In route A, in SN1 mechanism via a carbenium ion intermediate
would cause rotation around C4–C5 and produce cis and
trans-oxazolines, it is not likely carbenium ion intermediate
adjacent carbonyl group can be formed, whereas route
B will only lead to the trans-oxazoline products with the
nitrogen adjacent to the carbonyl group (trans-3).
Scheme 2
Ph
Ph
O
O
N
N
catalyst
O
CH3CN/r.t
O
Ph
Ph
Ph
Ph
3a
2a
Table 1
Ring expansion of trans-1,2-dibenzoyl-3-phenyl aziridines (2a) with dif-
ferent catalysts.
Entry
Catalyst (0.3 mmol)
Time (h)
Yield (%)a
1
2
3
4
5
6
7
8
H3BO3
ZnO
6
5
2
2
1
1
1
5
10
16
10
15
56
22
81b
0
Zn(HSO4)2
Co(HSO4)2
AlCl3
ZnCl2
Fe(NO3)3
–
aIsolated yield after purification.
bSuitable catalyst for the synthesis of trans-4-benzoyl-2,5-diphenyl oxazoline
(3a) from 2a.
Because the result shows only the formation of one
regioisomer of oxazolines, therefore the mechanism can
take place via route B. The mechanism of the isomeriza-
tions to oxazolines probably includes a four-center dis-
placement or the SNi. In route B, the aryl moiety at
position C-3 makes it a suitable position containing a par-
tial positive carbon on C-3 for intra nucleophilic reaction
of oxygen to give oxazoline 3. Consequently, the forma-
tion of only one stereo and regioisomer as well as the
retention of configuration at the carbon atom bearing the
aryl group confirmed that the reaction proceeds via
route B. In this reaction, trans-N-acyl-2-benzoylaziridines
can be activated by binding of Fe(III) to nitrogen followed
by the intra nucleophilic addition of oxygen.
results show 1,2-dibenzoyl-3-phenyl aziridine (2a) in the
presence of Fe(III) as a catalyst in CH3CN gives only
corresponding oxazolines and no imidazoles were obtained
in this reactions.
According to spectral data (1HNMR, 13CNMR and cou-
pling constants) of trans-5-benzoyl-2,4-diphenyl oxazoline
4a, reported in our previous work [11], by comparison
of the spectral data of trans-4-benzoyl-2,5-diphenyl oxazo-
line 3a, the formation of 3a can be visualized as a
regioisomer of 4a (Fig. 1). Chemical shifts of H4 and H5
in oxazoline ring 4a are 5.5 and 5.7 ppm, respectively,
but those of 3a are 5.6 and 6.3 ppm. (Fig. 1).
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Month 2014
Regio-controlled and Stereo-controlled Ring Expansion of N-Substituted-2
Benzoylaziridines Using Fe(NO3)3
Scheme 3
R2
R2
N
O
O
O
N
+
H
O
cis and trans-3
R1
Route A
H
Ph
R1
R2
O
H
N
Ph
R2
N
N
2
R2
N
Fe(NO3)3
O
R2
R1
O
R1
O
Ph
O
O
N
Ph
or
1
Route B
O
trans-3
O
O
R1
R1
R1
Ph
Ph
Ph
1
characterized by comparison with authentic samples (IR and H
NMR spectra, TLC, melting points, and boiling points). NMR
spectra were recorded on a Bruker AMX-400 spectrometer
(1H at 400 MHz and 13C at 100 MHz) in CDCl3with chemical
shift values in parts per million downfield from TMS, and
IR spectra were recorded on FTIR spectroscope JASCO, FT/
IR-6300. All solvents used were dried and distilled according
to standard procedures.
The ring expansion reaction was then extended to
a variety of trans-2-benzoyl-3-aryl aziridines (1a–g)
(Scheme 4). The results are summarized in Table 2.
The products were characterized by their spectral data
1
(13C NMR, H NMR, and IR) and melting points.
In summary, we report an efficient and novel method
for the synthesis of trans-4-benzoyl-2,5-diaryloxazolines
by the ring expansion of trans-N-acyl-2-benzoylaziridines
in a completely regio-controlled and stereo-controlled
reaction in the presence of Fe(NO3)3 at room tempera-
ture in acetonitrile, which gives only regioisomer 3 of
trans-5-benzoyl-2,4-diaryloxazolines and pave the way
for further functionalization of the oxazoline skeleton.
General procedure for preparation of 1,2-dibenzoyl-3-aryl
aziridines (2a, 2f).
Benzoyl chloride (0. 42 mL, 3.0 mmol)
was added dropwise to a solution of aziridines (1) (0.66 g,
3.0 mmol) and triethylamine (0.6 mL) in CH2Cl2 (20 mL) at
0 ꢀC. The mixture was stirred for 1 h at this temperature, 3–5 h
at room temperature, and then rinsed twice with water. The
organic layer was dried over anhydrous Na2SO4 and
concentrated under reduced pressure. The crude product was
purified by column chromatography (silica gel, EtOAc/Hexane:
2/5) to provide the desired keto-aziridine 2 (85–89%).
EXPERIMENTAL
General procedure for preparation of 4-benzoyloxazolines
All yields refer to isolated products after purification by
column chromatography or distillation in vacuum. Products were
(3a–f).
Iron (III) nitrate (0.24 g, 1 mmol) was added into a
solution of 2 (0.33 g, 1.0 mmol) in CH3CN (15 mL), and the
mixture was stirred at room temperature for 1–1.5 h. The
progress of the reaction was monitored by TLC (EtOAc–
Hexane:1/4). After completion of the reaction, organic layer was
rinsed twice with water and dried with anhydrous Na2SO4.
Evaporation of the solvent under reduced pressure and
subsequent purification of the residue by column chromatography
(silica gel, EtOAc–Hexane:1/4) provided 4-benzoyloxazoline 4
(67–92%) (Table 2).
Scheme 4
R2
O
R2
H
N
i
ii
N
2
O
O
N
R1
O
R1
O
Ph
R1
1
3
Ph
Ph
i) RCOCl,Et3N,CH2Cl2, rt. ii) Fe(NO3)3,CH3CN,r.t
trans-1,2-Dibenzoyl-3-phenylaziridine (2a).
White solid,
mp 86–88 ꢀC; IR (potassium bromide): 3060, 1675, 1596, 1452,
1
1328, 1228 cmÀ1. H NMR (deuteriochloroform): d 4.12 (d, 1H,
J = 2.1Hz), 4.37 (d, 1H, J = 2.1 Hz), 7.4–7.8 (m, 11H), 8.00–8.01
(m, 4H); 13C NMR (deuteriochloroform): d 48.0, 48.97, 126.93,
128.84, 128.86, 128.92, 129.10, 129.23, 129.33, 132.90, 134.11,
136.18, 136.82, 176.12, 192.15; Anal. Calcd for C22H17NO2
(327.13): C, 80.73; H, 5.20; N, 4.28. Found: C, 80.82; H, 5.15;
N, 4.25.
Table 2
Ring expansion of trans-1-acyl-2-benzoyl-3-phenyl aziridines (1) in the
presence of Fe(NO3)3.
Entry
R1
C6H5
R2
Time (h)
Yield (%)a
trans-1,2-Dibenzoyl-3-(3-nitrophenyl)aziridine (2f). White
solid, mp 129–130 ꢀC; IR (potassium bromide): 3066, 1689,
1a
1b
1c
1d
1e
1f
C6H5
4-NO2C6H4
C6H5
C6H5
C6H5
1
1.5
1
1
1
81
74
92
88
85b
67
1585, 1525, 1355, 1180, 721, 682 cmÀ1
;
1H NMR
C6H5
4-ClC6H4
2,4-Cl2C6H3
4-OMeC6H4
3-NO2C6H4
(deuteriochloroform): d 4.2 (d, 1H, J = 2.3 Hz), 4.4 (d, 1H,
J = 2.3 Hz), 7.4 (dd, 2H, J = 6.9, 7.9 Hz), 7.5 (m, 3H), 7.6
(dd, 2H, J = 2.0, 7.9 Hz), 7.8 (d, 1H, J = 7.7 Hz), 7.9 (dd,
2H, J = 1.3, 8.7 Hz), 8.0 (dd, 2H, J = 1.2, 8.6 Hz), 8.2–8.3
(m, 1H), 8.3 (dd, 1H, J = 1.9, 3.4 Hz); 13C NMR
C6H5
1.5
aIsolated yield after purification.
bMethoxy was converted to hydroxyl group.
(deuteriochloroform):
d 47.0, 49.0, 118.1, 122.2, 125.8,
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

H. A. Samimi and Z. Shams
Vol 000
126.2, 128.1, 128.8, 128.9, 129.5, 131.2, 133.1, 134.2, 135.8,
138.2, 148.1, 170.5, 198.1; Anal. Calcd for C22H16N2O4
(372.11): C, 70.98; H, 4.34; N, 7.52. Found: C, 71.2; H,
4.36; N, 7.68.
78.7, 80.8, 119.8, 120.9, 122.4, 123.7, 127.3, 128.7, 129.0,
130.0, 132.0, 133.0, 134.0, 135.3, 141.1, 148.8, 164.8, 193.7;
Anal. Calcd for C22H16N2O4 (372.11): C, 70.96; H, 4.33; N,
7.52; O, 17.19. Found: C, 70.90; H, 4.36; N, 7.50; O, 17.24.
trans-4-Benzoyl-2,5-dipheyloxazoline (3a).
Pale yellow
solid, mp 115–118 ꢀC; IR (potassium bromide): 3058, 2920,
1676, 1529, 1349, 777, 692cmÀ1; 1H NMR (deuteriochloroform):
d 5.5 (d, J = 7.2 Hz, 1H), 6.3 (d, J = 7.2 Hz, 1H), 7.3–7.5
(m, 11H),7.8 (m, 2H), 8.1 (dd, J = 6.8, 1.4 Hz, 2H); 13C
NMR (deuteriochloroform): d 78.2, 78.3.0, 125.0, 126.7,
127.6, 128.4, 128.8, 129.1, 129.9, 132.3, 133.8, 134.5,
135.2, 139.4 164.0 193.7; Anal. Calcd for C22H17NO2
(327.13): C, 80.73; H, 5.20; N, 4.28. Found: C, 80.82; H,
5.15; N, 4.24.
trans-4-Benzoyl-2-(4-nitrophenyl)-5-pheyloxazolines (3b).
Yellow solid, mp 137–141 ꢀC; IR (potassium bromide): 3055,
2922, 1687, 1641 cmÀ1;1H NMR (deuteriochloroform): d 5.5
(d, J = 7.2 Hz, 1H), 6.3 (d, J = 7.2 Hz, 1H), 6.9–7.0 (m, 2H), 7.1
(q, J = 7.1, 1H), 7.3–7.6 (m, 6H), 7.7 (d, J = 7.7 Hz, 1H), 7.9–8.2
(m, 4H) ; 13C NMR (deuteriochloroform): d 79, 81, 120.2, 122.0,
123.9, 127.0, 128.2, 129.0, 130.0, 132.7, 133.5, 135.1, 141.5,
148.9, 164.6, 193.9; Anal. Calcd for C22H16N2O4 (372.11): C,
70.96; H, 4.33; N, 7.52; O, 17.19. Found: C, 70.90; H, 4.36; N,
7.53; O, 17.20.
trans-4-Benzoyl-5-(4-chlorophenyl)-2-pheyloxazoline (3c).
Yellow solid, mp 132–135 ꢀC; IR (potassium bromide): 3060,
2927, 1682, 1641, 1591, 1478, 1448, 1259, 1088, 974, 821,
690 cmÀ1; 1H NMR (deuteriochloroform): d 5.4 (d, J=7.2Hz, 1H),
6.2 (d, J = 7.2 Hz, 1H), 7.2–7.4 (m, 8H), 7.5 (m, 1H), 7.8
(m, 1H), 8.0 (dd, J= 7.9, 1.3 Hz, 2H), 8.2 (dd, J=8.0, 1.6Hz, 2H);
13C NMR (deuteriochloroform): d 79.4, 81.0, 121.7, 127.2,
128.4, 128.6, 128.8, 129.1, 129.8, 132.3, 133.9, 134.5, 135.1,
138.5 164.5 194.5; Anal. Calcd for C22H16ClNO2 (361.09):
C, 73.03; H, 4.46; Cl, 9.80; N, 3.87; O, 8.84. Found: C,
73.07; H, 4.48; Cl, 9.76; N, 3.85; O, 8.84.
Acknowledgment. We are thankful to the Research Council of
Shahrekord University for the supporting this work.
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trans-4-Benzoyl-5-(2,4-dichlorophenyl)-2-pheyloxazoline (3d).
Yellow solid, mp 143–147 ꢀC; IR (potassium bromide): 3059,
1
2929, 1687, 1638cmÀ1; H NMR (deuteriochloroform): d 5.4 (d,
J = 5.6Hz, 1H), 6.5 (d, 1H, J = 5.6Hz), 7.3–7.6 (m, 9H), 7.96 (m,
2H),
8.1 (dd, J = 6.3,
1.1 Hz, 2H);
13C
NMR
(deuteriochloroform): d 79.0, 125.0, 126.7, 127.5, 128.5, 128.8,
128.7, 129.6, 131.8, 132.0, 133.8, 134.6, 135.1, 136.9, 139.4,
165.0, 194.0; Anal. Calcd for C22H15Cl2NO2 (395.05): C, 66.68;
H, 3.82; Cl, 17.89; N, 3.53; O, 8.08. Found: C, 66.71; H, 3.85;
Cl, 17.83; N, 3.50; O, 8.11.
trans-4-Benzoyl-5-(4-hydroxyphenyl)-2-pheyloxazoline (3e).
Yellow solid, mp 132–135 ꢀC; IR (potassium bromide): 3320,
3065, 1684, 1530, 1348, 1258, 977, 876 cmÀ1 1H NMR
.
(deuteriochloroform): d 5.6 (d, J = 6.8 Hz, 1H), 6.3 (d, J = 6.8,
1H), 6.5 (s, 1H), 7.2–7.5 (m, 6H), 7.6–7.8 (m, 2H), 7.9
(t, J=6.5, 2H), 8.1 (d, J= 7.2 Hz, 2H) ,8.25 (dd, J= 7.0, 1.6 Hz, 2H);
13C NMR (deuteriochloroform): d 79.0, 81.9, 123.8, 126.7, 127.5,
128.6, 128.8, 129.6, 129.8, 130.6, 132.4, 133.8, 136.9, 138.6,
164.2, 194.8; Anal. Calcd for C22H17NO3 (343.12): C, 76.95;
H, 4.99; N, 4.08; O, 13.98. Found: C, 77.05; H, 5.03; N, 4.02;
O, 13.90.
trans-4-Benzoyl-5-(3-nitroophenyl)-2-pheyloxazoline (3f).
Yellow solid, mp 134–137 ꢀC; IR (potassium bromide): 3063,
1667, 1529, 1349, 1258, 1085, 973, 876, 804, 690cmÀ1 1H
;
NMR (deuteriochloroform): d 5.4 (d, J = 7.2 Hz, 1H), 6.4 (d,
J= 7.21H), 7.1–7.2 (m, 4H), 7.3–7.4 (m, 5H), 7.9 (d, J=7.2Hz,
2H) ,8.1 (t, J = 6.8 Hz, 3H); 13C NMR (deuteriochloroform): d
Journal of Heterocyclic Chemistry
DOI 10.1002/jhet

Month 2014
Regio-controlled and Stereo-controlled Ring Expansion of N-Substituted-2
Benzoylaziridines Using Fe(NO3)3
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Journal of Heterocyclic Chemistry
DOI 10.1002/jhet