Br?nsted Base-Mediated Aziridination of 2-Alkyl-Substituted-1,3-Dicarbonyl Compounds and 2-Acyl-Substituted-1,4-Dicarbonyl Compounds by Iminoiodanes

Article abstract of DOI:10.1071/CH16580

The synthesis of α,α-diacylaziridines and α,α,β-triacylaziridines from reaction of 2-alkyl-substituted-1,3-dicarbonyl compounds and 2-acyl-substituted-1,4-dicarbonyl compounds with arylsulfonyliminoiodinanes (ArSO₂N=IPh) under Br?nsted base-med

Full text of DOI:10.1071/CH16580

RESEARCH FRONT
CSIRO PUBLISHING
Aust. J. Chem.
Communication
http://dx.doi.org/10.1071/CH16580
Brønsted Base-Mediated Aziridination of
2-Alkyl-Substituted-1,3-Dicarbonyl Compounds
and 2-Acyl-Substituted-1,4-Dicarbonyl Compounds
by Iminoiodanes
A
A
B
C
Ciputra Tejo, Davin Tirtorahardjo, David Philip Day, Dik-Lung Ma,
D
B E F
, ,
Chung-Hang Leung, and Philip Wai Hong Chan
A
Division of Chemistry and Biological Chemistry, School of Physical and Mathematical
Sciences, Nanyang Technological University, Singapore 637371, Singapore.
Department of Chemistry, University of Warwick, Coventry, CV4 7AL, UK.
B
C
Department of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong,
China.
D
State Key Laboratory of Quality Research in Chinese Medicine, Institute of Chinese
Medical Sciences, University of Macau, Macao, China.
E
School of Chemistry, Monash University, Clayton, Vic. 3800, Australia.
F
Corresponding author. Email: phil.chan@monash.edu; p.w.h.chan@warwick.ac.uk
The synthesis of a,a-diacylaziridines and a,a,b-triacylaziridines from reaction of 2-alkyl-substituted-1,3-dicarbonyl
compounds and 2-acyl-substituted-1,4-dicarbonyl compounds with arylsulfonyliminoiodinanes (ArSO2N¼IPh)
under Brønsted base-mediated atmospheric conditions is described. The reaction mechanism is thought to involve the
formal oxidation of the substrate followed by aziridination of the ensuing a,b-unsaturated intermediate by the hypervalent
iodine(III) reagent.
Manuscript received: 11 October 2016.
Manuscript accepted: 23 November 2016.
Published online: 3 January 2017.
Aziridines are versatile building blocks in organic synthesis as
well as a structural motif found in many bioactive natural pro-
ducts and compounds of pharmaceutical interest.[1–23] As a
consequence, this has prompted a significant amount of effort
towards the development of a myriad of synthetic methods to
efficiently and selectively prepare the three-membered nitro-
gen-containing heterocycle.[24–38] For example, as part of an
ongoing program exploring the reaction chemistry of iminoio-
danes,[39–70] we recently reported a facile synthetic approach to
prepare a,a-diacylaziridines involving CuII-catalyzed azir-
idination of 2-alkyl-substituted-1,3-dicarbonyl compounds with
p-TsN¼IPh (where p-Ts ¼ p-toluenesulfonyl; Scheme 1a).[38]
Building on this initial work, we queried whether the con-
struction of the aziridine motif in this manner could be achieved
in analogous reactions under transition metal-free-mediated
conditions (Scheme 1b).[64–66,71–81] Herein, we report the
aziridination of 2-alkyl-substituted diethyl malonates and
b-ketoesters in the presence of a Brønsted base and o-NsN¼IPh
(where o-Ns ¼ o-nitrobenzenesulfonyl) under atmospheric
conditions to give the corresponding a,a-diacylaziridine pro-
ducts in moderate-to-excellent yields. Under similar reaction
conditions, the aziridination of 2-acyl-substituted succinates
and dimethyl 2-(2-oxo-substituted)malonates by o-NsN¼IPh to
produce a,a,b-triacylaziridines in good yields is also presented.
We first examined the Brønsted base-mediated aziridination
of diethyl ethylmalonate (1a) by p-NsN¼IPh to establish the
optimum conditions for this reaction (Table 1). These results
revealed that treating the substrate with 2.2 equiv. of p-
NsN¼IPh and 1.1 equiv. of K2CO3 in acetonitrile at room
temperature under atmospheric conditions gave the 1,1-diacy-
laziridine 2a and a,b-unsaturated 1,3-dicarbonyl compound 3a
in 70 % and 23 % yields, respectively (Table 1, entry 1).
Changing the base to other inorganic bases such as t-BuOK or
Na2CO3 led to the recovery of the starting material (Table 1,
entries 2 and 3). On the other hand, replacing K2CO3 with 1,8-
diazabicyclo[5.4.0]undec-7-ene (DBU) as the base in reactions
using 3.3 or 2.2 equiv. of p-NsN¼IPh led to the formation of
aziridine adduct as the only product in 71 % and 72 % yields,
respectively (Table 1, entries 4 and 5). Lower product yields of
29 % and 21 % were observed when the amount of DBU was
reduced from 2.2 equiv. to 0.2 equiv. and 0.1 equiv. (Table 1,
entries 6 and 7). On the other hand, increasing the concentration
of the reaction mixture from 0.1 M to 0.2 M at the Brønsted base
catalyst loading of 0.2 equiv. was found to give a product yield
of 71 % (Table 1, entry 8). Replacing the Brønsted base catalyst
with other organic bases such as 7-methyl-1,5,7-triazabicyclo
[4.4.0]dec-5-ene (MTBD) and 1,4-diazabicyclo[2.2.2]octane
(DABCO) gave either a lower product yield of 58 % or no
www.publish.csiro.au/journals/ajc
Journal compilation ꢀ CSIRO 2017

B
C. Tejo et al.
Cu(OTf)2/
1,10-phenanthroline
O
O
Table 2. Brønsted base-mediated aziridination of 1d–1l
R1
R3
R2
(a)
(b)
O
O
O
O
previous work
N
Ts
2-p-Ts
O
O
Method i
R2
R1
R3
ϩ
o-NsNϭIPh
PhINSO2Ar
R1
R2
R1
R2
or Method ii
N
R3
o-Ns
R3
O
O
1
2
DBU or K2CO3
1
R2
R1
R3
O
O
O
O
this study
O
N
o-Ns
2-o-Ns
CO2Et
EtO
Et
OEt
Ph
OEt
N
N
N
o-Ns
2f (Ϫ)A, C
o-Ns
o-Ns
2e (25),A [98]B
2d (80),A [89]B
Scheme 1. Aziridination of 2-alkyl-substituted-1,3-dicarbonyl com-
pounds with arylsulfonylphenyliodinanes
O
O
O
O
O
O
Me
O
OEt
EtO
EtO
OEt
MeO
Ph
OMe
N
N
N
o-Ns
o-Ns
o-Ns
Table 1. Optimization of the reaction conditionsA
OEt
2g (61),D [99]B
O
O
2h (45)D
2i (56)D
Brønsted base
ArSO2NϭIPh
O
O
O
O
O
O
O
O
O
O
ϩ
EtO
Me
EtO
Me
OEt
EtO
Me
OEt
OEt
solvent, air
rt, 18 h
N
O
O
MeO
O
OMe MeO
OMe
SO2Ar
N
O
N
o-Ns
o-Ns
OEt
EtO
Ph
3a
1a
2a, Ar ϭ p-NO2C6H4
2b, Ar ϭ o-NO2C6H4
2c, Ar ϭ p-MeC6H4
N
o-Ns
O
Entry Brønsted base [equiv.] ArSO2N=IPh [equiv.] Solvent Yield [%]B
Me
2k (50)D
Cl
2l (41)D
2j (58)D
1
K2CO3 (1.1)
t-BuOK (1.1)
Na2CO3 (1.1)
DBU (1.1)
p-NsN¼IPh (3)
p-NsN¼IPh (3)
p-NsN¼IPh (3)
p-NsN¼IPh (2.2)
p-NsN¼IPh (2.2)
p-NsN¼IPh (2.2)
p-NsN¼IPh (2.2)
p-NsN¼IPh (2.2)
p-NsN¼IPh (2.2)
p-NsN¼IPh (2.2)
p-NsN¼IPh (2.2)
p-NsN¼IPh (2.2)
p-NsN¼IPh (2.2)
o-NsN¼IPh (2.2)
p-TsN¼IPh (2.2)
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
MeCN
THF
70C
2
–
AMethod i: reaction performed in 0.2 M MeCN at a o-NsN¼IPh/1/DBU ratio
of 11 : 5 : 1 at room temperature under atmospheric conditions for 18 h;
values in parentheses denote isolated product yields.
BValues in square brackets denote product yields obtained from the analo-
gous reactions of 1d, 1e, and 1g with p-TsN¼IPh and catalyzed by Cu
(OTf)2/1,10-phenanthroline under the conditions described in ref. [38].
CUnidentifiable decomposition products obtained.
DMethod ii: reaction carried out in 0.2 M CH2Cl2 at a o-NsN¼IPh/K2CO3/1
ratio of 3 : 1.1 : 1 at 408C under atmospheric conditions for 18 h; values in
parentheses denote isolated product yields.
3
–
4
71
72
29
21
71
58
5
DBU (1.1)
6D
7D
8D
9D
DBU (0.2)
DBU (0.1)
DBU (0.2)
MTBD (0.2)
10D DABCO (0.2)
11D DBU (0.2)
12D DBU (0.2)
13D DBU (0.2)
14D DBU (0.2)
15D DBU (0.2)
–
–
–
Toluene
CH2Cl2
MeCN
MeCN
74
97E
12 (81)F
instead of p-NsN¼IPh gave 2c in a 12% yield (Table 1, entry
15). In comparison, the analogous reaction catalyzed by Cu
(OTf)2/1,10-phenanthroline gave a product yield of 81%.[38]
A survey of the present DBU-catalyzed procedure involving
other 2-alkyl-substituted-1,3-dicarbonyl compounds showed
that reaction of the diethyl malonate (1d), containing a n-Pr
group at the C2 position, afforded 2d in 80 % yield (Table 2).
Under similar reaction conditions, the aziridination of the
2-methyl-substituted b-keto ester 1e was found to furnish the
corresponding product 2e in 25 % yield. However, the analogous
experiment with the cyclopentanone derivative 1f led to a
complex concoction of unidentifiable by-products based on 1H
NMR analysis of the crude reaction mixture. Reactions of the
2-acyl-substituted-1,4-dicarbonyl compounds 1g–1l afforded
higher product yields using the K2CO3-mediated conditions
described in entry 1 of Table 1 at 408C. The application of this
second set of conditions to the reactions of diethyl succinates
with a pendant methyl ketone (1g) or ethyl ester (1h) group gave
the corresponding aziridines 2g and 2h in respective yields of
61 % and 45 %. Likewise, the use of methyl and ethyl 4-oxo-
4-arylbutanoates containing a methyl ester (1i, 1k, 1l) or an ethyl
ester (1j) moiety gave favourable results. In these experiments,
the corresponding a,a,b-triacylaziridine adducts 2i–2l were
obtained in 37–58 % yield with the structure of 2i being
AAll reactions were performed with 1a (1 equiv.) at a concentration of 0.1 M
at room temperature under atmospheric conditions for 18 h.
BProduct yield of 2 was determined by 1H NMR analysis of the crude
mixture with CH2Br2 as the internal standard.
CIsolated yield of 2a. Compound 3a was also obtained in 23 % yield.
DReaction was performed with 1a at a concentration of 0.2 M.
EIsolated product yield.
FValue in parentheses denotes the yield of 2c obtained from the analogous
reaction catalyzed by Cu(OTf)2/1,10-phenanthroline under the conditions
described in ref. [38].
product formation, respectively (Table 1, entries 9 and 10).
Examination of the solvent effect on the aziridination reaction
revealed that with using THF or toluene instead of acetonitrile
(MeCN) as the solvent resulted in no reaction based on thin layer
1
chromatography analysis and H NMR measurements of the
crude mixtures. In contrast, a product yield of 74 % was obtained
when CH2Cl2 was used as solvent (Table 1, entries 11–13). At a
catalyst loading of 20 mol-%, our subsequent studies revealed
that changing the arylsulfonyl-substituted iminoiodane source
from p-NsN¼IPh to o-NsN¼IPh gave the best result, affording
2b in 97 % yield (Table 1, entry 14). Ina final control experiment,
performing the DBU-mediated reaction using p-TsN¼IPh

Catalysis
C
09
o-NsNϭIPh (1.1 equiv.)
O
O
DBU (20 mol-%)
(a)
C16
C17
EtO
Me
2b, 20 % yield
OEt
N2
MeCN, air, rt, 18 h
N
o-Ns
C15
06
08
C6
C18
C5
O
O
o-NsNH2 (1.1 equiv.)
DBU (20 mol-%)
C7
C14
C19
EtO
Me
OEt
(b)
(c)
(d)
o-Ns
MeCN, air, rt, 18 h
S1
N1
O
O
N
H
C4
C8
C3
01
C9
C2
EtO
Me
OEt
4b, 27 % yield
07
o-NsNϭIPh (1.1 equiv.)
o-NsNH2 (1.1 equiv.)
DBU (20 mol-%)
04
C12
C1
C10
O
O
3a
EtO
Me
2b, 79 % yield
OEt
MeCN, air, rt, 18 h
N
-Ns
o
03
02
05
C13
O
O
o-NsNH2 (1.1 equiv.)
DBU (20 mol-%)
C11
EtO
Me
OEt
-Ns
toluene, air, rt, 6 h
o
N
H
Fig. 1. ORTEP drawing of 2i with thermal ellipsoids at 50 % probability
levels.[82]
4b, 49 % yield
o-NsNH2 (1.1 equiv.)
MeCN, air, rt, 18 h
confirmed by X-ray crystallography (Fig. 1).[82] The reactions
involving 1d and 1g were also found to give product yields that
were either comparable or slightly lower than those obtained
from analogous experiments involving the same substrates and
p-TsN¼IPh and catalyzed by Cu(OTf)2/1,10-phenanthro-
line.[38] The only exception was the reaction involving 1e, which
was found to give a low product yield of 25 % under the present
Brønsted base-mediated conditions.
O
O
EtO
Me
OEt
N
o-Ns
2b, 40 % yield
Scheme 2. Control experiments using 3a. The yield of 4b was determined
by 1H NMR analysis using CH2Br2 as the internal standard.
Though fortuitous, the isolation of the a,b-unsaturated 1,3-
dicarbonyl compound 3a led us to speculate its possible involve-
ment in the reaction mechanism of the present transformation. It
would also imply the decomposition of o-NsN¼IPh to o-NsNH2
and PhI with the in situ formed sulfonamide subsequently
initiating a iminoiodane-mediated Michael-initiated ring clo-
sure (MIRC) reaction and product formation.[83–88] To verify
this hypothesis as well as gain a better understanding of how the
present aziridination process might proceed, we next conducted
a series of control reactions involving 3a (Scheme 2). In an
initial control reaction, subjecting 3a to 20 mol-% of DBU and
1.1 equiv. of o-NsN¼IPh in acetonitrile at room temperature for
18 h afforded 2b in 20 % yield (Scheme 2a). Conducting this
control experiment again using o-NsNH2 instead of o-NsN¼IPh
afforded the sulfonamide compound 4b in 27 % yield
(Scheme 2b). In a third control reaction, the N-heterocyclic
product was then furnished in 79 % yield when the a,b-unsaturated
1,3-dicarbonyl compound was treated under the DBU-catalyzed
conditions in the presence of equimolar amounts of the imi-
noiodane and sulfonamide (Scheme 2c). The possibility of a
pathway involving compound 4b was further supported by
reacting 3a with 0.2 equiv. of DBU and 1.1 equiv. of o-NsNH2
in toluene at room temperature for 6 h (Scheme 2d). Subsequent
addition of 1.1 equiv. of o-NsN¼IPh to the ensuing crude
reaction mixture containing the sulfonamide in 49 % yield
(as determined by 1H NMR analysis using CH2Br2 as the
internal standard) in acetonitrile at room temperature for 18 h
afforded aziridine 2b in 40 % yield. In a final set of control
experiments involving 3a, the recovery of the substrate only was
detected when each of the above control reactions were repeated
under the conditions described in Scheme 2 and in the absence of
the Brønsted base.
Based on the above results, a tentative mechanism for
the present Brønsted base-mediated aziridination reactions is
illustrated in Scheme 3. The mechanism could initially involve
the Brønsted base-promoted tautomerization of substrate 1 to
give the enol isomer I. Nucleophilic attack of this tautomer at the
iodine centre in o-NsN¼IPh might then produce the putative
iodinated species II.[89–100] Intramolecular deprotonation of the
b-methylene centre by the sulfonamide motif and deiodination
in this newly formed adduct would afford intermediate 3 along
with the release of o-NsNH2 and iodobenzene. At this juncture,
an iminoiodane-mediated MIRC may now come into play upon
the 1,4-conjugate addition of o-NsNH2 to the Michael acceptor
site of 3 to furnish the posited 1,3-amino enol III.[83–88]
A second nucleophilic addition step involving this adduct and
another molecule of o-NsN¼IPh could occur to give the iodinated
1,3-dicarbonyl compound IV. Subsequent deiodination of this
hypervalent iodine(III) adduct followed by deaminative cycliza-
tion of the ensuing disulfonamide adduct V might then deliver the
aziridine product 2.[89–100]
In conclusion, we have developed a transition metal-free
synthetic strategy to access a,a-diacylaziridines and a,a,b-
triacylaziridines. The nitrogen ring-forming process relies on the
aziridination of the respective 2-alkyl-substituted-1,3-dicarbonyl
compounds and 2-acyl-substituted-1,4-dicarbonyl compounds by
o-NsN¼IPh under Brønsted base-mediated reaction conditions.
Though the substrate scope of the present methodology is less
broad than the analogous CuII-catalyzed approach,[38] the present
methodology was shown to be more practical as it did not require

D
C. Tejo et al.
o-NsNϭIPh
O
O
I
O
O
Ϫϩ
o-NsN–IPh
H
O
O
B
R2
Ph
R1
R3
R1
R2
R1
R2
NHo-Ns
R3
R3
H
1
I
II
–PhI
–o-NsNH2
o-NsNϭIPh
O
O
H
O
O
O
O
Ϫϩ
o-NsN–IPh
R1
R3
R2
Ph
o-NsNH2
R2
R1
R1
R2
I
NHo-Ns
R3
N
R3
NHo-Ns
o-Ns
H
III
3
IV
–PhI
O
O
O
O
–NH2SO2Ar
R1
R2
R1
R2
N
NHo-Ns
R3
R3
o-Ns
NHo-Ns
V
2
Scheme 3. Proposed mechanism of the present Brønsted base-mediated aziridination reaction.
the need for inert reaction conditions. Efforts to explore the
synthetic applications of the present reactions are currently
underway and will be reported in due course.
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Supplementary Material
Detailed experiment procedures, characterization data, and 1H
and 13C NMR spectra for compounds 2, 3a, and 4a are available
on the Journal’s website.
[15] Recent reviews on the biological activity and natural product
constructed from aziridines, see refs [16–18].
[16] H.-Y. Lee, S.-B. Song, T. Kang, Y. J. Kim, S. J. Geum, Pure Appl.
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Co. KGaA: Wienheim).
Acknowledgements
This work was supported by start-up grants from the School of Chemistry,
MonashUniversity and the DepartmentofChemistry, University ofWarwick.
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