Visible-Light-Induced Regioselective C(sp3)-H Acyloxylation of Aryl-2 H-azirines with (Diacetoxy)iodobenzene

Article abstract of DOI:10.1021/acs.joc.9b01625

A visible-light-promoted regioselective coupling of C(sp³)-H of aryl-2H-azirine and (diacetoxy)iodobenzene has been reported. Rose Bengal as an organophotoredox catalyst has been used in this reaction. The reaction proceeds under aerobic condition at room temperature. A variety of aryl-2H-azirines gives the corresponding acyloxylated azirines under this reaction conditions. The reaction goes through a radical pathway. The protocol is also applicable on gram-scale synthesis.

Full text of DOI:10.1021/acs.joc.9b01625

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Article
Visible-Light-Induced Regioselective C(sp3)-H Acyloxylation
of Aryl-2H Azirines with (Diacetoxy)iodobenzene
Aramita De, Sougata Santra, Alakananda Hajra, Grigory V Zyryanov, and Adinath Majee
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b01625 • Publication Date (Web): 15 Aug 2019
Downloaded from pubs.acs.org on August 16, 2019
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Visible-Light-Induced Regioselective C(sp3)-H Acyloxylation of Aryl‑2H-
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Azirines with (Diacetoxy)iodobenzene
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Aramita De,§ Sougata Santra,† Alakananda Hajra,§ Grigory V. Zyryanov†,‡ and Adinath Majee*,§
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§ Department of Chemistry, Visva-Bharati (A Central University), Santiniketan 731235, India
† Department of Organic and Biomolecular Chemistry, Chemical Engineering Institute, Ural
Federal University, 19 Mira Street, 620002 Yekaterinburg, Russian Federation
‡ I. Ya. Postovskiy Institute of Organic Synthesis, Ural Division of the Russian Academy of
Sciences, 22 Sofi Kovalevskoy Street, 620219 Yekaterinburg, Russian Federation
Rose Bengal
N
34 W Blue LED
C(sp3)-H Acyloxylation
N
PhI(OAc)2
OAc
Metal-Free Conditions
Organophotocatalysis
Gram-Scale Synthesis
Toluene, 24 h
R
R
R = H, Me, tBu, Ph, Cl, Br, F, CF3
18 Examples
58-85% Yields
ABSTRACT: A visible-light-promoted regioselective coupling of C(sp3)-H of aryl-2H-azirine
and (diacetoxy)iodobenzene (PIDA) has been reported. Rose Bengal as an organophotoredox
catalyst has been used in this reaction. The reaction proceeds under aerobic condition at room
temperature. A variety of aryl-2H-azirine gives the corresponding acyloxylated azirines under
this reaction conditions. The reaction goes through a radical pathway. The protocol is also
applicable on gram-scale synthesis.
Introduction
In organic compounds having C(sp3)-H is inert and its functionalization is a significant work.
Particularly its oxidation is a challenge till date which is obvious from the meaningful efforts of
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the learned chemists.1 Accordingly, several methods are available in literature to achieve the
goal, using traditional metal1,2 as well as metal-free catalysis.3 Among the small ring system 2H-
azirines are important N-containing heterocycles, due to its significant role to construct a variety
of large heterocycles by ring-opening reaction.4 In addition, many naturally occurring
compounds contain the 2H-azirine moiety (Figure 1)5 and also the aziridine was found as
important building block for the synthesis of various N-heterocycles.6
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Figure 1. Azirine Containing Natural Product
N
CO2H
N
H
CO2H
H
R
Azirinomycin
(S)-(+)-Dysidazirine, when R = n-Pentane
Br
(S)-(+)-Antazirine, when R =
Br
Due to high strain in 2H-azirine the selective C(sp3)-H functionalization is very difficult
compared to the easy ring-opening. So, giving a sincere effort to achieve this goal is very
meaningful for a synthetic organic chemist. Now for C(sp3)-H oxidation, the use of
(diacetoxy)iodobenzene (phenyliodine(III) diacetate, PIDA) is well-known as it is easily
accessible, low cost, and environmentally benign.7 Very recently, Wang et al. used PIDA to
functionalize the 2H-azirines by iron catalysis.8 They found no reaction by the irradiation of light
and on heating (70 °C) generated low yield with the decomposition of the starting material.
Recently, direct C−H bond functionalization by irradiation of visible light using
organophotoredox catalyst has drawn a significant interest from the synthetic organic chemistry
community.9 The alternate of transition metal photoredox catalysts are some organic dyes like
eosin Y, rose bengal (RB), methylene blue, etc. The organophotocatalysts are low cost, nontoxic,
and environmentally benign.10 We are working to develop/modify some important
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transformations used in synthetic organic chemistry. Recently, we have reported some important
works involving the nitrogenous heterocycle aziridines11 and also some reactions using PIDA as
the reagent12 and organophotoredox catalysts. 13(a-d) Herein, we have applied our combined effort
involving nitrogen heterocycle 2H-azirine and PIDA as the reagent for the selective C(sp3)-H
oxidation using an organophotoredox catalyst (Scheme 1). There are several methods to
functionalize 2H-azirine using visible light,14 but, according to literature, this is the first
approach for the synthesis of acyloxylated aryl-2H-azirines using organophotoredox catalyst.
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Scheme 1. Visible-Light-Mediated Acyloxylation of Aryl-2H-azirines
N
Rose bengal
N
+ PIDA
Ar
OAc
Toluene, 24 h
Blue LED
Ar
1
2
Results and Discussion
Table 1. Optimization of the Reaction Conditionsa
N
N
photocatalyst (2 mol %)
PIDA
OAc
solvent (3 mL)
34 W Blue LED
1a
2a
entry photocatalyst (2 mol %)
solvent
toluene
toluene
toluene
yields (%)b
1
2
3
eosin Y
40
13
25
--
Ru(bpy)3Cl2∙6H2O
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Ir(ppy)3
toluene
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5
rose bengal
rose bengal
rose bengal
rose bengal
rose bengal
rose bengal
rose bengal
rose bengal
rose bengal
rose bengal
rose bengal
rose bengal
rose bengal
rose bengal
rose bengal
toluene
MeCN
DCM
85
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ndb
25
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1,2-DCE
benzene
acetone
CCl4
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THF
38
DMF
ndb
<10
35
DMSO
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MeOH
EtOH
ndb
<10
ndb
55c, 86d
H2O
toluene
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20e
rose bengal
toluene
trace
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aReaction conditions: 1a (1.0 mmol), PIDA (1.0 mmol), 2mol% of photocatalyst, 34 W blue
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b
LED at room temperature using different solvents (3 mL) for 24 h. nd = not detected in TLC. c1
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d
c
mol % rose bengal was used. 3 mol % rose bengal was used. The reaction was carried out in
dark condition.
Initially, we tested the reaction with 3-phenyl-2H-azirine (1a, 1 mmol) using
photocatalyst eosin Y (2 mol %) by irradiation with a blue LED lamp (34 W) in toluene. The
reaction was continued under ambient air for 24 h using PIDA (Table 1, entry 1). The desired
product 3-phenyl-2H-azirin-2-yl acetate (2a) has been isolated in 40% yield. The yield was not
improved even after 36 h. Only 13% of the desired product was isolated in the absence of
photocatalyst (Table 1, entry 2). The reaction by variation of different parameters have been
summarized in Table-1. We used photocatalysts like Ru(bpy)3Cl2·6H2O, Ir(ppy)3 and rose
bengal. Among these, rose bengal was found to be the best and afforded 85% yield of our
desired product (Table 1, entry 5). A variety of aprotic polar solvents like acetonitrile, DCM, 1,2-
DCE, benzene, acetone, CCl4, THF, DMF, DMSO, 1,4-dioxane (Table 1, entries 6-15), as well
as few protic polar solvent like MeOH, EtOH and H2O (Table 1, entries 16-18) have been tested
for this reaction. No solvents were found effective like toluene, which gave 85% acyloxylated
product (2a) (Table 1, entry 5). Increase of the amount of rose bengal from 2 mol% to 3 mol%
found no considerable change but from 2 mol% to 1 mol% decreased the yield (Table 1, entry
19). Furthermore, the desired coupling product was not observed in dark condition (Table 1,
entry 20). So, the reaction using 2 mol% of rose bengal as photoredox catalyst, PIDA, toluene as
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solvent on irradiation with 34 W blue LED under aerobic condition is the optimized reaction
conditions (Table 1, entry 5).
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Then we explored this reaction for acyloxylation of C(sp3)-H of various substituted aryl-
2H-azirines (Scheme 2). A series of acyloxylated azirines were obtained (2a-2r) using this
protocol. We observed that simple 3-phenyl-2H-azirine (1a) produced the desired 3-phenyl-2H-
azirin-2-yl acetate (2a) in 85% yield. 3-Aryl-2H-azirines bearing electron-donating group (like -
methyl) in -ortho, -meta and -para positions of the phenyl ring efficiently reacted with PIDA to
provide good yields (2b, 75%; 2c, 78%; 2d, 76%). As well as, reactions with disubstituted and
trisubstituted electron-donating methyl group proceeded efficiently (2e, 70%; 2f, 68%). We
further found that strong electron-donating substituent (like t-butyl) underwent smooth reaction
under optimal reaction conditions (2g, 60%). Similarly, 2H-azirines with electron withdrawing
groups like chloro-, bromo-, fluoro- (1h-1n) underwent smooth reaction and afforded the
products (2h, 72%; 2i, 65%; 2j, 71%; 2k, 64%; 2l, 61%; 2m, 72%; 2n, 67%). Furthermore, the
acyloxylation reaction proceeded smoothly in case of strong electron-withdrawing group (–CF3)
containing aryl-2H-azirine which afforded moderate yield (2o, 58%). Aryl-2H-azirine with 4-
biphenyl, 1- and 2-naphthyl moieties produced the desired products 2p (78%), 2q (80%), 2r
(84%). It is worthy to mention that, though this protocol is applicable for a wide range of aryl-
2H-azirine we could not apply it for 2H-azirine with alkyl- and heteroaryl- moieties. We
attempted to prepare many heteroaryl- and alkyl- substituted 2H-azirines with the alkenes such
as 3-vinyl pyridine and 3-vinylthiophene, n-octene, allyl bromide, cyclohexene, cyclooctene etc.
Unfortunately, we could not prepare these azirines following our adopted procedure5c,16. The
reactions have been carried out under aerobic conditions. Inert atmosphere is not required7 and
no other external additives or oxidants are needed for this reaction. Under the present reaction
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conditions no decomposition or polymerization has been observed. No by-products have been
isolated in any reaction. The reactions are regioselective and high yielding. Characterization of
the synthesized known compounds made by comparison of spectral data. For newly synthesized
compounds IR, analytical and HRMS data has been provided.
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Scheme 2. Substrates Scope for the C(SP3)-H acyloxylation of Aryl-2H-azirinesa
Rose bengal (2 mol %)
N
N
PIDA
Ar
Ar
OAc
PhMe, 24 h
1
2
34 W Blue LED
N
N
N
N
OAc
OAc
OAc
OAc
CH3
H3C
N
CH3
2a
, 85%
2d
, 76%
2b
2c
, 78%
, 75%
N
N
CH3
N
OAc
OAc
OAc
OAc
tBu
Cl
H3C
CH3
H3C
CH3
2g
, 60%
2h
, 72%
2e
, 70%
2f
, 68%
Cl
N
N
N
N
OAc
OAc
OAc
OAc
Cl
Cl
Cl
Br
2i
, 65%
2j
, 71%
2l
, 61%
2k
, 64%
N
N
N
N
OAc
Ph
OAc
OAc
OAc
F3C
Br
2o
, 58%
2m
F
, 72%
2n
, 67%
2p
, 78%
N
N
OAc
OAc
2r
, 84%
2q
, 80%
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aReaction conditions : 3-aryl-2H-azirine (1, 1 mmol), PIDA (1 mmol), rose bengal (2 mol %),
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toluene (3.0 mL) under 34 W Blue LED irradiation for 24 h, ambient air, room temperature.
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The reaction of 3-phenyl-2H-azirine (1a) has been carried out in large scale (10 mmol).
The reaction is very much effective and 80% (1.40 gm) yield of the desired product has been
isolated (Scheme 3).
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Scheme 3. Gram-Scale Synthesis
N
N
Rose bengal (2 mol %)
PIDA
+
Ph
1a
Ph
OAc
, 80%, 1.40 g)
PhMe, 24 h
(10 mmol)
(10 mmol)
2a
34 W Blue LED
(
To predict the probable mechanism, we performed few additional experiments (Scheme
4). In the absence of a photocatalyst a less amount of product was obtained (Scheme 4, eq A).
Use of radical scavengers like 2,6-di-tert-butyl-4-methyl phenol (BHT), 2,2,6,6-
tetramethylpiperidine-1-oxyl (TEMPO), and p-benzoquinone (BQ) the reaction did not proceed
(Scheme 4, eqn B). Moreover, in the dark condition a trace amount of desired product was
obtained (Scheme 4, eq C). So, the reaction involved a radical pathway which require light
irradiation. In addition, we have tested our approach by using other hypervalent iodine(III)
reagents such as [bis(trifluoroacetoxy)iodo]benzene (Scheme 4, eq D) and 1,3-dihydro-1-
hydroxy-3-oxo-1,2-benziodoxole-4-carboxylic acid 1-oxide (mIBX) but it remains ineffectual
under the optimized reaction conditions.
Furthermore, we have measured redox potentials of 1a and PIDA by cyclic voltammetry
(see Supporting Information, Figures S1-S3) and taken redox potential data of RB under same
conditions from very recent report by our group.13d,e By comparing excited state oxidation
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potential (-1.32 V vs Fc+/Fc) and reduction potential (+0.49 V vs Fc+/Fc) values of the
photocatalyst (RB*) with redox potentials of PIDA (Ered = -1.30 V, -0.83 V vs Fc+/Fc) and 1a
(Eoxid = +0.95 V; Ered = -1.11 V vs Fc+/Fc), it is reasonable to suggest that the excited state of
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rose bengal (RB*) has been oxidized by PIDA.
On the basis of our control experiments
(Scheme 4), literature8,13,15 and cyclic voltammetry, a probable mechanism of the reaction has
been proposed as shown in Scheme 5. The excited rose bengal (RB*) takes an electron (SET)
from PIDA and transforms it to acetoxy radical (CH3COO∙), PhI (detected from the reaction
mixture by GC-MS) and the acetate anion (CH3COO-), whereas RB became a cation radical
(RB+.). The hydrogen atom abstraction by acetoxy radical could lead to the formation of 2H-
azirine radical A. The 2H-azirine radical A could then transfer one electron to cation radical
(RB+.) leading to the formation of intermediate carbocation B and ground state of photocatalyst
(RB) and completes the photocatalytic cycle. Finally, carbocation B on subsequent reaction with
acetate anion affords the desired product 2.
Scheme 4. Control Experiments
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without rose bengal
N
N
(A)
(B)
+
PIDA
Ph
1a
Ph
OAc
PhMe, 24 h
(1 mmol)
(1 mmol)
N
2a
, 13%
34 W Blue LED
N
Standard conditions
PIDA
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+
Ph
i. TEMPO,
OAc
2a,
(1 mmol)
Radical Scavenger
Ph
0%
(3 equiv.)
1a
(1 mmol)
2a,
ii. BHT,
iii. BQ,
0%
0%
2a,
N
Rose Bengal (2 mol %)
N
PIDA
+
(C)
Ph
(1 mmol)
Ph
2a,
OAc
PhMe, 24 h
Dark condition
1a
(1 mmol)
N
trace
F3C
O
O
CF3
O
N
I
Rose Bengal (2 mol %)
+
O
O
Ar
O
CF3
(D)
Ph
1a
PhMe, 24 h
3a',
0%
(1 mmol)
34 W Blue LED
(1 mmol)
Scheme 5. Proposed Reaction Mechanism
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PhI(OAc)2
Ered = -0.83 V, -1.30 V
Rose Bengal
Cl
O
RB*
Cl
Cl
h
SET
PhI + AcO + AcO
Cl
COONa
I
.+
ERB /RB* = -1.32 V
I
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RB
RB
NaO
I
O
SET
I
N
N
N
N
AcO
OAc
AcO
H
Ar
H
Ar
H
Ar
Ar
H
A
B
Ered = -1.11 V
Eoxid = 0.95 V
Conclusion
In conclusion, a convenient route for the acyloxylation of C(sp3)-H of aryl-2H-azirines
has been reported using PIDA by irradiation of blue LED. In the present reactions conditions
aryl-2H-azirines with different functional groups were remained unaffected. The main
advantages of the protocol are (i) mild reaction conditions, (ii) use of organophotocatalyst, (iii)
large number of substrates scope, (iv) ambient air, (v) gram-scale synthesis and (vi) metal-free
conditions. We believe that, this is the first report of acyloxylation of C(sp3)-H of aryl-2H-
azirines using visible light irradiation. We hope our methodology is a meaningful addition to the
existing methods in literature.
EXPERIMENTAL SECTION
General Information. No purification of the chemicals has been carried out after purchasing
1
from commercial sources. H NMR spectra were determined as solutions in CDCl3 on a 400
MHz spectrometer. Chemical shifts are in parts per million (δ), and reported as s (singlet), d
(doublet), t (triplet), m (multiplet), dd (double doublet), and J (coupling constants) in Hz.
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13C{1H} NMR spectra were taken at 100 MHz in CDCl3 solution. Slide (made of glass) coated
with silica gel has been used for Thin Layer Chromatography. Silica gel (60-120 mesh) as
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stationary phase and ethyl acetate petroleum ether (60-80 C) were used for column
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chromatography. Oven dried glassware were used for reactants which are moisture sensitive. All
the 2H-azirines were prepared according to the reported methods.5c,16 The detailed information
about the blue LED is given in the Supporting Information. Borosilicate glass tube was used as a
reaction tube. The reaction tube was positioned 7 cm away from the exposed of Kessil 34 W blue
LED (450-530 nm). Regular fan was used to maintain the temperature 28 to 30 °C during the
reaction. We have not used any filters.
Typical Procedure for the Synthesis of 3-Phenyl-2H-azirine (1a). In a round bottom flask 10
mmol of styrene (1.041 g) was taken in CCl4 (8 mL) and stirred at room temperature. Bromine
(1.600 g, 10 mmol) in CCl4 (6 mL) was added slowly into it and was stirred for 2 h. Then the
CCl4 was removed in vacuo to get the 1-(1,2-dibromoethyl)benzene residue as crystalline solid
(2.481 g, 94%). 1-(1,2-Dibromoethyl)benzene (2.481 g, 9.4 mmol) was dissolved in 14 mL of
dimethyl sulfoxide. After a slow stream of N2 was passed through the apparatus, sodium azide
(0.975 g, 15 mmol) was slowly added into the solution and for 45 min afterward. The mixture
became thick with precipitated azido bromide and was stirred for a further 13 h at room
temperature. The reaction mixture after treatment with 0.4 g (10 mmol) of sodium hydroxide in
0.4 mL of deionized water was stirred at room temperature for 24 h. Then the mixture was
poured into 40 mL of 2% sodium bicarbonate aqueous solution and extracted with
dichloromethane. The extract was washed with deionized water. Dichloromethane was removed
in vacuo, and evaporated to yield crude 1-azidostyrene as red oil. The oil was passed through a
column of silica gel using petroleum ether as eluent. The eluent was removed in vacuo and the
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residual pale-yellow oil was dissolved in 20 mL of toluene. Then the solution was refluxed for 4
h. Removal of the solvent and distillation of the crude product, 0.820 g of 3-phenyl-2H-azirine
(70% yield) was obtained and used for the next experiment without further purification. The
schematic representation is shown in Scheme S1 (Supporting Information).
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General Procedure for the Synthesis of Compound 2. A mixture of 3-aryl-2H-azirine 1 (1.0
mmol), rose bengal (2.0 mol %, 20 mg) and freshly distilled toluene (3 mL) was taken in an
reaction vessel (oven dried) equipped with a magnetic stirrer bar. Then (diacetoxyiodo)benzene
(322 mg, 1 mmol) was added to the resultant mixture. The reaction vessel was irradiated using a
blue LED (34 W, 450-530 nm) at room temperature under open atmosphere for 24 h. The
reaction mixture was diluted with a mixture of 10 mL water/ethyl acetate (1:1) after completion
of the reaction (TLC). Anhydrous Na2SO4 was used to dry the combined organic layer.
Evaporation of solvent furnished the crude product. The pure product was obtained by column
chromatography on silica gel (60-120 mesh) using ethyl acetate-petroleum ether as
eluent.General Procedure for the Synthesis of 3-Phenyl-2H-azirin-2-yl acetate (2a) on the
Gram-Scale. In a oven dried reaction vessel a mixture of 3-phenyl-2H-azirine 1 (1.17 g, 10
mmol), rose bengal (2 mol %, 200 mg) and freshly distilled toluene (30 mL) was taken equipped
with a magnetic stirrer bar. Then (diacetoxyiodo)benzene (3.22 g, 10 mmol) was added to the
resultant mixture. The reaction vessel was irradiated using a blue LED (34 W, 450-530 nm) at
room temperature under open atmosphere for 24 h. After completion (TLC), the reaction mixture
was diluted with a 1:1 mixture of water/ethyl acetate (80 mL) and followed by brine solution (2 x
50 mL). Then the combined organic layer was dried over anhydrous Na2SO4. Evaporation of
solvent under vacuo furnished the crude product. The crude product was subjected to column
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chromatography on silica gel (60−120 mesh) using ethyl acetate-petroleum ether (60-80 C) as
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eluent to obtain the analytically pure product as pale yellow liquid (1.40 g, yield 80%).
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3-Phenyl-2H-azirin-2-yl acetate (2a).8 Pale yellow liquid (149 mg, yield 85%); Rf = 0.55
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(petroleum ether/EtOAc = 95/5); H NMR (CDCl3, 400 MHz): δ 8.00-7.98 (m, 2H), 7.67-7.63
(m, 1H), 7.60-7.56 (m, 2H), 5.19 (s, 1H), 2.06 (s, 3H). 13C{1H} NMR (CDCl3, 100 MHz): δ
171.6, 171.5, 134.2, 130.3, 129.4, 123.2, 58.6, 21.1.
3-(o-Tolyl)-2H-azirin-2-yl acetate (2b).8 Pale yellow liquid (132 mg, yield 75%); Rf = 0.50
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(petroleum ether/EtOAc = 96/4); H NMR (CDCl3, 400 MHz): δ 7.90-7.88 (m, 1H), 7.55-7.51
(m, 1H), 7.41-7.37 (m, 2H), 5.20 (s, 1H), 2.71 (s, 3H), 2.08 (s, 3H). C{1H} NMR (CDCl3, 100
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MHz): δ 171.8, 170.4, 141.7, 133.8, 132.4, 131.2, 126.6, 121.8, 57.4, 21.2, 19.9.
3-(m-Tolyl)-2H-azirin-2-yl acetate (2c).8 Pale yellow liquid (147 mg, yield 78%); Rf = 0.55
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(petroleum ether/EtOAc = 95/5); H NMR (CDCl3, 400 MHz): δ 7.81-7.79 (m, 2H), 7.47-7.46
(m, 2H), 5.19 (s, 1H), 2.45 (s, 3H), 2.07 (s, 3H). 13C{1H} NMR (CDCl3, 100 MHz): δ 171.7,
171.4, 139.4 135.0, 130.7, 129.3, 127.5, 123.1, 58.7, 21.4, 21.2.
3-(p-Tolyl)-2H-azirin-2-yl acetate (2d).8 Pale yellow liquid (144 mg, yield 76%); Rf = 0.45
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(petroleum ether/EtOAc = 94/6); H NMR (CDCl3, 400 MHz): δ 7.89 (d, J = 8.4 Hz, 2H), 7.38
(d, J = 8.0 Hz, 2H), 5.17 (s, 1H), 2.46 (s, 3H), 2.06 (s, 3H). 13C{1H} NMR (CDCl3, 100 MHz): δ
171.7, 170.9, 145.3, 130.3, 130.2, 120.4, 58.7, 22.1, 21.2.
3-(2,4-Dimethylphenyl)-2H-azirin-2-yl acetate (2e). Pale yellow liquid (142 mg, yield 70%); Rf
= 0.55 (petroleum ether/EtOAc = 95/5); IR (KBr) 3131, 1751, 1400, 1222, 1032 cm−1; 1H NMR
(CDCl3, 400 MHz): δ 7.76 (d, J = 8.4 Hz, 1H), 7.20-7.18 (m, 2H), 5.17 (s, 1H), 2.66 (s, 3H),
2.41 (s, 3H), 2.06 (s, 3H). 13C{1H} NMR (CDCl3, 100 MHz): δ 171.8, 169.8, 144.8, 141.6,
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132.4, 132.0, 127.3, 119.0, 57.4, 21.9, 21.2, 19.8. Anal. Calcd for C12H13NO2: C, 70.92; H, 6.45;
N, 6.89%; Found: C, 70.86; H, 6.39; N, 6.83%. HRMS (ESI) ([M + Na]+) Calcd. for
[C12H13NO2]+: 240.1001; Found 240.0995.
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3-Mesityl-2H-azirin-2-yl acetate (2f). Pale yellow liquid (148 mg, yield 68%); Rf = 0.60
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(petroleum ether/EtOAc = 95/5); IR (KBr) 3132, 1748, 1399, 1226, 1034, 861 cm−1; H NMR
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(CDCl3, 400 MHz): δ 7.00 (s, 2H), 5.30 (s, 1H), 2.60 (s, 6H), 2.36 (s, 3H), 2.08 (s, 3H). C{1H}
NMR (CDCl3, 100 MHz): δ 171.7, 167.5, 144.6, 142.3, 129.7, 117.8, 57.6, 21.7, 21.3, 20.2.
Anal. Calcd for C13H15NO2: C, 71.87; H, 6.96; N, 6.45%; Found: C, 71.81; H, 6.89; N, 6.40%.
HRMS (ESI) ([M + Na]+) Calcd. for [C13H15NO2]+: 406.1127; Found 406.1117.
3-(4-(Tert-butyl)phenyl)-2H-azirin-2-yl acetate (2g).8 Pale yellow liquid (139 mg, yield 60%); Rf
= 0.55 (petroleum ether/EtOAc = 95/5); 1H NMR (CDCl3, 400 MHz): δ 7.95-7.92 (m, 2H), 7.61-
7.59 (m, 2H), 5.17 (s, 1H), 2.05 (s, 3H), 1.36 (s, 9H). 13C{1H} NMR (CDCl3, 100 MHz): δ
171.8, 171.0, 158.3, 130.3, 126.5, 120.5, 58.7, 31.8, 31.3, 21.2.
3-(2-Chlorophenyl)-2H-azirin-2-yl acetate (2h).8 Pale yellow liquid (151 mg, yield 72%); Rf =
0.65 (petroleum ether/EtOAc = 94/6);1H NMR (CDCl3, 400 MHz): δ 8.03-8.01 (m, 1H), 7.58-
7.57 (m, 2H), 7.51-7.48 (m, 1H), 5.30 (s, 1H), 2.08 (s, 3H). 13C{1H} NMR (CDCl3, 100 MHz): δ
171.6, 170.1, 136.8, 134.9, 132.6, 130.9, 130.7, 127.5, 58.3, 21.2.
3-(3-Chlorophenyl)-2H-azirin-2-yl acetate (2i).8 Pale yellow liquid (136 mg, yield 65%); Rf =
1
0.50 (petroleum ether/EtOAc = 95/5); H NMR (CDCl3, 400 MHz): δ 7.99-7.98 (m, 1H), 7.91-
7.89 (m, 1H), 7.64-7.61 (m, 1H), 7.55-7.51 (m, 1H), 5.17 (s, 1H), 2.07 (s, 3H). 13C{1H} NMR
(CDCl3, 100 MHz): δ 171.5, 171.3, 135.6, 134.1, 130.8, 130.0, 128.3, 125.0, 58.6, 21.1.
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3-(4-Chlorophenyl)-2H-azirin-2-yl acetate (2j).8 Pale yellow liquid (149 mg, yield 71%); Rf =
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0.65 (petroleum ether/EtOAc = 94/6); H NMR (CDCl3, 400 MHz): δ 7.95-7.93 (m, 2H), 7.57-
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7.55 (m, 2H), 5.14 (s, 1H), 2.06 (s, 3H). C{1H} NMR (CDCl3, 100 MHz): δ 171.5, 171.0,
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140.7, 131.5, 129.9, 121.7, 58.5, 21.1.
3-(2,6-Dichlorophenyl)-2H-azirin-2-yl acetate (2k). Pale yellow liquid (156 mg, yield 64%); Rf
= 0.45 (petroleum ether/EtOAc = 95/5); IR (KBr) 3131, 1751, 1222, 1034, 785 cm−1; H NMR
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(CDCl3, 400 MHz): δ 7.48 (s, 3H), 5.39 (s, 1H), 2.08 (s, 3H). 13C{1H} NMR (CDCl3, 100 MHz):
δ 171.3, 168.7, 138.6, 134.6, 129.4, 120.7, 57.7, 21.2. Anal. Calcd for C10H7Cl2NO2: C, 49.21;
H, 2.89; N, 5.74%; Found: C, 49.13; H, 2.81; N, 5.82%. HRMS (ESI) ([M + Na]+) Calcd. for
[C10H7Cl2NO2]+: 265.9752; Found 265.9748.
3-(3-Bromophenyl)-2H-azirin-2-yl acetate (2l).8 Pale yellow liquid (155 mg, yield 61%); Rf =
0.50 (petroleum ether/EtOAc = 96/4); 1H NMR (CDCl3, 400 MHz): δ 8.145-8.137 (m, 1H), 7.96-
7.93 (m, 1H), 7.79-7.76 (m, 1H), 7.49-7.45 (m, 1H), 5.16 (s, 1H), 2.07 (s, 3H). 13C{1H} NMR
(CDCl3, 100 MHz): δ 171.5, 171.2, 137.0, 132.9, 131.0, 128.7, 125.2, 123.4, 58.6, 21.1.
3-(4-Bromophenyl)-2H-azirin-2-yl acetate (2m).8 Pale yellow liquid (183 mg, yield 72%); Rf =
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0.55 (petroleum ether/EtOAc = 96/4); H NMR (CDCl3, 400 MHz): δ 7.88-7.86 (m, 2H), 7.74-
7.72 (m, 2H), 5.14 (s, 1H), 2.06 (s, 3H). C{1H} NMR (CDCl3, 100 MHz): δ 171.4, 171.1,
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132.8, 131.4, 129.2, 122.0, 58.4, 21.0.
3-(3-Fluorophenyl)-2H-azirin-2-yl acetate (2n). Pale yellow liquid (129.4 mg, yield 67%); Rf =
0.45 (petroleum ether/EtOAc = 95/5); IR (KBr) 3132, 1753, 1400, 1222, 1036 cm−1; H NMR
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(CDCl3, 400 MHz): δ 7.82-7.79 (m, 2H), 7.72-7.69 (m, 1H), 7.60-7.55 (m, 1H), 7.60-7.55 (m,
1H), 7.38-7.33 (m, 1H), 5.16 (s, 1H), 2.07 (s, 3H). 13C{1H} NMR (CDCl3, 100 MHz): δ 171.5,
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3JC-F = 21 Hz), 116.8 (d, JC-F = 22 Hz), 58.6, 21.1. Anal. Calcd for C10H8FNO2: C, 62.18; H,
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[C10H8FNO2]+: 194.0617; Found 194.0610.
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3-(4-(Trifluoromethyl)phenyl)-2H-azirin-2-yl acetate (2o).8 Pale yellow liquid (141 mg, yield
58%); Rf = 0.60 (petroleum ether/EtOAc = 94/6); 1H NMR (CDCl3, 400 MHz): δ 8.15 (d, J = 8.4
Hz, 2H), 7.86 (d, J = 8.0 Hz, 2H), 5.18 (s, 1H), 2.08 (s, 3H). 13C{1H} NMR (CDCl3, 100 MHz):
δ 171.7, 171.4, 130.7 (q, J = 33 Hz), 129.1, 126.5, 126. 4 (q, J = 5 Hz), 124.9 (q, J = 102 Hz),
58.5, 21.1.
3-([1,1'-Biphenyl]-4-yl)-2H-azirin-2-yl acetate (2p).8 Pale yellow solid (196 mg, yield 78%); Rf
= 0.55 (petroleum ether/EtOAc = 93/7); 1H NMR (CDCl3, 400 MHz): δ 8.09-8.07 (m, 2H), 7.82-
7.80 (m, 2H), 7.67-7.64 (m, 2H), 7.51-7.43 (m, 3H), 5.21 (s, 1H), 2.08 (s, 3H). 13C{1H} NMR
(CDCl3, 100 MHz): δ 171.7, 171.1, 147.0, 139.7, 130.8, 129.2, 128.7, 128.1, 127.5, 121.9, 58.7,
21.2.
3-(Naphthalen-1-yl)-2H-azirin-2-yl acetate (2q).8 Pale yellow liquid (180 mg, yield 80%); Rf =
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0.55 (petroleum ether/EtOAc = 93/7); H NMR (CDCl3, 400 MHz): δ 8.96 (d, J = 8.4 Hz, 1H),
8.18-8.13 (m, 2H), 7.97 (d, J = 8.0 Hz, 1H), 7.76-7.72 (m, 1H), 7.67-7.63 (m, 2H), 5.29 (s, 1H),
2.10 (s, 3H). 13C{1H} NMR (CDCl3, 100 MHz): δ 172.0, 170.4, 135.0, 133.6, 133.4, 131.8,
128.9, 128.7, 127.4, 125.4, 124.7, 118.9, 56.5, 21.2.
3-(Naphthalen-2-yl)-2H-azirin-2-yl acetate (2r).8 Pale yellow liquid (189 mg, yield 84%); Rf =
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0.45 (petroleum ether/EtOAc = 94/6); H NMR (CDCl3, 400 MHz): δ 8.49 (s, 1H), 8.06-8.00
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(CDCl3, 100 MHz): δ 171.7, 171.5, 136.0, 132.9, 132.8, 129.50, 129.48, 129.2, 128.2, 127.4,
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Supporting information: CV measurements, IR and mass spectra analysis, GC-MS data,
Synthetic route for the synthesis of 2H-azirines, light information, reaction setup and scanned
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copies of H and 13C{1H} NMR spectra of the synthesized compounds are available as
supporting information. This material is available free of charge via the Internet at
http://pubs.acs.org.
Acknowledgements: A. Majee acknowledges financial support from the DST-RSF Major
Research Project (Ref. No. INT/RUS/RSF/P-08). S. Santra is thankful to the Russian Science
Foundation – Russia (Ref. # 18-73-00301) for funding. We are thankful to the DST-FIST and
UGC-SAP program. We are thankful to Dr. Susanta Ghosh and Dr. Debashis Ghosh for helping
the CV experiments.
Author Information
Email
*Adinath Majee: adinath.majee@visva-bharati.ac.in (Corrresponding Author)
Aramita De: aramitade91@gmail.com
Sougata Santra: sougatasantra85@gmail.com
Alakananda Hajra: alakananda.hajra@visva-bharati.ac.in
Grigory V. Zyryanov: gvzyryanov@gmail.com
ORCID
Adinath Majee: 0000-0002-5439-6851
Sougata Santra: 0000-0002-4186-6105
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Alakananda Hajra: 0000-0001-6141-0343
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Grigory V. Zyryanov: 0000-0002-9692-2346
Notes
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The authors declare no competing financial interest.
REFERENCES
(1) (a) Wang, D.; Weinstein, A. B.; White, P. B.; Stahl, S. S. Chem. Ligand-Promoted
Palladium-Catalyzed Aerobic Oxidation Reactions. Chem. Rev. 2018, 118 (5), 2636−2679. (b)
Liang, Y.-F.; Jiao, N. Oxygenation via C−H/C−C Bond Activation with Molecular Oxygen. Acc.
Chem. Res. 2017, 50 (7), 1640-1653. (c) Wu, W.; Jiang, H. Palladium-Catalyzed Oxidation of
Unsaturated Hydrocarbons Using Molecular Oxygen. Acc. Chem. Res. 2012, 45 (10), 1736-1748.
(d) Alonso, D. A.; Najera, C.; Pastor, I. M.; Yus, M. Transition-Metal-Catalyzed Synthesis of
Hydroxylated Arenes. Chem. Eur. J. 2010, 16 (18), 5274-5284. (e) Mack, J. B. C.; Gipson, J.
D.; Du Bois, J.; Sigman, M. S. Ruthenium-Catalyzed C−H Hydroxylation in Aqueous Acid
Enables Selective Functionalization of Amine Derivatives. J. Am. Chem. Soc. 2017, 139 (28),
9503-9506. (f) Lee, M.; Sanford, M. S. Platinum-Catalyzed, Terminal-Selective C(sp3)-H
Oxidation of Aliphatic Amines. J. Am. Chem. Soc. 2015, 137 (40), 12796-12799.
(2) (a) Chen, M. S.; White, M. C. A Predictably Selective Aliphatic C−H Oxidation Reaction for
Complex Molecule Synthesis. Science 2007, 318 (5851), 783-787. (b) Que, L., Jr; Tolman, W. B.
Biologically inspired oxidation catalysis. Nature 2008, 455, 333-340.
(3) Majji, G.; Rout, S. K.; Rajamanickam, S.; Guin, S.; Patel, B. K. Synthesis of Esters via sp3 C-
H Functionalisation. Org. Biomol. Chem. 2016, 14 (35), 8178-8211.
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(4) (a) Palacios, F.; Retana, A. M. O.; Marigorta, E. M.; Los Santos, J. M. Preparation, Properties
and Synthetic Applications of 2H-Azirines: A Review. Org. Prep. Proced. Int. 2002, 34 (3), 219-
269. (b) Palacios, F.; Retana, A. N. O.; Marigorta, E. M.; Los Santos, J. M. 2H-Azirines as
Synthetic Tools in Organic Chemistry. Eur. J. Org. Chem. 2001, 2001 (13), 2401-2414. (c)
Chen, L.; Li, H.; Li, P.; Wang, L. Visible-Light Photoredox Catalyzed Three-Component
Cyclization of 2H-Azirines, Alkynyl Bromides, and Molecular Oxygen to Oxazole Skeleton.
Org. Lett. 2016, 18 (15), 3646-3649. (d) Okamoto, K.; Mashida, A.; Watanabe, M.; Ohe, K. An
Unexpected Disproportional Reaction of 2H-Azirines Giving (1E,3Z)-2-Aza-1,3-dienes and
Aromatic Nitriles in the Presence of Nickel Catalysts. Chem. Commun. 2012, 48 (29), 3554-
3556.
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(5) (a) Skepper, C. K.; Dalisay, D. S.; Molinski, T. F. Synthesis and Antifungal Activity of (-)-
(Z)-Dysidazirine. Org. Lett. 2008, 10 (22), 5269-5271. (b) Palacios, F.; Ochoa de Retana, A. M.;
Martínez de Marigorta, E.; Manuel de los Santos, J. Eur. J. Org. Chem. 2001, 2001 (13), 2401-
2414. (c) Miller, T. W.; Tristram, E. W.; Wolf, F. J. Azirinomycin. II Isolation and Chemical
Characterization as 3-Methyl-2(2H) Azirinecarboxylic Acid. J. Antibiot. 1971, 24 (1), 48-50. (d)
Salomon, C. E.; Williams, D. H.; Faulkner, D. J. New Azacyclopropene Derivatives from
Dysidea fragilis Collected in Pohnpei. J. Nat. Prod. 1995, 58 (9), 1463-1466. (e) Davis, F. A.;
Liu, H.; Liang, C.-H.; Reddy, G. V.; Zhang, Y.; Fang, T.; Titus, D. D. Asymmetric Synthesis of
2H-Azirine 2-Carboxylate Esters. J. Org. Chem. 1999, 64 (24), 8929-8935.
(6) Singh, G. S.; D’hooghe, M.; Kimpe, N. D. Synthesis and Reactivity of C-Heteroatom-
Substituted Aziridines. Chem. Rev. 2007, 107, 2080-2135.
ACS Paragon Plus Environment

Page 21 of 25
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
(7) For selected reviews, see: (a) Lyons, T. W.; Sanford, M. S. Palladium-Catalyzed Ligand-
Directed C-H Functionalization Reactions. Chem. Rev. 2010, 110 (2), 1147-1169. (b) Liu, B.;
Hu, F.; Shi, B.-F. Recent Advances on Ester Synthesis via Transition-Metal Catalyzed C-H
Functionalization. ACS Catal. 2015, 5 (3), 1863-1881. (c) Chen, F.-J.; Zhao, S.; Hu, F.; Chen,
K.; Zhang, Q.; Zhang, S.- Q.; Shi, B.-F. Pd(II)-Catalyzed Alkoxylation of Unactivated C(sp3 )–H
and C(sp2 )–H Bonds Using a Removable Directing Group: Efficient Synthesis of Alkyl Ethers.
Chem. Sci. 2013, 4 (11), 4187-4192. (d) Nakano, Y.; Lupton, D. W. Palladium[II] catalysed
C(sp3)–H oxidation of dimethyl carbamoyl tetrahydrocarbazoles. Chem. Commun. 2014, 50 (14),
1757-1760. (e) Wang, C.; Zhang, L.; You, J. Nickel-Catalyzed Aminoxylation of Inert Aliphatic
C(sp3 )−H Bonds with Stable Nitroxyl Radicals under Air: One-Pot Route to α-Formyl Acid
Derivatives. Org. Lett. 2017, 19 (7), 1690-1693. (f) Yoshimura, A.; Zhdankin, V. V. Advances in
Synthetic Applications of Hypervalent Iodine Compounds. Chem. Rev. 2016, 116 (5), 3328-
3435. For photocatalytic transformations of PIDA, see: (g) Xie, J.; Xu, P.; Li, H.; Xue, Q.; Jin,
H.; Cheng, Y.; Zhu, C. A room temperature decarboxylation/C–H functionalization cascade by
visible-light photoredox catalysis. Chem. Commun. 2013, 49 (50), 5672-5674. (h) Paul, A.;
Chatterjee, D.; Rajkamal, Halder, T.; Banerjee, S.; Yadav, S. Metal Free Visible Light
Photoredox Activation of PhI(OAc)2 for the Conversion of Arylboronic Acids to Phenols.
Tetrahedron Lett. 2015, 56 (19), 2496–2499. (i) He, Z.; Bae, M.; Wu, J.; Jamison, T. F.
Synthesis of Highly Functionalized Polycyclic Quinoxaline DerivativesUsing Visible-Light
Photoredox Catalysis. Angew. Chem. Int. Ed. 2014, 53 (52), 14451–14455. (j) Duhamel, T.;
Martínez, M. D.; Sideri, I. K.; Muñiz, K. 1,3-Diamine Formation from an Interrupted
Hofmann−Löffler Reaction: Iodine Catalyst Turnover through Ritter-Type Amination. ACS
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
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37
38
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41
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45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
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The Journal of Organic Chemistry
Page 22 of 25
1
2
3
4
5
6
Catal. 2019, 9, 7741-7745. (k) Mondal, R. R.; Khamarui, S.; Maiti, D. K. Photocatalytic
Generation of Nitrenes for Rapid Diaziridination. Org. Lett. 2017, 19 (21), 5964-5967.
7
8
9
(8) Wang, L.; Li, H.; Wang, L. Iron-Catalyzed C(sp3)–H Acyloxylation of Aryl-2H Azirines with
Hypervalent Iodine(III) Reagents. Org. Lett. 2018, 20 (6), 1663-1666.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(9) (a) Ganley, J. M.; Christensen, M.; Lam, Y. H.; Peng, Z.; Angeles, A. R.; Yeung, C. S.
Metal- and Acid-Free C-H Formylation of Nitrogen Heterocycles: Using Trioxane as an
Aldehyde Equivalent Enabled by an Organic-Soluble Oxidant. Org. Lett. 2018, 20 (18), 5752−
5756. (b) Narayanam, J. M. R.; Stephenson, C. R. J. Visible Light Photoredox Catalysis:
Applications in Organic Synthesis. Chem. Soc. Rev. 2011, 40 (1), 102−113. (c) Shaw, M. H.;
Twilton, J.; MacMillan, D. W. C. Photoredox Catalysis in Organic Chemistry. J. Org. Chem.
2016, 81 (16), 6898−6926. (d) Ghosh, I.; Marzo, L.; Das, A.; Shaikh, R.; König, B. Visible Light
Mediated Photoredox Catalytic Arylation Reactions. Acc. Chem. Res. 2016, 49 (8), 1566−1577.
(e) Zhou, Q.-Q.; Zou, Y.-Q.; Lu, L.- Q.; Xiao, W.-J. Visible-Light-Induced Organic
Photochemical Reactions via Energy Transfer Pathways. Angew. Chem. Int. Ed. 2019, 58 (6),
1586-1604. (f) Li, J.; Zhang, J.; Tan, H.; Wang, D. Z. Visible Light-Promoted Vinylation of
Tetrahydrofuran with Alkynes through Direct C-H Bond Functionalization. Org. Lett. 2015, 17
(10), 2522−2525. (g) Marzo, L.; Pagire, S. K.; Reiser, O.; König, B. Visible-Light
Photocatalysis: Does It Make a Difference in Organic Synthesis? Angew. Chem. Int. Ed. 2018,
57 (32), 10034−10072. (h) Wang, C. S.; Dixneuf, P. H.; Soule, J. F. Photoredox Catalysis for
Building C-C Bonds from C(Sp2)-H Bonds. Chem. Rev. 2018, 118 (16), 7532−7585. (i) Sharma,
S.; Sharma, A. Recent Advances in Photocatalytic Manipulations of Rose Bengal in Organic
Synthesis. Org. Biomol. Chem. 2019, 17 (18), 4384-4405.
ACS Paragon Plus Environment

Page 23 of 25
The Journal of Organic Chemistry
1
2
3
4
5
6
7
8
9
(10) (a) Romero, N. A.; Nicewicz, D. A. Organic Photoredox Catalysis. Chem. Rev. 2016, 116
(17), 10075-10166. (b) Ravelli, D.; Fagnoni, M. Dyes as Visible Light Photoredox
Organocatalysts. ChemCatChem 2012, 4 (2), 169-171. (c) Fukuzumi, S.; Ohkubo, K. Selective
photocatalytic reactions with organic photocatalysts. Chem. Sci. 2013, 4 (2), 561-574. (d) Sun, P.;
Yang, D.; Wei, W.; Jiang, M.; Wang, Z.; Zhang, L.; Zhang, H.; Zhang, Z.; Wang, Y.; Wang, H.
Visible-Light-Induced C–H Sulfenylation Using Sulfinic Acids. Green Chem. 2017, 19 (20),
4785-4791.
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
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42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
(11) (a) Chatterjee, R.; Samanta, S.; Mukherjee, A.; Santra, S.; Zyryanov, G. V.; Majee, A. Use
of allylzinc halide as a source of halide: Differential addition of nucleophiles to Ts-aziridines and
aldehydes under similar reaction conditions. Tetrahedron Lett. 2019, 60 (3), 276-283. (b)
Ghosal, N. C.; Santra, S.; Das, S.; Hajra, A.; Zyryanov, G. V. Majee, A. Organocatalysis by an
aprotic imidazolium zwitterion: regioselective ring-opening of aziridines and applicable to gram scale
synthesis. Green Chem. 2016, 18 (2), 565-574.
(12) (a) Mahato, S.; Santra, S.; Zyryanov, G. V.; Majee, A. Metal-Free Amidation Reactions of
Terminal Alkynes with Benzenesulfonamide. J. Org. Chem. 2019, 84 (6), 3176-3183. (b)
Mandal, S.; Hajra, A. Metal-Free C-5 Hydroxylation of 8-Aminoquinoline Amide. J. Org. Chem.
2018, 83 (18), 11392-11398.
(13) (a) Singsardar, M.; Laru, S.; Mondal, S.; Hajra, A. Visible-Light-Induced Regioselective
Cross Dehydrogenative Coupling of 2H-Indazoles with Ethers. J. Org. Chem. 2019, 84 (7),
4543-4550. (b) Singsardar, M.; Dey, A.; Sarkar, R.; Hajra, A. Visible-Light-Induced
Organophotoredox Catalyzed Phosphonylation of 2H-Indazoles with Diphenylphosphine Oxide.
J. Org. Chem. 2018, 83 (20), 12694-12701. (c) Kibriya, G.; Mondal, S.; Hajra, A. Visible-Light-
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Page 24 of 25
1
2
3
4
5
6
Mediated Synthesis of Unsymmetrical Diaryl Sulfides via Oxidative Coupling of Arylhydrazine
with Thiol. Org. Lett. 2018, 20 (23), 7740-7743. (d) Singsardar, M.; Mondal, S.; Laru, S.; Hajra,
7
8
9
A.
Organophotoredox
catalyzed
C(SP2)-H
difluoromethylenephosphonation
of
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12
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43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
imidazoheterocycles. Org. Lett. 2019, 21 (14), 5606-5610.
(14) (a) Khlebnikov, A. F.; Novikov, M. S.; Rostovskii, N. V. Advances in 2H-azirine chemistry:
A seven-year update. Tetrahedron 2019, 75 (18), 2555-2624. (b) Cai, B. -G.; Chen, Z. -L.; Xu,
G. -Y.; Xuan, J.; Xiao, W. -J. [3 + 2]-Cycloaddition of 2H-Azirines with Nitrosoarenes: Visible-
Light-Promoted Synthesis of 2,5-Dihydro-1,2,4-oxadiazoles. Org. Lett. 2019, 21 (11), 4234-
4238. (c) Zeng, T.-T.; Xuan, J.; Ding, W.; Wang, K.; Lu, L.-Q.; Xiao W.-J. [3 + 2]
Cycloaddition/Oxidative Aromatization Sequence via Photoredox Catalysis: One-Pot Synthesis
of Oxazoles from 2H-Azirines and Aldehydes. Org. Lett. 2015, 17 (16), 4070-4073. (d)
Osisioma, O.; Chakraborty, M.; Ault, B. S.; Gudmundsdottir, A. D. Wavelength-Dependent
Photochemistry of 2-Azidovinylbenzene and 2-Phenyl-2H-azirine. J.
2018, 1172, 94-101. (e) Schmidt, F. G.; Barner-Kowollik, C.; Mueller, J.; Blinco, J.
Cycloaddition for polymerization or crosslinking
Mol. Struct.
using azirine compounds induced by visible light. Eur. Pat. Appl. 2016, EP 3053905
A1 20160810.
(15) (a) Sürig, T.; Grützmacher. H. F.; De Kimpe, N. Destabilized Carbenium Ions: α-Imidoyl
Carbenium Ions and the Electron Impact Mass Spectra of α-Haloaldimines and α-Haloketimines.
Org. Mass Spectrom. 1991, 26 (10), 882-888. (b) De Kimpe, N.; Stevens, C. Silver Ion Induced
Reactions of α-Haloimines. Tetrahedron, 1990, 46 (19), 6753–6770. (c) De Kimpe, N.; Verhé,
R.; De Buyck, L.; Schamp, N.; Charpentier-Morize, M. Friedel-Crafts Reaction of α-
Chloroaldimines: Possible Intermediacy of α-Imidoylcarbenium Ions. Tetrahedron Lett., 1982,
ACS Paragon Plus Environment

Page 25 of 25
The Journal of Organic Chemistry
1
2
3
4
5
6
23 (28), 2853–2856. (d) Wolczanski, P. T.; Bercaw, J. E. On the Mechanisms of Carbon
Monoxide Reduction with Zirconium Hydrides. Acc. Chem. Res. 1980, 13 (4), 121-127.
7
8
9
(16) (a) Wang, R.; Yu, F.; Liu, P.; Chen, L. A Turn-on Fluorescent Probe Based
on Hydroxylamine Oxidation for Detecting Ferric Ion Selectively in Living Cells. Chem.
Commun. 2012, 48 (43), 5310-5312. (b) Wang, Y.; Kah, T.; Lee, J.; Chiba, S. Synthesis of
Isoquinolines from α‐Aryl Vinyl Azides and Internal Alkynes by Rh–Cu Bimetallic Cooperation.
Angew. Chem. Int. Ed. 2011, 50 (26), 5927-5931. (c) Timen, A. S.; Risberg, E.; Somfai, P.
Improved Procedure for Cyclization of Vinyl Azides into 3-Substituted-2H-azirines. Tetrahedron
Lett. 2003, 44 (28), 5339-5341.
10
11
12
13
14
15
16
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20
21
22
23
24
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26
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