Visible light-driven azidation/difunctionalization of vinyl arenes with azidobenziodoxole under copper catalysis

Article abstract of DOI:10.1021/acs.joc.9b01569

Visible light-driven azidation of vinyl arenes with azidobenziodoxole as the azidating agent was investigated in acetonitrile by using Cu(I)(phenanthroline)₂ complex [Cu(dap)₂]PF₆ as photocatalyst. The reactions generated three types of difunctionalization products, which correspond to reaction patterns of amido-azidation, benzoyloxy-azidation, and diazidation. The electronic nature of the aryl group attached to the olefin moiety was found to play a crucial role in determining the reaction consequence: When the aryl group was electron-rich, the reactions afforded benzoyloxy-azidation products exclusively; for highly electron-deficient vinyl arenes, by contrast, diazidation products were generated in moderate yields. When the aryl group was moderately electron-rich or electron-deficient, on the other hand, a three-component reaction involving acetonitrile as well as azidobenziodoxole took place to give predominantly amido-azidation products. A plausible mechanism is proposed based on the mechanistic studies to rationalize these results. The reactions of electronically less biased vinyl arenes probably proceed via a redox catalysis pathway, while the electron-rich alkenes are believed to be converted through a radical chain process. The present reactions may be of synthetic usefulness as they provide a new means for the amido-azidation of vinyl arenes.

Full text of DOI:10.1021/acs.joc.9b01569

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Article
Visible Light-Driven Azidation/Difunctionalization of Vinyl
Arenes with Azidobenziodoxole under Copper Catalysis
Danhua Wu, Shuang-Shuang Cui, Yajun Lin, Lin Li, and Wei Yu
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.9b01569 • Publication Date (Web): 08 Aug 2019
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Visible Light-Driven Azidation/Difunctionalization of Vinyl
Arenes with Azidobenziodoxole under Copper Catalysis
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Danhua Wu, Shuang-Shuang Cui, Yajun Lin, Lin Li and Wei Yu*
State Key Laboratory of Applied Organic Chemistry, College of Chemistry and
Chemical Engineering, Lanzhou University, Lanzhou, Gansu 730000, P. R. China
Graphic abstract
N3
N3
Ar
Electron-deficient Ar
O
O
I
IBA-N3 (2.0 equiv)
N
[Cu(dap)2]PF6 (5 mol %)
Ar
Electronically less
biased Ar
CH CN,
Ar
blue LED, rt
3
N3
N3
I O
Electron-rich Ar
Major product
O
O
I
O
Ar
IBA-N3
N3
Abstract
Visible light-driven azidation of vinyl arenes with azidobenziodoxole as the azidating
agent was investigated in acetonitrile by using Cu(I)(phenanthroline)2 complex
[Cu(dap)2]PF6 as photocatalyst. The reactions generated three types of
difunctionalization products, which correspond to reaction patterns of
amido-azidation, benzoyloxy-azidation and diazidation. Electronic nature of the aryl
group attached to the olefin moiety was found to play a crucial role in determining the
reaction consequence: when the aryl group was electron-rich, the reactions afforded
benzoyloxy-azidation products exclusively; for highly electron-deficient vinyl arenes,
by contrast, diazidation products were generated in moderate yields. When the aryl
group was moderately electron-rich or electron-deficient, on the other hand, a
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three-component reaction involving acetonitrile as well as azidobenziodoxole took
place to give predominantly amido-azidation products. A plausible mechanism is
proposed based on the mechanistic studies to rationalize these results. The reactions
of electronically less biased vinyl arenes probably proceed via a redox catalysis
pathway, while the electron-rich alkenes are believed to be converted through a
radical chain process. The present reactions may be of synthetic usefulness as they
provide a new means for the amido-azidation of vinyl arenes.
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KEYWORDS: azidation, azidobenziodoxole, acetonitrile, [Cu(dap)2]PF6, visible light
photocatalysis, vinyl arenes
1. INTRODUCTION
Visible light photoredox catalysis has evolved to be a most versatile and powerful tool
in organic synthesis during the last decades, with numerous applications being found
for it by using ruthenium and iridium-based complexes,1 or organic dyes as
photoccatalyst.2 Besides ruthenium and iridium complexes, the complexes of
earth-abundant first raw transition metals are also capable of initiating radical
reactions under visible light irradiation.3,4 From the view point of practical synthesis,
using cheaper earth abundant transition metal catalysts is highly preferable, but their
potential usefulness in this aspect has yet to been fully explored.
Alkene azidation/difunctionalization reactions are highly effective for the preparation
of densely functionalized azides, which are versatile precursors for the preparation of
other nitrogen-containing compounds.5 Much attention has been paid recently to the
development of various types of difunctionalization of alkenes, such as diazidation,6
amino-azidation,7 carboazidation,8 oxy-azidation9 and sufonyl azidation.10 In this
context, some intriguing results have been reported on copper-catalyzed azidation of
activated alkenes. In 2015, Greaney reported that copper complex [Cu(dap)2]Cl (dap
= 2,9-bis(4-anisyl)-1,10-phenanthroline) can effectively catalyze the azidation of
vinyl arenes with hypervalent iodine reagent 1-azido-1,2-benziodoxole (Zhdankin
reagent) as the azidating reagent (Scheme 1, (a)).11 Notably, they found that when the
reaction was performed under visible light irradiation in methanol, methoxy-azidation
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products were obtained in high yield. However, when the reactions were carried out in
the dark, diazidation products were generated predominantly instead. In the same
year, Loh et al. reported a similar copper-catalyzed azidating protocol for the
oxy-azidation and diazidation of vinyl arenes ((Scheme 1, (b)).12 It was found that the
catalyst and solvent play a key role on the reaction consequence: Under the catalysis
of Cu(OTf)2 in dichloromethane the reactions afforded mainly oxy-azidation products
into which an ortho-iodo benzoyloxy was introduced along with the azidyl group.
When CuI was used as catalyst and DMSO was used as the solvent, on the other hand,
the substrates were converted to diazidation products. Very recently, Rehbein and
Reiser et al. managed to convert vinyl arenes to -azidoketones under the conditions
of [Cu(dap)2]Cl-mediated visible light photoredox catalysis by using TMSN3 as
azidating reagent and air as oxidant.13 These studies indicate that azidations of alkenes
under copper-catalysis are highly useful for the preparation of functionalized organic
azides, and by adjusting the reaction conditions, different functionalities can be being
introduced selectively into the products. As a further demonstration of the diversity of
this methodology, herein we report that a three-component amido-azidation of vinyl
arenes can be realized in acetonitrile with Zhdankin reagent as azidating agent by
visible light photoredox catalysis with [Cu(dap)2]PF6 as catalyst (Scheme 1, (c)). Both
acetonitrile and the ortho-iodo benzoyloxy group from the Zhdankin reagent can be
introduced into products as the amido moiety. Interestingly, the electron nature of the
alkenes was found to play a profound effect on the reaction consequence, which was
not found in previous reports.11-13
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Scheme 1. Copper-Catalyzed Azidation/Difunctionalization of Vinyl Arenes with
Zhdankin Reagent
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Previous work:
N3
IBA-N3
IBA-N3
OMe
[Cu(dap)2]Cl (cat)
[Cu(dap)2]Cl (cat)
N3
N3
(a)
(b)
R
R
MeOH, dark, rt
R
R
MeOH, vis light, rt
7
8
9
ref. 11
ref. 12
N3
IBA-N3
Cu(OTf)2 (cat)
IBA-N3
CuI (cat)
DMSO, 40 o
OCOAr
N3
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N3
DCM, 40 o
C
R
R
C
This work:
N3
N3
Ar
Electron-deficient Ar
IBA-N3
[Cu(dap)2]PF6 (cat)
O
O
I
N
Ar
(c)
CH CN,
blue LED, rt
Electronically less
biased Ar
Ar
3
N3
N3
I O
Major product
Electron-rich Ar
O
O
I
O
Ar
IBA-N3
N3
2. RESULTS AND DISCUSSION
On the course of our studies on the azidations of alkenes,14 we found that when
irradiated by visible light (blue LED), para-bromostyrene 1a can be converted to
amido-azidation product 2a in acetonitrile by reacting with Zhdankin reagent under
the catalysis of [Cu(dap)2]+ (Table 1, entries 1 and 2). [Cu(dap)2]PF6 proved to be
more efficient than [Cu(dap)2]Cl under the current circumstance. By using
[Cu(dap)2]PF6 as the photocatalyst, 2a can be obtained in 78% yield at a concentration
of 0.05 M in CH3CN with 5 mol % of catalyst loading. The reaction also took place
when white LED was used as the light source, but the yield was lower (Table 1, entry
5). When the reaction was conducted in the dark, no 2a was obtained (Table 1, entry
6);
instead,
diazidation
product
3a
and
oxo-azidation
product
2-azido-1-(4-bromophenyl)ethan-1-one13 were generated in yields of 10% and 5%,
respectively (Equation 1). Control experiment indicated that the photocatalyst was
necessary for complete conversion of 1a (Table 1, entry 7). Oxygen exhibited a
negative effect on the reaction (Table 1, entry 9). As such, when the reaction
proceeded in the air, 2a was generated in only 22% yield, beside which
2-azido-1-(4-bromophenyl)ethan-1-one was obtained in 19% yield.
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Table 1. Examination of Reaction Conditionsa
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O
I
N3
I
O
photocat
MeCN, vis light, rt
O
N
O
+
N3
Br
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Br
1a
IBA-N3
2a
entry
photocat (mol %)
IBA-N3 (equiv)
yield (%)b
1
2
3
4
5
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9
[Cu(dap)2]Cl (5.0)
[Cu(dap)2]PF6 (5.0)
[Cu(dap)2]PF6 (2.5)
[Cu(dap)2]PF6 (5.0)
[Cu(dap)2]PF6 (5.0)
[Cu(dap)2]PF6 (5.0)
--
2.0
2.0
2.0
1.5
2.0
2.0
2.0
2.0
2.0
43
78
59
72
54c
0d
7e
72f
22g
[Cu(dap)2]PF6 (5.0)
[Cu(dap)2]PF6 (5.0)
aThe reactions were performed on 0.2 mmol scale in 4.0 mL of acetonitrile (0.05 M) under argon
atmosphere with blue LEDs as the light source. Irradiation time was 4 h unless otherwise
b
c
d
e
specified. Isolated yield. With white LED as the light source. Run in dark for 8 h. In the
absence of photocatalyst. fIn 2.0 mL of acetonitrile (0.1 M). gRun in the air.
N3
I
O
N3
O
Cu(dap)2PF6 (5 mol %)
O
N3
N3
+
+
MeCN, Ar, dark, rt, 4 h
Br
Br
Br
1a
3a
, 10%
5%
IBA-N3
1a
+ recovered
(20%)
Equation 1. Reaction of 1a with IBA-N3 under Dark
This result is interesting because the transformation has not been revealed in previous
reports. Apparently, both the solvent and 2-iodobenzoyloxy moiety from IBA-N3
were involved in the formation of 2a. From the synthetic point of view, it is highly
desirable to develop new protocols for the amido-azidation of alkenes as this type of
reactions would be useful for the preparation of synthetically important 1,2-diamino
compounds and their derivatives. In this context, the present reaction might provide a
convenient approach toward this goal. To test the scope of the reaction, we applied the
optimal conditions (Table 1, entry 2) to variously substituted styrenes and analogous
vinyl arenes, and the results are illustrated in Schemes 2 to 5. It can be seen from
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Scheme 2 that halogen-substituted, alkyl-substituted or acetyl-substituted styrenes can
be transformed into the amido-azidation products in moderated to good yields.
2-Vinylnaphthalene, 1,2-dihydronaphthalene and 1H-indene reacted in the same way.
For several tested substrates, benzoyloxy-azidation products were formed as well in
varying yields. In case that the vinyl alkenes are of a 1,2-disubstituted pattern, the
products were obtained as a mixture of diastereoisomers (2v-2x). The reactions of
trisubstituted vinyl arenes (2y-2af) also gave mainly amido-azidation products, along
with benzoyloxy-azidation products 4 (Scheme 3). The structure of 2ac was
confirmed by X-ray crystallographic analysis (CCDC No. 1878259).
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Scheme 2. Scope of Amido-Azidation Reactions of Vinyl Arenes-1
I
O
O
N3
I
O
[Cu(dap)2]PF6 (5 mol %)
MeCN
R2
N
O
R2
R1
N3
+
Ar
(0.05 M)
blue LED, Ar, rt, 4 h
R1
Ar
(2.0 equiv)
1
2
I
O
O
O
O
I
2a
: R = 4-Br, 78%;
: R = 2-Br, 66%
: R = 3-Br, 60%
: R = 3-F, 60%
: R = 4-F, 70%
: R = 2-Cl, 70%
2h
: R = 4-Cl, 51%
2n
: R = 4-tBu,
88%
N
2b
2c
2d
2e
2f
2g
2i
2o
2p
2q
:
R = H,
73%
: R = 4-CH2Cl, 80%
: R = 4-CH3CO, 81%
: R = 2,6-diCl, 35%
(50%)a
N
2j
2k
2l
2m
:
R= 2-Me, 78%
: R = 3-Me, 74%
R = 4-Me, 62%b
N3
2r
:
R = 2,5-diMe, 75%
R
b
N3
2s
:
: R = 2,4,6-triMe, 34%
: R = 4-Ph, 61%b
: R = 3-Cl, 54%
b
2t
, 54%
O
O
I
I
O
O
I
O
O
I
O
O
N
N
N
N
N3
N3
N3
N3
2x
, 82% (dr = 1.7:1)
b
2u
, 55%
2v
, 83% (dr = 6.6:1)
2w
, 82% (dr = 9:1)
O
I
The reactions were conducted on 0.2 mmol scale. The yields were isolated yields.
O
aThe reaction was conducted on 12 mmol scale with 2.5 mol % of photocatalyst and 15 mmol of IBA-N3.
b
Ar
2l, 2m, 2s, 2t and 2u
4
, o-iodo-benzoyloxy-azidation products ( ) were obtained in yields of 5%, 9%,
Besides
N3
35%, 6% and 9%, respectively.
4
Scheme 3. Scope of Amido-Azidation Reactions of Vinyl Arenes-2
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O
I
O
O
I
IBA-N3 (2.0 equiv)
R1
[Cu(dap)2]PF6 (5 mol %)
O
N
R2
R2
R3
R2
R3
Ar
+
Ar
CH CN,
blue LED, rt
3
Ar
R3
R1
R1
N3
N3
4y 4ad
-
1y 1af
-
2y 2af
-
7
8
9
O
I
O
I
O
O
I
O
O
I
O
O
I
O
O
I
O
O
N
N
N
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N3
N3
N3
N3
N3
N3
4aa
, 25%
2aa
, 51%
2y
, 70%
4z
, 17%
4y
, 11%
2z
, 62%
O
I
O
O
I
O
I
O
I
O
O
I
O
O
I
O
N
O
O
N
N
N3
N3
N3
N3
N3
N3
2ad, 51%
F
F
Cl
Cl
4ab
4ad,
37%
, 15%
2ab
, 50%
4ac
, 16%
O
2ac
, 68%
O
O
I
O
I
N
N
N3
N3
2ae
, 70%
2af
, 82%
When the standard conditions were applied to 4-nitro and 4-cyano-substituted
styrenes, however, no amido-azidation products were obtained. The reactions only
delivered diazidation products 3ag and 3ah in moderate yields (Scheme 4). The same
result was obtained when 2-vinylpyridine was used as the substrate. By contrast, when
electron rich 4-methoxy styrene was used as the substrate, the major product became
oxy-azidation product 4aj. The reactions of -phenyl styrene, 2-vinylthiophene and
N-vinylbenzenesulfonamides generated the same type of products as well (Scheme 5).
Scheme 4. Reactions of Electron-Deficient Vinyl Arenes
N3
I
O
N3
[Cu(dap)2]PF6 (5 mol %)
MeCN, blue, LED, Ar, rt
O
Ar
N3
+
Ar
1ag 1ai
-
(2.0 equiv)
3ag-3ai
N3
N3
N3
N3
N3
N
N3
O2N
NC
3ag,
30%
3ai
3ah
, 22%
, 33%
Scheme 5. Reactions of Electron-Rich Olefins
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N3
I
O
R2
R1 R2
O
I
[Cu(dap)2]PF6 (5 mol %)
O
N3
+
R1
O
MeCN, blue LED, Ar, rt, 20 min
6
7
1aj 1an
(2.0 equiv)
4aj 4an
-
-
8
9
I
I
I
I
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O
O
O
O
O
O
O
O
O
O
N3
N3
S
N3
S
N3
N
Ph
MeO
X
4am
4an
4ak,
, X = Cl, 75%
, X = Br, 70%
64%
4aj
, 65%
4al
, 63%
These results demonstrate that the electronic nature of the carbon-carbon double bond
exerted a profound effect on the reaction consequence, which was not found in
previous reports.11,12 These three types of products were definitely formed via
different pathways. We believe that the reactions were initiated by the single electron
reduction of IBA-N3 by photo-excited [Cu(dap)2]+, which would generate an azidyl
radical. The azidyl radical then adds to olefin moiety to give a carbon radical. This
was confirmed by the inhibition experiment with 2,2,6,6-tetramethylpiperidin-1-oxyl
(TEMPO) and butylated hydroxytoluene (BHT) (Scheme 6) as well as by radical
clock experiments (Scheme 7). In the radical clock experiments, although no
ring-opening products were obtained for compound 1ao, they were generated from
compound 1ap under the standard conditions.
Scheme 6. Inhibition Experiment
O
O
I
[Cu(dap)2]PF6 (5 mol %)
IBA-N3 (2.0 equiv)
N
N
O
TEMPO (2.0 equiv)
+
N3
Br
MeCN, blue LED, Ar, rt
N3
Br
Br
1a
2a
, 0%
5a
%
, 90
[Cu(dap)2]PF6 (5 mol %)
IBA-N3 (2.0 equiv)
BHT (2.0 equiv)
2a
1a
MeCN, blue LED, Ar, rt
0%
Scheme 7. Radical Clock Experiments
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I
I
N3
[Cu(dap)2]PF6 (5 mol %)
IBA-N3 (2.0 equiv)
O
N
O
O
N3
+
MeCN, blue LED, Ar, rt
O
7
8
9
1ao
2ao
, 5%
N3
4ao
, 36%
Ph
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[Cu(dap)2]PF6 (5 mol%)
IBA-N3 (2.0 equiv.)
Ph
O
N
MeCN, blue LED, Ar, rt
O
I
1ap
6ap
After the carbon radical is formed, the subsequent reactions would lead to different
types of products depending on the electronic properties of the aryl group adjacent to
the carbon-carbon double bond (Scheme 8). For electron-deficient substrates 1ag-1ai,
this radical would abstract an azidyl group to give diazidation products 3. Compounds
2, with an acetonitrile moiety incorporated in their structure, must be generated via
intermediacy of a Ritter-type intermediate (B) (Scheme 8, (a)), while the formation of
compound 4 also indicates the involvement of a carbocation (C) (Scheme 8, (b)). In
the latter case, C probably derives from direct oxidation of carbon radical A, which
should be favorable for electron rich alkenes. As the reactions of 1aj-1an did not give
amido-azidation products, Carbocation C should be in proximity with benzoyloxylate
anion, most likely located in the same solvent cage, so that it can be captured by
benzoyloxylate anion, rather than reacts with the solvent. If it was the case, IBA-N3
should act as oxidant for the conversion of A to C. For the formation of Ritter-type
intermediate B, on the other hand, a different mechanism should operate, which most
likely involves the participation of the copper catalyst. It is well known that Cu(II)
can facilely combine with a carbon radical to form a Cu(III) species, which would
then undergo C-Nu coupling via reductive elimination. Based on the literature
precedents, we assumed that in the present case the Ritter-type intermediate B was
possibly formed following the same pattern. It is also possible that radical A was first
oxidized by copper Cu(II) to carbocation C, which then coupled with acetonitrile to
give B.15 These two mechanisms are difficult to distinguish under current
circumstances, but we believe that the former one is more likely based on the
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literature reports on analogous transformations.16 It should be noted that apart from 2,
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no Ritter-type products with H2O as the nucleophile were found under the current
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circumstances.
9
Scheme 8. Possible Pathways for the Formation of 2 and 4
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[Cu(I)]
N
CH3CN-[Cu(II)]
2
N3
N3
N3
Ar
CO2
I
(a)
(b)
B
C
N3
Ar
Ar
A
4
Ar
IBA-N3
CO2
+
N3
I
Base on the above analysis, a possible mechanism is proposed to rationalize the
present results, which is illustrated in Scheme 9. The reaction is initiated by single
+
electron transfer (SET) between IBA-N3 and [Cu(dap)2 ]*, which results in the
formation of azidyl radical and [Cu(dap)2]2+. The azidyl radical then adds to the
carbon-carbon double bond to generate radical A. [Cu(dap)2]2+ generated in the SET
step binds with acetonitrile to form a complex of CH3CN-[Cu]2+. For electronically
less-biased aryl alkenes, intermediate A would couples with the CH3CN-[Cu]2+
complex to afford intermediate D (path (a)), which then undergoes reductive
elimination to give Ritter-type intermediate B. The latter is readily captured by o-iodo
benzoyloxylate anion to give E, from which product 2 is formed via rearrangement.
In case that the substrates are electron-rich alkenes, the initially formed radical
intermediate A is oxidized to the corresponding carbocation C by IBA-N3 (path (b)).
C then couples with o-iodo benzoyloxylate anion incorporated in the same solvent
cage to afford oxy-azidation products 4. When the vinyl group was attached with a
strong electron-withdrawing group, on the other hand, intermediate A neither binds
with CH3CN-[Cu]2+ species, nor is it further oxidized; it can only abstract an azidyl
group from IBA-N3 to give diazidation products 3 (path (c)).
Scheme 9. Proposed Mechanism
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CH3CN
[Cu(dap)2]2+
CH3CN-[Cu]2+
5
6
7
8
N3
R1
Ar
I
O
R2
[Cu(dap)2]+*
CO2
+
O
N3
3
hv
[Cu(dap)2]+
I
IBA-N3
(c)
+
CH3
N
9
N3
N3
I
O
R1
R1
H3CCN
[Cu]3+
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CH3CN-[Cu]2+
(a)
- [Cu(dap)2]+
O
R2
R2
R1
Ar
R2
Ar
Ar
R1
Ar
R2
N3
N3
N3
IBA-N3
D
1
A
B
(b)
CO2
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CO2
I
R1
I
I
R2
N3
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O
O
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O
C
N3
R1
Ar
O
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C
N3
H3C
O
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N
O
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R1
Ar
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I
O
O
H3C
O
N3
N
E
O
R2
N
R2
R1
R1
Ar
Ar
N3
N3
2
To get more evidence for this mechanism, quantum yield measurements were
conducted for the reactions of 1a and 1aj.17 It was anticipated that if IBA-N3 acted as
an oxidant for the oxidative transformation from A to C, the quantum yield for the
reaction should be larger than 1 because the reaction of IBA-N3 with A would result
in the formation of the azidyl radical, and thus the oxy-azidation can be effected in a
chain process. By contrast, the formation of compounds 2 should involve the
copper-mediated redox catalysis, which corresponds to a quantum yield of   1.
Indeed, the quantum yield for the reaction of 1a and 1aj were measured to be 0.17 and
1.15, respectively (The measurement details are presented in Supporting Information),
in consistence with the proposed mechanism shown in Scheme 9.
As there are three competitive pathways toward the products from the initially formed
radical intermediate A, the electronic nature of the aryl group delicately determines
which one is more favorable for each substrates. For path (b) toward products 4 to be
competitive, a strong electron-donating group is required to render the oxidation of A
by IBA-N3 readily occur. This oxidation is much less efficient for less electron-rich
substrates, and thus capture of A by CH3CN-[Cu]2+ becomes dominant. That highly
electron-deficient vinyl arenes cannot be converted to amido-azidation products
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indicates that the coupling of CH3CN-[Cu]2+ with A is also subjected to the electronic
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effect.
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3. CONCLUSIONS
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We have found that the reactions of vinyl arenes with azidobenziodoxole in
acetonitrile under the conditions of visible light irradiation with [Cu(dap)2]PF6 as
catalyst can give rise to three types of azidation/difunctionalization products,
depending on the electronic nature of the substrates. For alkenes incorporating an
electron-rich aryl group, benzoyloxy-azidation products was generated exclusively.
When the aryl group attached to the olefin moiety was highly electron-deficient,
diazidation products were generated in moderate yields. When the aryl group was less
electronically-biased, a three-component reaction involving azidobenziodoxole and
the solvent acetonitrile took place, affording mainly amido-azidation product. This
crucial impact of substituent’s electronic nature on the reaction consequence has not
been observed in previous studies. A plausible mechanism is proposed based on
mechanistic investigations to rationalize the observed results, where the electronic
effect is attributed to its influence on the subsequent reactions of the key carbon
radical intermediate formed via addition of azidyl radical to the carbon-carbon double
bond. This carbon radical can either couple with the Cu(II) species, or be oxidized by
azidobenziodoxole to the corresponding carbocation, or undergo azido transfer with
azidobenziodoxole. Besides the mechanistic implications, the present reactions are of
potential synthetic usefulness as they provide a new protocol for amido-azidation of
vinyl arenes.
EXPERIMENTAL SECTION
General Methods. The 1H and 13C NMR spectra were recorded on a Bruker AM-300
MHz spectrometer, a Bruker AM-400 MHz spectrometer or a Bruker AM-600 MHz
spectrometer with CDCl3 or DMSO-d6 as the solvent. In CDCl3, the chemical shifts in
1H NMR spectra were determined with Si(CH3)4 as the internal standard (δ = 0.00
ppm); the chemical shifts in 13C NMR spectra were determined based on the chemical
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shift of CDCl3 (δ = 77.00 ppm). In DMSO-d6, the chemical shifts in 1H NMR and 13C
NMR spectra were determined based on the chemical shift of DMSO-d6 (δ = 2.50
ppm for 1H NMR spectra and δ = 40.00 ppm for 13C NMR spectra, respectively). The
coupling constant(s) (J value) are reported in Hz (s = singlet, d = doublet, t = triplet, q
= quadruplet, m = multiplet or unresolved, br = broad signal). The high resolution
mass spectra (HRMS) were measured on a Bruker micrOTOF QII by ESI. The
infrared spectra (FT-IR) were measured on a NEXUS 670 FT-IR spectrometer.
Melting points (m.p.) were measured on an XT-4 melting point apparatus and are
uncorrected. Single-crystal X-ray analysis was carried on a SuperNova, Eos
diffractometer. A UV-visible spectrophotometer with a D2 lamp was used for the
quantum yield measurements. A blue LED apparatus (6 W; peak wavelength: 456.2
nm; half-wave width: 21 nm) equipped with a cooling fan were used as the light
source. The reaction vessel is a 15 mL Pyrex glass tube (diameter: 2.0 cm) put at 1.0
cm distance from the light. No filter was used for irradiation. For the gram scale
preparation, a common 10 W blue LED ribbon was used as the light source. Flash
column chromatography (FCC) was conducted on silica gel (200300 mesh).
Anhydrous acetonitrile were purchased from Energy Chemical and used without
further treatment. Other solvents were treated before use following the standard
procedures. 1-Azido-1,2-benziodoxole (Zhdankin reagent, IBA-N3) was prepared
according to the reported methods.18 2,9-Bis-(4-methoxy-phenyl)-1,10-phenanthroline
(dap) and [Cu(dap)2]Cl was prepared following the reported procedures.19
[Cu(dap)2]PF6 was prepared following the reported procedures.20 1am and 1an were
prepared according to literature methods.21 1ao and 1ap were prepared as reported.22
All the other materials were obtained from commercial suppliers, and were used
without further purification.
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General Procedure for the Reaction of 1 with Zhdankin Reagent. Into an oven
dried 15 mL Pyrex glass tube equipped with a magnetic stirring bar and a rubber
stopper were added [Cu(dap)2]PF6 (9.9 mg, 0.01 mmol, 5 mol %) and IBA-N3 (115.6
mg, 0.4 mmol, 2.0 equiv). The tube was evacuated and backfilled with argon for three
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times. Then 4 mL of anhydrous acetonitrile was added into the tube with a syringe
under argon atmosphere (argon balloon), followed by addition of 1 (0.2 mmol, 1.0
equiv) with a syringe under the same condition. The tube was put at the distance of 1
cm from the blue LED lamps and irradiated under stirring at room temperature (< 28
oC) for specific time (4 h unless otherwise specified). After the reaction was complete
as indicated by TLC, the mixture was diluted with dichloromethane (20 mL). The
solution was concentrated under reduced pressure on a rotary evaporator, and the
residual was treated with silica gel column chromatography (eluent: petroleum ether
(PE)/ethyl acetate (EA) = 20:1 to 10:1 unless otherwise specified) to afford the pure
product (s).
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Gram-Scale Synthesis of 3i. Into an oven dried 100 mL round-bottom flask equipped
with a magnetic stirring bar and a rubber stopper were added [Cu(dap)2]PF6 (0.289 g,
0.3 mmol, 2.5 mol %) and IBA-N3 (4.335 g, 15 mmol, 1.25 equiv). The flask was
evacuated and backfilled with argon for three times. Then 60 mL of anhydrous
acetonitrile was added into the flask with a syringe under argon atmosphere (argon
balloon), followed by addition of 1i (1.25g, 12 mmol) with a syringe. The flask was
irradiated by a common 10 W blue LED ribbon (at a distance of 3 cm) under cooling
(with an external cooling fan) for 5 h. After the reaction completed as indicated by
TLC, the solution was directly concentrated under reduced pressure on a rotary
evaporator, and the residual was treated with silica gel column chromatography
(eluent: PE/EA = 20:1) to afford the pure product 2i in 50% yield (2.588 g).
Safety statement: Organic azides are potentially explosive compounds that might
decompose dramatically. 1-Azido-1,2-benziodoxole (IBA-N3) also has its safety
concerns.23 Care should be taken to handle these compounds. However, we haven’t
experienced a safety problem during our experiments. All organic azides prepared in
this work are stable enough to be stored at room temperature at least for a month in
the dark.
4-Chloro-N-methyl-N-vinylbenzenesulfonamide (1am).White solid (on 8.7 mmol
o
1
scale, 1.872 g, 92%), mp 5860 C, Rf = 0.34 (PE:EA = 10:1). H NMR (400 MHz,
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CDCl3, δ ppm ) 7.737.68 (m, 2H), 7.537.47 (m, 2H), 6.97 (dd, J = 15.6, 9.0 Hz,
1H), 4.39 (dd, J = 9.0, 1.5 Hz, 1H), 4.24 (dd, J = 15.6, 1.5 Hz, 1H), 2.88 (s, 3H);
13C{1H} NMR (100 MHz, CDCl3, δ ppm) 139.5, 135.9, 133.2, 129.4, 128.3, 94.1,
31.3; HRMS (ESI-TOF) m/z: [M+H]+ calcd for [C9H11ClNO2S]+: 232.0194, found:
232.0197.
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4-Bromo-N-methyl-N-vinylbenzenesulfonamide (1an). White solid (on 6.6 mmol
o
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scale, 1.635 g, 90%), mp 7172 C, Rf = 0.34 (PE:EA = 10:1). H NMR (400 MHz,
CDCl3, δ ppm) 7.707.59 (m, 4H), 6.96 (dd, J = 15.6, 9.0 Hz, 1H), 4.38 (dd, J = 9.0,
1.5 Hz, 1H), 4.24 (dd, J = 15.7, 1.5 Hz, 1H), 2.88 (s, 3H); 13C{1H} NMR (100 MHz,
CDCl3, δ ppm) 136.6, 133.3, 133.4, 128.4, 128.0, 94.1, 31.3; HRMS (ESI-TOF) m/z:
[M+H]+ calcd for [C9H11BrNO2S]+: 275.9688, found: 275.9690.
N-Acetyl-N-(2-azido-1-(4-bromophenyl)ethyl)-2-iodobenzamide (2a). White solid
(80 mg, 78%), mp 8485 oC, Rf = 0.22 (PE:EA = 10:1). 1H NMR (400 MHz, CDCl3,
δ ppm): 7.93 (dd, J = 7.9, 3.0 Hz, 1H), 7.47 (dd, J = 8.3, 1.9 Hz, 2H), 7.39 (td, J = 7.6,
2.5 Hz, 1H), 7.31 (d, J = 8.2 Hz, 2H), 7.24 (dd, J = 7.6, 1.3 Hz, 1H), 7.17 (t, J = 7.6
Hz, 1H), 5.685.54 (m, 1H), 4.44 (t, J = 10.3 Hz, 1H), 3.97 (dd, J = 12.3, 6.1 Hz, 1H),
13
1.99 (s, 3H); C{1H} NMR (100 MHz, CDCl3, δ ppm): 173.6, 172.4, 141.4, 140.7,
135.6, 132.2, 131.7, 129.8, 128.5, 128.3, 122.3, 93.6, 58.9, 51.9, 27.6; FT-IR (KBr,
cm-1): 2104, 1714, 1669; HRMS (ESI-TOF) m/z: [M+H]+ calcd for
[C17H15BrIN4O2 ]+: 512.9418, found 512.9425.
N-Acetyl-N-(2-azido-1-(2-bromophenyl)ethyl)-2-iodobenzamide (2b). Colorless
liquid (68 mg, 66%), Rf = 0.21 (PE:EA = 10:1). 1H NMR (400 MHz, CDCl3, δ ppm):
7.91 (d, J = 7.9 Hz, 1H), 7.67 (d, J = 7.7 Hz, 1H), 7.52 (d, J = 8.0 Hz, 1H), 7.34 (t, J =
8.0 Hz, 2H), 7.15 (q, J = 8.4 Hz, 3H), 5.85 (s, 1H), 4.25 (t, J = 11.2 Hz, 1H), 3.95 (dd,
J = 12.2, 5.7 Hz, 1H), 2.13 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3, δ ppm): 173.7,
172.6, 141.2, 140.5, 133.0, 132.0, 130.5, 129.9, 128.4, 128.2, 127.8, 123.8, 93.4, 59.9,
50.6, 27.3; FT-IR (KBr, cm-1): 2105, 1714, 1672; HRMS (ESI-TOF) m/z: [M+H]+
calcd for [C17H15BrIN4O2]+: 512.9418, found 512.9413.
N-Acetyl-N-(2-azido-1-(3-bromophenyl)ethyl)-2-iodobenzamide (2c). Colorless
liquid (62 mg, 60%), Rf = 0.14 (PE:EA = 10:1). 1H NMR (400 MHz, CDCl3, δ ppm):
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7.93 (d, J = 7.9 Hz, 1H), 7.56 (s, 1H), 7.467.39 (m, 2H), 7.397.33 (m, 1H),
7.287.21 (m, 2H), 7.217.15 (m, 1H), 5.62 (dd, J = 9.0, 6.3 Hz, 1H), 4.45 (t, J =
10.6 Hz, 1H), 3.98 (dd, J = 12.3, 6.0 Hz, 1H), 2.02 (s, 3H); 13C{1H} NMR (100 MHz,
CDCl3, δ ppm): 173.6, 172.4, 141.3, 140.7, 136.7, 132.2, 131.3, 131.1, 130.1, 128.4,
128.3, 126.5, 122.6, 93.6, 58.7, 51.8, 27.6; FT-IR (KBr, cm-1): 2104, 1713, 1669;
HRMS (ESI-TOF) m/z: [M+H]+ calcd for [C17H15BrIN4O2 ]+: 512.9418; found:
512.9426.
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N-Acetyl-N-(2-azido-1-(3-fluorophenyl)ethyl)-2-iodobenzamide (2d). Colorless
liquid (54 mg, 60%), Rf = 0.14 (PE:EA = 10:1). 1H NMR (400 MHz, CDCl3, δ ppm):
7.93 (d, J = 7.9 Hz, 1H), 7.40 (t, J = 7.5 Hz, 1H), 7.31 (dd, J = 14.1, 8.1 Hz, 1H),
7.287.23 (m, 1H), 7.127.23 (m, 3H), 7.036.96 (m, 1H), 5.725.57 (m, 1H), 4.45
(t, J = 10.3 Hz, 1H), 4.00 (dd, J = 12.3, 6.0 Hz, 1H), 2.02 (s, 3H); 13C{1H} NMR (100
MHz, CDCl3, δ ppm): 173.6, 172.4, 162.7 (d, J = 246.0 Hz), 141.4, 140.7, 139.0 (d, J
= 7.0 Hz), 132.2, 130.1 (d, J = 8.0 Hz), 128.5, 128.4, 123.6 (d, J = 3.0 Hz), 115.3 (d, J
19
= 10.0 Hz), 115.0 (d, J = 11.0 Hz), 93.6, 58.9, 52.0, 27.6; F NMR (376 MHz,
CDCl3, δ ppm) -112.0; FT-IR (KBr, cm-1): 2106, 1713, 1670; HRMS (ESI-TOF) m/z:
[M+H]+ calcd for [C17H15FIN4O2 ]+: 453.0218, found: 453.0225.
N-Acetyl-N-(2-azido-1-(4-fluorophenyl)ethyl)-2-iodobenzamide (2e). Colorless
liquid (63 mg, 70%), Rf = 0.20 (PE:EA = 10:1). 1H NMR (400 MHz, CDCl3, δ ppm):
7.93 (dd, J = 7.9, 0.6 Hz, 1H), 7.467.39 (m, 2H), 7.37 (dd, J = 7.6, 0.9 Hz, 1H), 7.22
(dd, J = 7.7, 1.5 Hz, 1H), 7.16 (td, J = 7.7, 1.6 Hz, 1H), 7.03 (t, J = 8.7 Hz, 2H), 5.64
(dd, J = 9.1, 6.4 Hz, 1H), 4.46 (t, J = 10.8 Hz, 1H), 3.96 (dd, J = 12.3, 6.1 Hz, 1H),
13
1.99 (s, 3H); C{1H} NMR (75 MHz, CDCl3, δ ppm): 173.7, 172.5, 162.4 (d, J =
246.8 Hz), 141.4, 140.7, 138.6, 132.3, 132.1, 130.1 (d, J = 8.2 Hz), 128.4 (d, J = 15.0
19
Hz), 115.5 (d, J = 21.0 Hz), 93.6, 58.9, 52.2, 27.7; F NMR (376 MHz, CDCl3, δ
ppm) -113.3; FT-IR (KBr, cm-1): 2106, 1712, 1678; HRMS (ESI-TOF) m/z: [M+H]+
calcd for [C17H15FIN4O2]+: 453.0218, found: 453.0210.
N-Acetyl-N-(2-azido-1-(2-chlorophenyl)ethyl)-2-iodobenzamide (2f). Colorless
liquid (66 mg, 70%), Rf = 0.22 (PE:EA = 10:1). 1H NMR (600 MHz, CDCl3, δ ppm):
7.91 (d, J = 7.8 Hz, 1H), 7.64 (d, J = 7.4 Hz, 1H), 7.377.31 (m, 2H), 7.29 (td, J =
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5
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Hz, 1H), 5.95 (s, 1H), 4.30 (t, J = 10.2 Hz, 1H), 3.98 (s, 1H), 2.09 (s, 3H); C{1H}
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NMR (150 MHz, CDCl3, δ ppm): 173.5, 172.4, 141.4, 140.5, 133.5, 131.9, 130.4,
129.6, 129.6, 128.4, 128.2, 127.1, 93.4, 57.2, 50.7, 27.2; FT-IR (KBr, cm-1): 2105,
1714, 1672; HRMS (ESI-TOF) m/z: [M+H]+ calcd for [C17H15ClIN4O2]+: 468.9923,
found: 468.9929.
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N-Acetyl-N-(2-azido-1-(3-chlorophenyl)ethyl)-2-iodobenzamide (2g). Colorless
liquid (51 mg, 54%), Rf = 0.15 (PE:EA = 10:1). 1H NMR (400 MHz, CDCl3, δ ppm):
7.93 (d, J = 7.9 Hz, 1H), 7.457.36 (m, 2H), 7.347.23 (m, 4H), 7.18 (td, J = 7.8, 1.6
Hz, 1H), 5.63 (dd, J = 8.9, 6.4 Hz, 1H), 4.45 (t, J = 10.5 Hz, 1H), 3.99 (dd, J = 12.3,
13
6.0 Hz, 1H), 2.02 (s, 3H); C{1H} NMR (75 MHz, CDCl3, δ ppm): 173.6, 172.4,
141.3, 140.7, 138.5, 134.4, 132.2, 129.8, 128.5, 128.4, 128.3, 128.2, 126.1, 93.6, 58.8,
51.8, 27.7; FT-IR (KBr, cm-1): 2105, 1713, 1669; HRMS (ESI-TOF) m/z: [M+Na]+
calcd for [C17H14ClIN4O2Na]+: 490.9742, found: 490.9733.
N-Acetyl-N-(2-azido-1-(4-chlorophenyl)ethyl)-2-iodobenzamide
(2h).
Slight
o
1
yellow solid (48 mg, 51%), mp 8687 C, Rf = 0.23 (PE:EA = 10:1). H NMR (400
MHz, CDCl3, δ ppm): 7.94 (d, J = 7.9 Hz, 1H), 7.437.35 (m, 3H), 7.357.29 (m,
2H), 7.24 (dd, J = 7.7, 1.5 Hz, 1H), 7.17 (td, J = 7.8, 1.4 Hz, 1H), 5.63 (dd, J = 9.0,
6.3 Hz, 1H), 4.45 (t, J = 10.7 Hz, 1H), 3.97 (dd, J = 12.3, 6.1 Hz, 1H), 2.00 (s, 3H);
13C{1H} NMR (100 MHz, CDCl3, δ ppm): 173.7, 172.4, 141.4, 140.7, 135.0, 134.2,
132.2, 129.5, 128.7, 128.5, 128.3, 93.6, 58.9, 52.0, 27.7; FT-IR (KBr, cm-1): 2104,
1713, 1669; HRMS (ESI-TOF) m/z: [M-N2+Na]+ calcd for [C17H14ClIN2O2Na]+:
462.9681, found: 462.9679.
N-Acetyl-N-(2-azido-1-phenylethyl)-2-iodobenzamide (2i). Slight yellow solid (63
o
1
mg, 73%), mp 7273 C, Rf = 0.36 (PE:EA = 10:1). H NMR (400 MHz, CDCl3, δ
ppm): 7.92 (d, J = 7.9 Hz, 1H), 7.447.27 (m, 6H), 7.22 (dd, J = 7.7, 1.5 Hz, 1H),
7.15 (td, J = 7.7, 1.6 Hz, 1H), 5.65 (t, J = 8.0 Hz, 1H), 4.49 (t, J = 10.9 Hz, 1H), 4.00
13
(dd, J = 12.3, 6.0 Hz, 1H), 2.02 (s, 3H); C{1H} NMR (100 MHz, CDCl3, δ ppm):
173.8, 172.6, 141.5, 140.6, 136.5, 132.0, 128.6, 128.5, 128.3, 128.2, 127.9, 93.6, 59.5,
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52.2, 27.6; FT-IR (KBr, cm-1): 2104, 1713, 1669; HRMS (ESI-TOF) m/z: [M+H]+
calcd for [C17H16IN4O2]+: 435.0312, found: 435.0319.
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N-Acetyl-N-(2-azido-1-(o-tolyl)ethyl)-2-iodobenzamide (2j). Colorless liquid (70
mg, 78%), Rf = 0.31 (PE:EA = 10:1). 1H NMR (400 MHz, CDCl3, δ ppm): 7.91 (dd, J
= 7.9, 0.7 Hz, 1H), 7.55 (s, 1H), 7.32 (td, J = 7.6, 1.0 Hz, 1H), 7.247.17 (m, 2H),
7.14 (td, J = 7.7, 1.6 Hz, 2H), 7.08 (dd, J = 7.6, 1.4 Hz, 1H), 5.89 (s, 1H), 4.41 (s,
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1H), 3.86 (s, 1H), 2.31 (s, 3H), 1.96 (s, 3H); C{1H} NMR (100 MHz, CDCl3, δ
ppm): 174.0, 172.4, 141.6, 140.6, 136.4, 134.5, 131.9, 130.6, 128.6, 128.3, 128.2,
126.3, 93.7, 56.8, 52.0, 27.6, 19.2; FT-IR (KBr, cm-1): 2104, 1714, 1669; HRMS
(ESI-TOF) m/z: [M-N2+H]+ calcd for [C18H18IN2O2 ]+: 421.0407, found: 421.0398.
N-Acetyl-N-(2-azido-1-(m-tolyl)ethyl)-2-iodobenzamide (2k). Colorless liquid (66
mg, 74%), Rf = 0.25 (PE:EA = 10:1). 1H NMR (400 MHz, CDCl3, δ ppm): 7.91 (d, J
= 7.9 Hz, 1H), 7.36 (t, J = 7.5 Hz, 1H), 7.177.26 (m, 4H), 7.14 (td, J = 7.8, 1.5 Hz,
1H), 7.10 (d, J = 6.6 Hz, 1H), 5.675.54 (m, 1H), 4.47 (t, J = 10.9 Hz, 1H), 3.98 (dd,
J = 12.3, 6.0 Hz, 1H), 2.34 (s, 3H), 2.04 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3, δ
ppm): 173.8, 172.6, 141.5, 140.6, 138.1, 136.4, 131.9, 128.9, 128.5, 128.4, 128.4,
128.2, 124.9, 93.6, 59.5, 52.2, 27.6, 21.4; FT-IR (KBr, cm-1): 2104, 1713, 1669;
HRMS (ESI-TOF) m/z: [M-N2+H]+ calcd for [C18H18IN2O2 ]+: 421.0407, found:
421.0398.
N-Acetyl-N-(2-azido-1-(p-tolyl)ethyl)-2-iodobenzamide (2l). Colorless liquid (56
mg, 62%), Rf = 0.29 (PE:EA = 10:1). 1H NMR (400 MHz, CDCl3, δ ppm): 7.957.89
(m, 1H), 7.36 (td, J = 7.6, 0.9 Hz, 1H), 7.30 (d, J = 8.1 Hz, 2H), 7.22 (dd, J = 7.7, 1.5
Hz, 1H), 7.187.12 (m, 3H), 5.685.54 (m, 1H), 4.47 (t, J = 10.9 Hz, 1H), 3.97 (dd, J
13
= 12.3, 6.0 Hz, 1H), 2.32 (s, 3H), 2.02 (s, 3H); C{1H} NMR (100 MHz, CDCl3, δ
ppm): 173.8, 172.6, 141.6, 140.7, 138.0, 133.5, 132.0, 129.3, 128.5, 128.3, 127.9,
93.7, 59.4, 52.3, 27.7, 21.1; FT-IR (KBr, cm-1): 2104, 1713, 1669; HRMS (ESI-TOF)
m/z: [M+H]+ calcd for [C18H18IN4O2 ]+: 449.0469, found: 449.0475.
2-Azido-1-(p-tolyl)ethyl 2-iodobenzoate (4l).12 Colorless liquid (4 mg, 5%), Rf =
0.52 (PE:EA = 10:1). 1H NMR (400 MHz, CDCl3, δ ppm): 8.00 (dd, J = 7.9, 1.2 Hz,
1H), 7.90 (dd, J = 7.8, 1.7 Hz, 1H), 7.42 (td, J = 7.6, 1.2 Hz, 1H), 7.35 (d, J = 8.0 Hz,
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2H), 7.20 (d, J = 7.9 Hz, 2H), 7.16 (td, J = 7.7, 1.7 Hz, 1H), 6.11 (dd, J = 7.8, 4.3 Hz,
1H), 3.78 (dd, J = 13.1, 7.8 Hz, 1H), 3.62 (dd, J = 13.1, 4.3 Hz, 1H), 2.35 (s, 3H);
13C{1H} NMR (100 MHz, CDCl3, δ ppm): 165.1, 141.5, 138.8, 134.3, 133.7, 132.9,
131.1, 129.4, 127.9, 126.6, 94.3, 75.6, 55.1, 21.2.
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N-(1-([1,1'-Biphenyl]-4-yl)-2-azidoethyl)-N-acetyl-2-iodobenzamide
(2m).
1
Colorless liquid (62 mg, 61%), Rf = 0.14 (PE:EA = 10:1). H NMR (400 MHz,
CDCl3, δ ppm): 7.92 (d, J = 7.9 Hz, 1H), 7.63-7.53 (m, 4H), 7.48 (d, J = 8.3 Hz, 2H),
7.42 (t, J = 7.5 Hz, 2H), 7.397.30 (m, 2H), 7.27 (dd, J = 7.6, 1.5 Hz, 1H), 7.15 (td, J
= 7.7, 1.6 Hz, 1H), 5.785.63 (m, 1H), 4.52 (t, J = 10.7 Hz, 1H), 4.03 (dd, J = 12.3,
13
6.0 Hz, 1H), 2.04 (s, 3H); C{1H} NMR (150 MHz, CDCl3, δ ppm): 173.8, 172.6,
141.5, 141.0, 140.6, 140.3, 135.4, 132.0, 128.7, 128.5, 128.4, 128.3, 127.4, 127.2,
127.0, 93.6, 59.3, 52.2, 27.6; FT-IR (KBr, cm-1): 2104, 1713, 1668; HRMS
(ESI-TOF) m/z: [M+H]+ calcd for [C23H20IN4O2]+: 511.0625, found: 511.0627.
2-([1,1'-Biphenyl]-4-yl)-1-azidopropan-2-yl 2-iodobenzoate (4m).12 Colorless
1
liquid (8 mg, 9%), Rf = 0.30 (PE:EA = 10:1). H NMR (400 MHz, CDCl3, δ ppm):
8.01 (dd, J = 8.0, 1.1 Hz, 1H), 7.93 (dd, J = 7.8, 1.8 Hz, 1H), 7.657.49 (m, 6H), 7.43
(t, J = 7.5 Hz, 3H), 7.34 (t, J = 7.2 Hz, 1H), 7.16 (td, J = 7.7, 1.7 Hz, 1H), 6.18 (dd, J
= 7.7, 4.2 Hz, 1H), 3.82 (dd, J = 13.1, 7.7 Hz, 1H), 3.68 (dd, J = 13.2, 4.3 Hz, 1H);
13C{1H} NMR (150 MHz, CDCl3, δ ppm): 165.1, 141.8, 141.6, 140.4, 135.6, 134.2,
133.0, 131.2, 128.8, 128.0, 127.5, 127.5, 127.1, 127.0, 94.3, 75.6, 55.1.
N-Acetyl-N-(2-azido-1-(4-(tert-butyl)phenyl)ethyl)-2-iodobenzamide
(2n).
1
Colorless liquid (86 mg, 88%), Rf = 0.34 (PE:EA = 10:1). H NMR (400 MHz,
CDCl3, δ ppm): 7.92 (d, J = 7.9 Hz, 1H), 7.397.30 (m, 5H), 7.277.23 (m, 1H), 7.14
(td, J = 7.5, 1.2 Hz, 1H), 5.62 (dd, J = 9.3, 6.1 Hz, 1H), 4.49 (t, J = 10.9 Hz, 1H), 3.97
(dd, J = 12.3, 6.0 Hz, 1H), 2.03 (s, 3H), 1.29 (s, 9H); 13C{1H} NMR (75 MHz, CDCl3,
δ ppm): 173.8, 172.6, 151.1, 141.6, 140.6, 133.4, 131.2, 128.5, 128.2, 127.6, 125.4,
93.7, 59.3, 52.3, 34.5, 31.2, 27.6; FT-IR (KBr, cm-1): 2104, 1713, 1670; HRMS
(ESI-TOF) m/z: [M+H]+ calcd for [C21H24IN4O2]+: 491.0938, found: 491.0929.
N-Acetyl-N-(2-azido-1-(4-(chloromethyl)phenyl)ethyl)-2-iodobenzamide
(2o).
1
Colorless liquid (70 mg, 80%), Rf = 0.18 (PE:EA = 10:1). H NMR (400 MHz,
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CDCl3, δ ppm): 7.92 (dd, J = 7.9, 0.6 Hz, 1H), 7.347.44 (m, 5H), 7.25 (dd, J = 7.7,
1.5 Hz, 1H), 7.16 (td, J = 7.7, 1.6 Hz, 1H), 5.65 (dd, J = 9.2, 6.2 Hz, 1H), 4.55 (s,
2H), 4.46 (t, J = 10.7 Hz, 1H), 3.99 (dd, J = 12.3, 6.0 Hz, 1H), 2.01 (s, 3H); 13C{1H}
NMR (75 MHz, CDCl3, δ ppm): 173.7, 172.5, 141.4, 140.7, 137.4, 136.8, 132.1,
128.7, 128.5, 128.3, 128.3, 93.6, 59.1, 52.1, 45.6, 27.7; FT-IR (KBr, cm-1): 2105,
1713, 1668; HRMS (ESI-TOF) m/z: [M+H]+ calcd for [C18H17ClIN4O2]+: 483.0079,
found: 483.0076.
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N-Acetyl-N-(1-(4-acetylphenyl)-2-azidoethyl)-2-iodobenzamide (2p). Colorless
liquid (77 mg, 81%), Rf = 0.16 (PE:EA = 5:1), eluent for column chromatography:
1
PE/EA = 10:1 to 3:1. H NMR (400 MHz, CDCl3, δ ppm): 7.93 (d, J = 7.9 Hz, 1H),
7.45 (d, J = 8.5 Hz, 2H), 7.38 (t, J = 7.6 Hz, 1H), 7.25 (d, J = 7.6 Hz, 1H), 7.16 (t, J =
7.7 Hz, 1H), 7.08 (d, J = 8.6 Hz, 2H), 5.65 (dd, J = 9.2, 6.1 Hz, 1H), 4.49 (t, J = 10.5
13
Hz, 1H), 3.95 (dd, J = 12.4, 6.0 Hz, 1H), 2.29 (s, 3H), 2.00 (s, 3H); C{1H} NMR
(100 MHz, CDCl3, δ ppm): 173.7, 172.6, 169.2, 150.4, 141.4, 140.7, 134.0, 132.1,
129.4, 128.6, 128.3, 121.7, 93.6, 59.1, 52.1, 27.7, 21.1; FT-IR (KBr, cm-1): 2105,
1760, 1713, 1668; HRMS (ESI-TOF) m/z: [M-N2+H]+ calcd for [C19H18IN2O3]+:
449.0357, found: 449.0366.
N-Acetyl-N-(2-azido-1-(2,6-dichlorophenyl)ethyl)-2-iodobenzamide (2q). White
solid (35 mg, 35%), mp 137138 oC, Rf = 0.14 (PE:EA = 10:1). 1H NMR (600 MHz,
CDCl3, δ ppm): 7.92 (d, J = 7.9 Hz, 1H), 7.37 (t, J = 7.5 Hz, 1H), 7.32 (d, J = 8.0 Hz,
2H), 7.29 (dd, J = 7.6, 1.5 Hz, 1H), 7.197.14 (m, 2H), 6.14 (s, 1H), 4.54 (dd, J =
13
12.4, 9.5 Hz, 1H), 4.19 (s, 1H), 1.92 (s, 3H); C{1H} NMR (150 MHz, CDCl3, δ
ppm): 173.1, 171.7, 141.6, 140.8, 136.1, 132.1, 131.8, 129.8, 129.6, 129.0, 128.2,
94.0, 58.6, 51.4, 27.7; FT-IR (KBr, cm-1): 2106, 1719, 1674; HRMS (ESI-TOF) m/z:
[M+H]+ calcd for [C17H14Cl2IN4O2]+:502.9533, found:502.9538.
N-Acetyl-N-(2-azido-1-(2,5-dimethylphenyl)ethyl)-2-iodobenzamide (2r). White
o
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solid (69 mg, 75%), mp 99100 C, Rf = 0.28 (PE:EA = 10:1). H NMR (400 MHz,
CDCl3, δ ppm): 7.90 (d, J = 7.9 Hz, 1H), 7.31 (t, J = 7.1 Hz, 2H), 7.12 (t, J = 7.7 Hz,
1H), 7.04 (dd, J = 7.8, 1.1 Hz, 1H), 7.00 (d, J = 8.5 Hz, 2H), 5.82 (s, 1H), 4.39 (t, J =
13
10.5 Hz, 1H), 3.83 (s, 1H), 2.30 (s, 3H), 2.22 (s, 3H), 2.00 (s, 3H); C{1H} NMR
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(100 MHz, CDCl3, δ ppm): 174.1, 172.5, 141.6, 140.5, 135.7, 134.1, 133.2, 132.0,
130.5, 129.1, 129.1, 128.6, 128.2, 93.7, 56.8, 52.1, 27.6, 21.2, 18.8; FT-IR (KBr,
cm-1): 2104, 1714, 1670; HRMS (ESI-TOF) m/z: [M-N2+Na]+ calcd for
[C19H20IN2O2Na]+: 457.0383, found: 457.0376.
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N-Acetyl-N-(2-azido-1-mesitylethyl)-2-iodobenzamide (2s). White solid (32 mg,
o
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34%), mp 118119 C, Rf = 0.30 (PE:EA = 10:1). H NMR (400 MHz, CDCl3, δ
ppm): 7.90 (dd, J = 7.9, 0.8 Hz, 1H), 7.31 (t, J = 7.3 Hz, 1H), 7.13 (td, J = 7.7, 1.6 Hz,
1H), 7.08 (s, 1H), 6.79 (s, 2H), 5.64 (s, 1H), 4.55 (dd, J = 12.4, 10.9 Hz, 1H), 3.73 (s,
13
1H), 2.33 (s, 6H), 2.22 (s, 3H), 2.00 (s, 3H); C{1H} NMR (150 MHz, CDCl3, δ
ppm): 174.2, 172.8, 141.5, 140.5, 137.7, 137.1, 132.0, 130.7, 130.1, 129.4, 128.2,
93.7, 59.3, 51.9, 29.6, 27.5, 20.6; FT-IR (KBr, cm-1): 2106, 1715, 1670; HRMS
(ESI-TOF) m/z: [M+H]+ calcd for [C20H22IN4O2]+: 477.0782, found: 477.0786.
2-Azido-1-mesitylethyl 2-iodobenzoate (4s).12 Colorless liquid (30 mg, 35%), Rf =
0.53 (PE:EA = 10:1). 1H NMR (400 MHz, CDCl3, δ ppm): 7.98 (dd, J = 7.9, 1.1 Hz,
1H), 7.85 (dd, J = 7.8, 1.7 Hz, 1H), 7.40 (td, J = 7.6, 1.1 Hz, 1H), 7.13 (td, J = 7.7, 1.7
Hz, 1H), 6.85 (s, 2H), 6.54 (dd, J = 9.4, 4.7 Hz, 1H), 4.02 (dd, J = 13.2, 9.3 Hz, 1H),
3.52 (dd, J = 13.2, 4.7 Hz, 1H), 2.49 (s, 6H), 2.24 (s, 3H); 13C{1H} NMR (100 MHz,
CDCl3, δ ppm): 165.1, 141.5, 138.2, 136.7, 134.3, 132.7, 130.8, 130.2, 129.4, 127.9,
94.3, 73.1, 52.8, 20.8, 20.7.
N-Acetyl-N-(2-azido-1-(naphthalen-1-yl)ethyl)-2-iodobenzamide (2t). White solid
o
1
(52 mg, 54%), mp 164165 C, Rf = 0.14 (PE:EA = 10:1). H NMR (400 MHz,
CDCl3, δ ppm): 8.29 (s, 1H), 7.85 (dd, J = 8.1, 1.8 Hz, 2H), 7.80 (d, J = 8.2 Hz, 1H),
7.67 (d, J = 7.5 Hz, 1H), 7.59 (t, J = 7.7 Hz, 1H), 7.51 (t, J = 7.4 Hz, 1H), 7.44 (t, J =
7.8 Hz, 1H), 7.12 (t, J = 7.5 Hz, 1H), 7.03 (td, J = 7.7, 1.8 Hz, 1H), 6.84 (s, 1H), 6.70
13
(s, 1H), 4.67 (s, 1H), 4.14 (dd, J = 11.8, 5.6 Hz, 1H), 1.84 (s, 3H); C{1H} NMR
(150 MHz, CDCl3, δ ppm): 173.7, 172.5, 141.4, 140.8, 133.7, 132.1, 131.4, 129.3,
129.1, 128.9, 128.2, 127.3, 127.0, 125.8, 124.9, 122.7, 94.1, 55.1, 52.7, 27.7; FT-IR
(KBr, cm-1): 2104, 1712, 1668; HRMS (ESI-TOF) m/z: [M+H]+ calcd for
[C21H18IN4O2]+: 485.0469, found: 485.0474.
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2-Azido-1-(naphthalen-1-yl)ethyl 2-iodobenzoate (4t).12 Colorless liquid (5 mg,
6%), Rf = 0.30 (PE:EA = 10:1). 1H NMR (400 MHz, CDCl3, δ ppm): 8.14 (d, J = 8.4
Hz, 1H), 8.03 (dd, J = 8.0, 1.2 Hz, 1H), 7.99 (dd, J = 7.8, 1.7 Hz, 1H), 7.88 (dd, J =
16.8, 8.0 Hz, 2H), 7.71 (d, J = 7.1 Hz, 1H), 7.657.56 (m, 1H), 7.567.42 (m, 3H),
7.19 (td, J = 7.7, 1.7 Hz, 1H), 6.97 (dd, J = 8.1, 3.7 Hz, 1H), 3.92 (dd, J = 13.3, 8.1
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Hz, 1H), 3.80 (dd, J = 13.3, 3.6 Hz, 1H); C{1H} NMR (150 MHz, CDCl3, δ ppm):
165.2, 141.7, 134.2, 133.8, 133.1, 132.4, 131.3, 130.1, 129.4, 129.2, 128.1, 127.0,
126.1, 125.3, 124.4, 122.5, 94.5, 73.1, 54.9.
N-Acetyl-N-(2-azido-1-(naphthalen-2-yl)ethyl)-2-iodobenzamide (2u). Colorless
liquid (53 mg, 55%), Rf = 0.14 (PE:EA = 10:1). 1H NMR (400 MHz, CDCl3, δ ppm):
7.92 (d, J = 7.9 Hz, 1H), 7.887.77 (m, 4H), 7.55 (d, J = 8.5 Hz, 1H), 7.517.44 (m,
2H), 7.34 (t, J = 7.5 Hz, 1H) 7.23 (d, J = 6.6 Hz, 1H), 7.13 (td, J = 7.8, 1.5 Hz, 1H),
5.895.77 (m, 1H), 4.61 (t, J = 10.6 Hz, 1H), 4.10 (dd, J = 12.3, 6.0 Hz, 1H), 2.04 (s,
13
3H); C{1H} NMR (150 MHz, CDCl3, δ ppm): 173.9, 172.6, 140.6, 128.5, 128.4,
128.3, 128.1, 127.5, 127.3, 126.4, 125.6, 93.6, 59.6, 52.2, 27.7; FT-IR (KBr, cm-1):
2104, 1712, 1668; HRMS (ESI-TOF) m/z: [M+H]+ calcd for [C21H18IN4O2]+:
485.0469, found: 485.0460.
2-Azido-1-(naphthalen-2-yl)ethyl 2-iodobenzoate (4u).12 Colorless liquid (8 mg,
9%), Rf = 0.34 (PE:EA = 10:1). 1H NMR (400 MHz, CDCl3, δ ppm): 8.00 (dd, J = 7.9,
1.2 Hz, 1H), 7.967.90 (m, 2H), 7.907.80 (m, 3H), 7.55 (dd, J = 8.4, 1.8 Hz, 1H),
7.527.46 (m, 2H), 7.43 (td, J = 7.6, 1.2 Hz, 1H), 7.16 (td, J = 7.6, 1.7 Hz, 1H), 6.30
(dd, J = 7.8, 4.3 Hz, 1H), 3.88 (dd, J = 13.1, 7.8 Hz, 1H), 3.71 (dd, J = 13.1, 4.3 Hz,
13
1H); C{1H} NMR (150 MHz, CDCl3, δ ppm): 165.2, 141.6, 134.3, 134.0, 133.4,
133.1, 133.0, 131.2, 128.8, 128.1, 128.0, 127.7, 126.6, 126.5, 126.3, 123.9, 94.3, 75.9,
55.1.
N-Acetyl-N-(2-azido-1,2,3,4-tetrahydronaphthalen-1-yl)-2-iodobenzamide (2v).
Colorless liquid (76 mg, cis:trans = 6.6:1, 83%), Rf = 0.19 (PE:EA = 10:1). FT-IR
(KBr, cm-1): 2102, 1717, 1671; HRMS (ESI-TOF) m/z: [M+H]+ calcd for
[C19H18IN4O2]+: 461.0469, found: 461.0472. (cis)-Isomer (major) ： 1H NMR (600
MHz, CDCl3, δ ppm): 7.91 (d, J = 8.0 Hz, 1H), 7.44 (s, 1H), 7.40 (t, J = 7.1 Hz, 1H),
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7.28 (d, J = 7.3 Hz, 1H), 7.207.08 (m, 4H), 6.08 (d, J = 6.0 Hz, 1H), 4.11 (s, 1H),
3.15 (d, J = 16.7 Hz, 1H), 2.862.78 (m, 1H), 2.57 (s, 1H), 2.152.08 (m, 1H), 1.89
(s, 3H); 13C{1H} NMR (150 MHz, CDCl3, δ ppm): 174.2, 172.0, 142.3, 140.6, 137.0,
132.4, 131.5, 128.8, 128.2, 128.1, 127.6, 127.2, 126.3, 93.9, 60.4, 55.1, 28.1, 27.0,
24.9. (trans)-Isomer (minor)：1H NMR (600 MHz, CDCl3, δ ppm): 7.92 (d, J = 9.1
Hz, 1H), 7.44 (s, 1H), 7.40 (t, J = 7.1 Hz, 1H), 7.23 (d, J = 7.9 Hz, 1H), 7.207.08 (m,
4H), 5.48 (s, 1H), 4.56 (t, J = 9.6 Hz, 1H), 3.07 (dd, J = 23.4, 10.6 Hz, 1H), 2.89 (d, J
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= 16.9 Hz, 1H), 2.392.34 (m, 1H), 2.152.08 (m, 1H), 1.89 (s, 3H); C{1H} NMR
(150 MHz, CDCl3, δ ppm): 173.6, 172.0, 141.7, 140.6, 136.0, 134.3, 132.4, 131.6,
128.7, 128.1, 127.0, 126.6, 124.8, 93.9, 61.4, 60.5, 29.6, 28.7, 28.3.
N-Acetyl-N-(2-azido-2,3-dihydro-1H-inden-1-yl)-2-iodobenzamide (2w). Colorless
liquid (73 mg, cis:trans = 9:1, 82%), Rf = 0.18 (PE:EA = 10:1). FT-IR (KBr, cm-1):
2106, 1716, 1672; HRMS (ESI-TOF) m/z: [M+H]+ calcd for [C18H16IN4O2]+:
1
447.0312, found: 447.0315. (cis)-Isomer (major): H NMR (600 MHz, CDCl3, δ
ppm): 7.91 (d, J = 7.9 Hz, 1H), 7.497.43 (m, 2H), 7.36 (d, J = 7.3 Hz, 1H),
7.277.18 (m, 3H), 7.16 (t, J = 7.6 Hz, 1H), 5.79 (s, 1H), 4.39 (q, J = 8.3 Hz, 1H),
3.54 (dd, J = 15.3, 7.8 Hz, 1H), 3.33 (dd, J = 15.6, 8.6 Hz, 1H), 2.12 (s, 3H); 13C{1H}
NMR (150 MHz, CDCl3, δ ppm): 173.5, 172.2, 142.0, 141.4, 140.3, 137.5, 131.7,
128.8, 128.4, 128.4, 127.2, 124.7, 124.1, 93.0, 61.9, 60.4, 37.5, 27.5. (trans)-Isomer
(minor)：1H NMR (600 MHz, CDCl3, δ ppm): 7.90 (d, J = 4.3 Hz, 1H), 7.497.43
(m, 2H), 7.36 (d, J = 7.3 Hz, 1H), 7.277.18 (m, 3H), 7.187.15 (m, 1H), 5.41 (s,
1H), 4.84 (q, J = 6.9 Hz, 1H), 3.56 (dd, J = 15.3, 8.3 Hz, 1H), 2.91 (dd, J = 16.1, 6.7
Hz, 1H), 2.35 (s, 3H); 13C{1H} NMR (150 MHz, CDCl3, δ ppm): 173.5, 172.2, 142.2,
141.3, 140.2, 138.0, 131.8, 128.2, 127.9, 127.2, 124.9, 124.2, 122.5, 93.0, 68.4, 65.5,
36.8, 27.5.
N-Acetyl-N-(2-azido-1-phenylpropyl)-2-iodobenzamide (2x).11 anti-Isomer (2x-1)：
o
1
White solid (47 mg, 52%), mp. 7475 C, Rf = 0.31 (PE:EA = 10:1). H NMR (400
MHz, CDCl3, δ ppm): 7.91 (d, J = 7.9 Hz, 1H), 7.52 (d, J = 6.9 Hz, 2H), 7.377.28
(m, 4H), 7.18 (s, 1H), 7.13 (t, J = 7.7 Hz, 1H), 5.36 (d, J = 10.8 Hz, 1H), 4.99 (s, 1H),
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1.90 (s, 3H), 1.23 (d, J = 6.4 Hz, 3H); C{1H} NMR (100 MHz, CDCl3, δ ppm):
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173.8, 172.4, 141.6, 140.7, 136.1, 132.0, 129.7, 128.8, 128.4, 128.3, 128.2, 94.0, 65.3,
57.3, 27.7, 18.1; FT-IR (KBr, cm-1): 2114, 1714, 1668; HRMS (ESI-TOF) m/z:
[M+H]+ calcd for [C18H18IN4O2]+: 449.0469, found: 449.0472. (syn)-Isomer (2x-2)：
Colorless liquid (27 mg, 30%), Rf = 0.21 (PE:EA = 10:1). 1H NMR (400 MHz, CDCl3,
δ ppm): 7.90 (d, J = 7.9 Hz, 1H), 7.51 (d, J = 7.0 Hz, 3H), 7.407.24 (m, 4H), 7.12 (t,
J = 7.7 Hz, 1H), 6.80 (d, J = 7.2 Hz, 1H), 5.47 (s, 1H), 5.074.93 (m, 1H), 1.89 (s,
3H), 1.47 (d, J = 6.4 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3, δ ppm): 173.5, 172.3,
141.5, 140.8, 136.7, 132.2, 129.1, 128.5, 128.4, 128.2, 128.0, 94.0, 63.5, 57.9, 27.4,
17.4; FT-IR (KBr, cm-1): 2123, 2090, 1714, 1669; HRMS (ESI-TOF) m/z: [M+H]+
calcd for [C18H18IN4O2]+: 449.0469, found: 449.0473.
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N-Acetyl-N-(1-azido-2-phenylpropan-2-yl)-2-iodobenzamide (2y). Colorless liquid
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(62 mg, 70%), Rf = 0.16 (PE:EA = 10:1). H NMR (400 MHz, CDCl3, δ ppm): 7.97
(d, J = 7.9 Hz, 1H), 7.60 (d, J = 7.4 Hz, 1H), 7.52 (d, J = 7.7 Hz, 2H), 7.42 (t, J = 7.6
Hz, 1H), 7.37 (t, J = 7.7 Hz, 2H), 7.28 (d, J = 7.3 Hz, 1H), 7.207.13 (m, 1H), 4.53 (s,
13
1H), 3.80 (s, 1H), 1.97 (s, 3H), 1.92 (s, 3H); C{1H} NMR (100 MHz, CDCl3, δ
ppm): 174.4, 171.0, 142.9, 141.3, 140.7, 132.4, 130.1, 128.5, 128.2, 127.4, 125.4,
95.3, 66.9, 59.8, 29.1, 24.7; FT-IR (KBr, cm-1): 2107, 1712, 1671; HRMS (ESI-TOF)
m/z: [M-N2+H]+ calcd for [C18H18IN2O2]+: 421.0407, found: 421.0400.
1-Azido-2-phenylpropan-2-yl 2-iodobenzoate (4y).12 Colorless liquid (9 mg, 11%),
1
Rf = 0.41 (PE:EA = 10:1). H NMR (400 MHz, CDCl3, δ ppm): 7.98 (d, J = 7.9 Hz,
1H), 7.86 (dd, J = 7.8, 1.7 Hz, 1H), 7.467.35 (m, 5H), 7.31 (t, J = 7.0 Hz, 1H), 7.15
(td, J = 7.7, 1.7 Hz, 1H), 3.84 (d, J = 12.8 Hz, 1H), 3.63 (d, J = 12.8 Hz, 1H), 2.08 (s,
13
3H); C{1H} NMR (75 MHz, CDCl3, δ ppm): 164.8, 141.3, 141.1, 135.7, 132.6,
130.9, 128.6, 128.0, 128.0, 124.9, 93.8, 84.5, 60.7, 22.4.
N-Acetyl-N-(1-azido-2-(o-tolyl)propan-2-yl)-2-iodobenzamide (2z). Colorless
liquid (57 mg, 62%), Rf = 0.19 (PE:EA = 10:1). 1H NMR (600 MHz, CDCl3, δ ppm):
7.94 (d, J = 7.9 Hz, 1H), 7.46 (d, J = 7.6 Hz, 1H), 7.38 (t, J = 7.5 Hz, 1H), 7.34 (d, J =
7.7 Hz, 1H), 7.227.11 (m, 4H), 4.76 (d, J = 10.8 Hz, 1H), 4.12 (d, J = 11.9 Hz, 1H),
13
2.64 (s, 3H), 2.05 (s, 3H), 1.85 (s, 3H); C{1H} NMR (75 MHz, CDCl3, δ ppm):
175.7, 170.5, 141.6, 141.1, 139.9, 134.2, 132.9, 132.0, 129.1, 128.1, 127.5, 126.5,
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126.1, 95.0, 68.1, 59.4, 29.8, 26.0, 21.1; FT-IR (KBr, cm-1): 2105, 1729, 1668; HRMS
(ESI-TOF) m/z: [M+H]+ calcd for [C19H20IN4O2]+: 463.0625, found: 463.0626.
1-Azido-2-(o-tolyl)propan-2-yl 2-iodobenzoate (4z). Colorless liquid (14 mg, 17%),
Rf = 0.37 (PE:EA = 10:1). 1H NMR (400 MHz, CDCl3, δ ppm): 8.00 (dd, J = 7.9, 1.2
Hz, 1H), 7.91 (dd, J = 7.8, 1.7 Hz, 1H), 7.43 (td, J = 7.6, 1.2 Hz, 1H), 7.397.34 (m,
1H), 7.277.19 (m, 2H), 7.197.12 (m, 2H), 4.05 (d, J = 12.9 Hz, 1H), 3.53 (d, J =
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12.8 Hz, 1H), 2.42 (s, 3H), 2.13 (s, 3H); C{1H} NMR (75 MHz, CDCl3, δ ppm):
164.1, 141.6, 138.3, 134.7, 134.6, 132.8, 132.7, 131.1, 128.1, 128.0, 126.4, 126.2,
94.2, 85.2, 59.0, 23.4, 22.1; FT-IR (KBr, cm-1): 2103, 1732; HRMS (ESI-TOF) m/z:
[M-N2+H]+ calcd for [C17H17INO2]+: 394.0298, found: 394.0303.
N-Acetyl-N-(1-azido-2-(p-tolyl)propan-2-yl)-2-iodobenzamide (2aa). Colorless
liquid (47 mg, 51%), Rf = 0.28 (PE:EA = 10:1). 1H NMR (600 MHz, CDCl3, δ ppm):
7.97 (d, J = 7.8 Hz, 1H), 7.59 (d, J = 7.2 Hz, 1H), 7.457.36 (m, 3H), 7.207.12 (m,
3H), 4.53 (s, 1H), 3.78 (s, 1H), 2.32 (s, 3H), 1.95 (s, 3H), 1.91 (s, 3H); 13C{1H} NMR
(150 MHz, CDCl3, δ ppm): 174.6, 171.0, 141.3, 140.9, 139.9, 137.0, 132.3, 130.0,
129.3, 128.2, 125.4, 95.2, 66.8, 59.9, 29.1, 21.0; FT-IR (KBr, cm-1): 2106, 1712,
1672; HRMS (ESI-TOF) m/z: [M-N2+H]+ calcd for [C19H20IN2O2]+: 435.0564, found:
435.0568.
1-Azido-2-(p-tolyl)propan-2-yl 2-iodobenzoate (4aa). Colorless liquid (21 mg,
1
25%), Rf = 0.51 (PE:EA = 10:1). H NMR (400 MHz, CDCl3, δ ppm): 7.99 (dd, J =
8.1, 1.2 Hz, 1H), 7.85 (dd, J = 7.8, 1.7 Hz, 1H), 7.43 (td, J = 7.6, 1.2 Hz, 1H), 7.32 (d,
J = 8.1 Hz, 2H), 7.19 (d, J = 7.9 Hz, 2H), 7.16 (td, J = 7.7, 1.8 Hz, 1H), 3.84 (d, J =
13
12.8 Hz, 1H), 3.62 (d, J = 12.8 Hz, 1H), 2.34 (s, 3H), 2.07 (s, 3H); C{1H} NMR
(100 MHz, CDCl3, δ ppm): 164.8, 141.3, 138.1, 137.8, 135.7, 132.6, 130.9, 129.3,
128.0, 124.8, 93.8, 84.5, 60.8, 22.3, 21.0; FT-IR (KBr, cm-1): 2102, 1732; HRMS
(ESI-TOF) m/z: [M-N2+H]+ calcd for [C17H17INO2]+: 394.0298, found: 394.0304.
N-Acetyl-N-(1-azido-2-(4-fluorophenyl)propan-2-yl)-2-iodobenzamide
(2ab).
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Colorless liquid (47 mg, 50%), Rf = 0.16 (PE:EA = 10:1). H NMR (600 MHz,
CDCl3, δ ppm): 7.99 (d, J = 7.8 Hz, 1H), 7.57 (d, J = 7.4 Hz, 1H), 7.51 (dd, J = 8.0,
5.2 Hz, 2H), 7.44 (t, J = 7.2 Hz, 1H), 7.18 (td, J = 7.7, 1.4 Hz, 1H), 7.05 (t, J = 8.6
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Hz, 2H), 4.48 (s, 1H), 3.76 (s, 1H), 1.96 (s, 3H), 1.92 (s, 3H); C{1H} NMR (150
MHz, CDCl3, δ ppm): 174.4, 170.8, 161.9 (d, J = 245.0 Hz), 141.4, 140.7, 138.8,
132.5, 130.0, 128.3, 127.3 (d, J = 7.5 Hz), 115.4 (d, J = 21.0 Hz), 95.2, 66.4, 59.9,
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29.1, 24.9; F NMR (376 MHz, CDCl3, δ ppm) -115.2; FT-IR (KBr, cm-1): 2107,
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1712, 1672; HRMS (ESI-TOF) m/z: [M+H]+ calcd for [C18H17FIN4O2]+: 467.0375,
found: 467.0377.
1-Azido-2-(4-fluorophenyl)propan-2-yl 2-iodobenzoate (4ab). Colorless liquid (12
mg, 15%), Rf = 0.38 (PE:EA = 10:1). 1H NMR (400 MHz, CDCl3, δ ppm): 7.99 (dd, J
= 7.9, 1.2 Hz, 1H), 7.84 (dd, J = 7.8, 1.7 Hz, 1H), 7.487.38 (m, 3H), 7.17 (td, J = 7.7,
1.7 Hz, 1H), 7.117.03 (m, 2H), 3.81 (d, J = 12.8 Hz, 1H), 3.63 (d, J = 12.8 Hz, 1H),
13
2.08 (s, 3H); C{1H} NMR (100 MHz, CDCl3, δ ppm): 164.8, 162.3 (d, J = 246.0
Hz), 141.4, 136.9 (d, J = 3.0 Hz), 135.4, 132.8, 130.9, 128.0, 126.8 (d, J = 8.0 Hz),
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115.5 (d, J = 21.0 Hz), 93.8, 84.0, 60.7, 22.3; F NMR (376 MHz, CDCl3, δ ppm)
-114.2; FT-IR (KBr, cm-1): 2105, 1732; HRMS (ESI-TOF) m/z: [M+H]+ calcd for
[C16H14FIN3O2]+: 426.0109, found: 426.0116.
N-Acetyl-N-(1-azido-2-(4-chlorophenyl)propan-2-yl)-2-iodobenzamide
(2ac).
White solid (65 mg, 68%), mp 144145 oC, Rf = 0.20 (PE:EA = 10:1). 1H NMR (600
MHz, CDCl3, δ ppm): 7.98 (d, J = 7.8 Hz, 1H), 7.57 (d, J = 7.4 Hz, 1H), 7.47 (d, J =
8.3 Hz, 2H), 7.43 (td, J = 7.6, 0.9 Hz, 1H), 7.33 (d, J = 8.7 Hz, 2H), 7.18 (td, J = 7.7,
1.5 Hz, 1H), 4.45 (s, 1H), 3.78 (s, 1H), 1.92 (s, 6H); 13C{1H} NMR (150 MHz,
CDCl3, δ ppm): 174.2, 170.7, 141.6, 141.4, 140.6, 133.2, 132.5, 130.0, 128.7, 128.2,
126.9, 95.2, 66.3, 59.7, 29.0; FT-IR (KBr, cm-1): 2107, 1711, 1671; HRMS
(ESI-TOF) m/z: [M+H]+ calcd for [C18H17ClIN4O2]+: 483.0079, found: 483.0084.
1-Azido-2-(4-chlorophenyl)propan-2-yl 2-iodobenzoate (4ac). Colorless liquid (14
mg, 16%), Rf = 0.37 (PE:EA = 10:1). 1H NMR (400 MHz, CDCl3, δ ppm): 7.99 (dd, J
= 7.9, 1.2 Hz, 1H), 7.83 (dd, J = 7.7, 1.7 Hz, 1H), 7.43 (td, J = 7.6, 1.2 Hz, 1H), 7.36
(s, 4H), 7.16 (td, J = 7.7, 1.7 Hz, 1H), 3.80 (d, J = 12.8 Hz, 1H), 3.64 (d, J = 12.8 Hz,
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1H), 2.06 (s, 3H); C{1H} NMR (100 MHz, CDCl3, δ ppm): 164.8, 141.4, 138.1,
139.7, 135.4, 134.0, 132.8, 130.9, 128.8, 128.0, 126.5, 93.8, 83.9, 60.5, 22.3; FT-IR
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[C16H13ClIN3O2Na]+: 463.9633, found: 463.9641.
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(2ad).
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Colorless liquid (51 mg, 51%), Rf = 0.11 (PE:EA = 10:1). H NMR (600 MHz,
CDCl3, δ ppm): 7.96 (d, J = 7.8 Hz, 1H), 7.90 (s, 1H), 7.85 (t, J = 8.9 Hz, 2H), 7.81
(d, J = 7.5 Hz, 1H), 7.757.71 (m, 1H), 7.60 (d, J = 7.5 Hz, 1H), 7.517.44 (m, 2H),
7.42 (t, J = 7.5 Hz, 1H), 7.15 (t, J = 7.3 Hz, 1H), 4.65 (s, 1H), 3.91 (s, 1H), 2.06 (s,
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3H), 1.96 (s, 3H); C{1H} NMR (150 MHz, CDCl3, δ ppm): 174.8, 170.8, 141.3,
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140.9, 140.3, 133.1, 132.5, 132.3, 130.0, 128.5, 128.2, 128.2, 127.5, 126.2, 126.1,
124.4, 123.7, 95.2, 67.0, 59.8, 29.2, 25.1; FT-IR (KBr, cm-1): 2106, 1712, 1671;
HRMS (ESI-TOF) m/z: [M+H]+ calcd for [C22H19IN4O2]+: 499.0625, found:
499.0630.
1-Azido-2-(naphthalen-2-yl)propan-2-yl 2-iodobenzoate (4ad). Colorless liquid
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(34 mg, 37%), Rf = 0.31 (PE:EA = 10:1). H NMR (400 MHz, CDCl3, δ ppm): 8.00
(dd, J = 7.9, 1.2 Hz, 1H), 7.927.79 (m, 5H), 7.55 (dd, J = 8.7, 2.0 Hz, 1H),
7.527.42 (m, 3H), 7.18 (td, J = 7.7, 1.7 Hz, 1H), 3.96 (d, J = 12.8 Hz, 1H), 3.71 (d, J
= 12.8 Hz, 1H), 2.19 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3, δ ppm): 164.9, 141.3,
138.4, 135.6, 133.0, 132.8, 132.3, 132.7, 130.9, 128.5, 128.3, 128.0, 127.6, 126.4,
126.4, 124.3, 122.6, 93.8, 84.6, 60.6, 22.4; FT-IR (KBr, cm-1): 2102, 1731; HRMS
(ESI-TOF) m/z: [M+H]+ calcd for [C20H17IN3O2]+: 458.0360, found: 458.0358.
N-Acetyl-N-(1-azido-2-phenylbutan-2-yl)-2-iodobenzamide (2ae). Colorless liquid
(65 mg, 70%), Rf = 0.14 (PE:EA = 10:1). 1H NMR (400 MHz, CDCl3, δ ppm):7.92 (d,
J = 7.9 Hz, 1H), 7.50 (d, J = 7.5 Hz, 2H), 7.46 (dd, J = 7.6, 1.4 Hz, 1H), 7.37 (td, J =
7.8, 3.6 Hz, 3H), 7.26 (t, J = 7.3 Hz, 1H), 7.11 (t, J = 7.7 Hz, 1H), 4.67 (d, J = 11.2
Hz, 1H), 4.22 (d, J = 12.2 Hz, 1H), 2.24 (d, J = 6.2 Hz, 2H), 2.06 (s, 3H), 0.84 (t, J =
7.2 Hz, 3H); C{1H} NMR (75 MHz, CDCl3, δ ppm): 177.0, 169.0, 142.0, 141.1,
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140.9, 131.9, 129.5, 128.3, 128.0, 127.2, 125.9, 94.8, 69.7, 54.4, 30.1, 29.4, 8.8;
FT-IR (KBr, cm-1): 2105, 1735, 1668; HRMS (ESI-TOF) m/z: [M+Na]+ calcd for
[C19H19IN4O2Na]+: 485.0445, found: 485.0436.
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N-Acetyl-N-(2-azido-2-methyl-1-phenylpropyl)-2-iodobenzamide (2af). Colorless
liquid (76 mg, 82%), Rf = 0.21 (PE:EA = 10:1). 1H NMR (400 MHz, CDCl3, δ ppm):
7.89 (d, J = 7.9 Hz, 1H), 7.56 (dd, J = 6.5, 2.9 Hz, 2H), 7.317.22 (m, J = 2.9 Hz,
3H), 7.18 (s, 1H), 7.06 (td, J = 7.7, 1.3 Hz, 1H), 6.94 (s, 1H), 5.90 (s, 1H), 1.99 (s,
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3H), 1.54 (d, J = 18.2 Hz, 6H); C{1H} NMR (100 MHz, CDCl3, δ ppm): 174.5,
172.4, 141.0, 140.8, 135.9, 131.8, 130.7, 128.9, 128.1, 128.1, 127.8, 94.6, 65.4, 64.5,
27.5, 25.8, 25.6; FT-IR (KBr, cm-1): 2107, 1721, 1674; HRMS (ESI-TOF) m/z:
[M+H]+ calcd for [C19H20IN4O2]+: 463.0625, found: 463.0631.
1-(1,2-Diazidoethyl)-4-nitrobenzene (3ag).12 Slight yellow liquid (14 mg, 30%), Rf
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= 0.22 (PE:EA = 10:1). H NMR (400 MHz, CDCl3, δ ppm): 8.368.22 (m, 2H),
7.647.48 (m, 2H), 4.81 (dd, J = 7.2, 5.5 Hz, 1H), 3.643.42 (m, 2H); 13C{1H} NMR
(100 MHz, CDCl3, δ ppm): 148.2, 143.5, 127.9, 124.2, 64.5, 55.8; FT-IR (KBr, cm-1):
2103, 1522, 1349.
4-(1,2-Diazidoethyl)benzonitrile (3ah).12 Colorless liquid (14 mg, 33%), Rf = 0.16
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(PE:EA = 10:1). H NMR (300 MHz, CDCl3, δ ppm): 7.767.68 (m, 2H), 7.517.44
(m, 2H), 4.74 (dd, J = 7.2, 5.5 Hz, 1H), 3.583.42 (m, 2H); 13C{1H} NMR (100 MHz,
CDCl3, δ ppm): 141.6, 132.8, 127.7, 118.1, 112.9, 64.7, 55.7; FT-IR (KBr,cm-1):
2233, 2106.
2-(1,2-Diazidoethyl)pyridine (3ai).6a Colorless liquid (8 mg, 22%), Rf = 0.16
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(PE:EA = 10:1). H NMR (400 MHz, CDCl3, δ ppm): 8.62 (d, J = 4.7 Hz, 1H), 7.76
(td, J = 7.7, 1.6 Hz, 1H), 7.42 (d, J = 7.8 Hz, 1H), 7.29 (dd, J = 7.6, 4.9 Hz, 1H), 4.72
(dd, J = 7.6, 4.8 Hz, 1H), 3.82 (dd, J = 12.7, 4.8 Hz, 1H), 3.69 (dd, J = 12.7, 7.7 Hz,
1H); C{1H} NMR (100 MHz, CDCl3, δ ppm): 155.8, 149.8, 137.2, 123.6, 122.0,
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65.5, 54.5; FT-IR (KBr, cm-1): 2103, 1590.
2-Azido-1-(4-methoxyphenyl)ethyl 2-iodobenzoate (4aj).12 Colorless liquid (55 mg,
65%), Rf = 0.31 (PE:EA = 10:1). 1H NMR (600 MHz, CDCl3, δ ppm): 8.00 (d, J = 7.9
Hz, 1H), 7.88 (dd, J = 7.7, 1.2 Hz, 1H), 7.447.38 (m, 3H), 7.16 (t, J = 7.7 Hz, 1H),
6.92 (d, J = 8.6 Hz, 2H), 6.10 (dd, J = 7.7, 4.4 Hz, 1H), 3.80 (s, 3H), 3.79 (dd, J = 7.9
Hz, 5.3 Hz, 1H), 3.61 (dd, J = 13.1, 4.3 Hz, 1H); 13C{1H} NMR (150 MHz, CDCl3, δ
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ppm): 165.2, 160.0, 141.5, 134.4, 132.9, 131.1, 128.7, 128.2, 127.9, 114.1, 94.2, 75.4,
55.3, 55.1; FT-IR (KBr, cm-1): 2102, 1730.
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2-Azido-1,1-diphenylethyl 2-iodobenzoate (4ak). Colorless liquid (60 mg, 64%), Rf
= 0.40 (PE:EA = 10:1). 1H NMR (600 MHz, CDCl3, δ ppm): 7.98 (dd, J = 7.8, 3.5 Hz,
1H), 7.93 (s, 1H), 7.497.27 (m, 11H), 7.16 (t, J = 7.7 Hz, 1H), 4.71 (d, J = 5.8 Hz,
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2H); C{1H} NMR (75 MHz, CDCl3, δ ppm): 164.9, 141.5, 141.3, 135.4, 132.7,
130.7, 128.3, 128.0, 126.4, 93.9, 86.4, 56.7; FT-IR (KBr, cm-1): 2102, 1734; HRMS
(ESI-TOF) m/z: [M+Na]+ calcd for [C21H16IN3NaO2]+: 492.0179, found: 492.0186.
2-Azido-1-(thiophen-2-yl)ethyl 2-iodobenzoate (4al).12 Colorless liquid (50 mg,
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63%), Rf = 0.36 (PE:EA = 10:1). H NMR (400 MHz, CDCl3, δ ppm): 8.01 (dd, J =
8.0, 1.2 Hz, 1H), 7.88 (dd, J = 7.8, 1.7 Hz, 1H), 7.42 (td, J = 7.6, 1.2 Hz, 1H), 7.36
(dd, J = 5.1, 1.2 Hz, 1H), 7.23 (dd, J = 3.6, 1.2 Hz, 1H),7.17 (td, J = 7.7, 1.7 Hz, 1H),
7.03 (dd, J = 5.1, 3.6 Hz, 1H), 6.45 (dd, J = 7.2, 4.6 Hz, 1H), 3.86 (dd, J = 13.0, 7.2
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Hz, 1H), 3.76 (dd, J = 13.1, 4.5 Hz, 1H); C{1H} NMR (150 MHz, CDCl3, δ ppm):
164.9, 141.5, 138.6, 133.9, 133.0, 131.2, 127.9, 127.2, 126.9, 126.5, 94.3, 71.1, 54.9;
FT-IR (KBr, cm-1): 2104, 1732.
2-Azido-1-(4-chloro-N-methylphenylsulfonamido)ethyl 2-iodobenzoate (4am).
Colorless liquid (78 mg, 75%), Rf = 0.12 (PE:EA = 10:1), eluent for column
chromatography: PE/EA = 10:1 to 3:1. 1H NMR (400 MHz, CDCl3, δ ppm): 7.98 (d, J
= 7.8 Hz, 1H), 7.77 (d, J = 8.6 Hz, 2H), 7.427.30 (m, 4H), 7.17 (td, J = 7.9, 2.0 Hz,
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1H), 6.83 (t, J = 6.6 Hz, 1H), 3.753.61 (m, 2H), 3.02 (s, 3H); C{1H} NMR (150
MHz, CDCl3, δ ppm): 163.9, 141.6, 139.7, 136.5, 133.5, 132.7, 131.0, 129.4, 128.8,
127.8, 94.2, 80.2, 50.6, 30.0; FT-IR (KBr, cm-1): 2108, 1735; HRMS (ESI-TOF) m/z:
[M+Na]+ calcd for [C16H14ClIN4O4SNa]+: 542.9361, found: 542.9360.
2-Azido-1-(4-bromo-N-methylphenylsulfonamido)ethyl 2-iodobenzoate (4an).
Colorless liquid (79 mg, 70%), Rf = 0.12 (PE:EA = 10:1), eluent for column
chromatography: PE/EA = 10:1 to 3:1. 1H NMR (400 MHz, CDCl3, δ ppm): 7.99 (d, J
= 7.8 Hz, 1H), 7.69 (d, J = 8.6 Hz, 2H), 7.53 (d, J = 8.6 Hz, 2H), 7.397.31 (m, 2H),
7.18 (td, J = 7.9, 2.5 Hz, 1H), 6.82 (t, J = 6.6 Hz, 1H), 3.773.63 (m, 2H), 3.02 (s,
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3H); C{1H} NMR (150 MHz, CDCl3, δ ppm): 164.0, 141.7, 139.2, 133.5, 132.9,
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