NFSI-participated intermolecular aminoazidation of alkene through iron catalysis

Article abstract of DOI:10.1039/c8ob00699g

An iron-catalysed intermolecular vicinal aminoazidation of alkenes, using N-fluorobenzenesulfonimide (NFSI) and trimethylsilyl azide (TMSN₃) as the imidating and azidating reagents, respectively, is described, which could potentially provide a valuable route toward diverse vicinal diamine derivatives of great significance in medicinal chemistry and organic synthesis. Such iron-catalysed aminative bisfunctionalization of alkenes with NFSI has not been reported yet. Comparing to previously employed copper or palladium catalysts, the iron catalyst, FeCl₂, was demonstrated to be a good alternative for its comparable efficiency and broad alkene scope. Preliminary mechanistic study suggested that this iron-catalysed reaction is realized through radical processes.

Full text of DOI:10.1039/c8ob00699g

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Further Respond to Reviewers
(
OB-COM-03-2018-000699)
Reviewer 3
The revised manuscript has addressed the main questions properly. It is recommended for
publication after a few minor changes.
We are grateful to the reviewer for positive comments and kind suggestions on our revised
manuscript. Corresponding changes have been made according to the reviewer’s suggestions as
bellow:
1
, Remove the citation (reference 10) in the sentence “…we would like to report our recent
study on the iron-catalysed intermolecular vicinal aminoazidation of alkenes10 (Scheme 1c).”
No reference should be cited before “(Scheme 1c)”
We appreciate the reviewer’s suggestion, and have remove the cited reference in this sentence.
2
, Change the citation 10 to 10a in the sentence “…On the contrary, no matter how much the
reaction time was, the yields of 2a remained poor in absence of ligand when changing the iron
catalyst to CuCl10 (entry 12),..”
We appreciate the reviewer’s suggestion, and have changed the citation 10 to 10a in this sentence.
3
, The following paragraph should be revised for clarity. The information is somehow
confusing and doesn’t fit well the cited references.
“
In 2014, Zhang and Studer reported a novel copper-catalysed aminoazidation of styrenes
(
Scheme 1b),10a which has drawn our attention since organic azides could serve as versatile
intermediates to easily transform to other nitrogen-containing functional groups including
amines,10, 15 albeit their protocol could only be effective on styrenes and could not react in
absence of a ligand. Zhang and Studer also demonstrated that both benzenesulfonyl and azide
two different protecting groups of amines, which can be deprotected under different conditions
sequentially,10a allowing maximal synthetic flexibility and providing an opportunity to prepare
vicinal diamines with two miscellaneously functionalized amino groups. “
Consider the revision as below:
In 2014, Zhang and Studer reported a novel copper-catalysed aminoazidation of styrenes
(
Scheme 1b),10a which has drawn our attention since organic azides could serve as versatile
intermediates to easily transform to other nitrogen-containing functional groups including
amines.10, 15 They also demonstrated that both benzenesulfonyl and azide two different
protecting groups of amines can be deprotected under different conditions sequentially.10a

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Although it offers maximal synthetic flexibility and an opportunity to prepare vicinal diamines
with two miscellaneously functionalized amino groups, this copper-catalysed protocol was only
be effective on styrenes and could not react in absence of a ligand.
We appreciate the reviewer’s suggestion, and have changed this paragraph as the reviewer
suggested, highlighted in yellow background.
4
, remove the yellow highlight in the manuscript for the accepted version.
We appreciate the reviewer’s kind suggestion. Beside the revised manuscript with yellow highlight
to point out the changes we have made, we also provide a DOC file and a PDF file without the
yellow highlight for the accepted version.
In summary, we would like to gratefully thank all the editors and reviewers again for the above
positive comments and constructive suggestions on our manuscript.
Best regards,
Ziyuan Li, PhD
Department of Pharmaceutical and Biological Engineering
Sichuan Universit, No.24 South Section 1, Yihuan Road, Chengdu, 610065, P. R. China
Fax: 0086-28-85405221, Tel: 0086-18200172403
E-mail: liziyuan@scu.edu.cn

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NFSI-participated Intermolecular Aminoazidation of Alkene
through Iron Catalysis†
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
a
a
a
Bowen Lei, Xiaojiao Wang, Lifang Ma, Yan Li, and Ziyuan Li*
DOI: 10.1039/x0xx00000x
www.rsc.org/
1
1a
11b
An iron-catalysed intermolecular vicinal aminoazidation of oxidative benzylic and aromatic C-H aminations with NFSI,
alkenes, using N-fluorobenzenesulfonimide (NFSI) and followed by the widely applications of this imidating reagent in
trimethylsilyl azide (TMSN
reagents respectively, is described, which could potentially
provide valuable route toward diverse vicinal diamine
derivatives of great significance in medicinal chemistry and
organic synthesis. Such iron-catalysed aminative
1
2
13
14
3
) as the imidating and azidating C-H amination of arenes , alkanes and alkenes .
a) Aminative difunctionalization of alkenes with NFSI3-9
(
a
R
2
Nu
SO
SO
2
Ph
Ph
Cu or Pd
1
+
F
N
+
Nu
N(SO
2 2
Ph)
R
R1
R2
R3
2
R3
Nu = aryl, -CN, -OR, -SR, -F, -NHR, -NR2
b) Ligand-enabled aminoazidation of styrenes via copper catalysis
bisfunctionalization of alkene with NFSI has not yet been reported
before. Comparing to previously employed copper or palladium
10
(
2
R
N
3
F
N(SO
2
Ph)
2
CuI
N(SO
2 2
Ph)
( R1 = aryl )
catalysts, the iron catalyst, FeCl
2
, was demonstrated to be a good
R1
+
R1
Ligand
R2
R3
TMS
N
3
R3
alternative for its comparable efficiency and broad alkene scope.
Preliminary mechanistic study suggested that this iron-catalysed
reaction is realized through radical process.
(
c) This work: efficient iron-catalysed aminoazidation of alkenes
R2
N
F
N(SO
2
Ph)
2
FeII
3
( R1 = aryl, alkyl, alkoxyl,
acyloxyl, imidyl )
R1
+
N(SO
2 2
Ph)
1
R
R2
R3
TMS
N
3
R3
the first Fe-catalysed aminative bisfunctionalization of alkenes with NFSI
Vicinal diamine is a ubiquitous scaffold of great significance,
which widely resides in miscellaneous ligands, organocatalysts, Scheme 1 Transition-metal catalyzed aminative functionalization with NFSI
synthetic building blocks, and biologically active natural or
1
artificial molecules. To acquire such significant moiety, many
Among these bisfunctionalization of alkenes with NFSI, the
diamination and aminoazidation could provide a potential
approach toward the above-mentioned significant vicinal
efforts have been spent on transition metal-catalysed 1,2-
diamination of alkenes, but the catalysts used in these
5
a, 9a-b,
2
diamine moiety. However, all these reactions were Cu-
1
reactions were generally limited to copper and palladium.
0a
9c-f
or Pd- catalysed, and require assistance of a ligand
5a, 9a,e-f
Recently, NFSI (N-fluorobenzenesulfonimide), which could
easily generate an electrophilic disulfonimidyl radical, has been
broadly used as an oxidative imidating reagent in transition
metal-catalysed or metal-free amination reactions through
cascade radical processes. Since Michael group and Liu group
9
b-d
or an additive
to realize the reaction or to guarantee
gratifying yields. More importantly, most of these reactions
5
a, 9a-b
were only effective on active alkenes like styrenes
or
9
allylic ethers . Michael group reported a series of significant
c
9
d-f
3
a
works on 1,2-diamination of inactive alkenes with NFSI, but
one of the two amination steps was proceeded
intramolecularly, affording aminated N-heterocycles only,
which limited the diversity of vicinal diamine products. Up to
now, no NFSI-participated intermolecular diamination of
inactive alkenes has been reported.
disclosed two pioneering works on NFSI-involved diamination
3
b
and aminofluorination of alkene, NFSI has been widely
employed as a powerful nitrogen donor in vicinal aminative
4
-10
difunctionalization of alkenes (Scheme 1a)
, such as
4
5
aminoarylation , aminocyanation , aminooxygenation , amino-
6
7
thionation , aminofluorination , diamination
8
5a, 9
, and amino-
1
0a
In 2014, Zhang and Studer reported a novel copper-catalysed
azidation . Beside aminative difunctionalization of alkene,
Zhang group reported the first two examples on Pd-catalysed
1
0a
aminoazidation of styrenes (Scheme 1b), which has drawn
our attention since organic azides could serve as versatile
intermediates to easily transform to other nitrogen-containing
1
0, 15
functional groups including amines.
They also
demonstrated that both benzenesulfonyl and azide group, two
different protecting groups of amines, can be deprotected
1
0a
under different conditions sequentially. Although it offers
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Journal Name
maximal synthetic flexibility and an opportunity to prepare in order to investigate whether the relatively long reaction
1
8
vicinal diamines with two miscellaneously functionalized time is necessary. The results showed that the reaction
amino groups, this copper-catalysed protocol was only catalysed by FeCl was fast, providing 2a in 90% NMR yield
2
effective on styrenes and could not react in absence of a ligand. after 3 hours (entry 11), and no ligand or additive is required,
Though limitations were observed, these previous reports indicating that elevating temperature solely is sufficient to
have enlightened us to develop new transition metal catalysts promote the efficiency of this iron-catalysed aminoazidation.
with comparable efficiency but broader alkene scope for the Prolonging the reaction time could not further promote the
NFSI-participated aminative bisfunctionalization. Herein, as an yield (entry 10). On the contrary, no matter how much the
advancement
of
our previous
studies
on
C-H reaction time was, the yields of 2a remained poor in absence
10a
1
6
functionalization
including the first iron-catalysed C-H of ligand when changing the iron catalyst to CuCl (entry 12),
1
6a
imidation with NFSI , as well as other works on transition suggesting that, for the copper-catalysed reaction, increasing
metal-catalysed annulations with simple nitrogen donors temperature is less helpful than the employment of an
1
7
including azide, we would like to report our recent study on appropriate ligand. In addition, no aminoazidated product was
the iron-catalysed intermolecular vicinal aminoazidation of generated when the reaction was conducted without FeCl
2
alkenes (Scheme 1c). To our knowledge, the iron-catalysed (entry 13). Therefore, the reaction conditions in entry 11 were
aminative bisfunctionalization of alkenes with NFSI has not selected as the optimized conditions for subsequent
been disclosed previously.
exploration of alkene scope.
a
Table 1 Optimization of the reaction conditions
Entry Solvent
2 ml)
Temperature
o
( C)
Time
(h)
Yield
b
(%)
(
1
2
3
4
5
6
7
8
9
1
1
1
1
DCE
70
15
15
15
15
15
15
15
15
15
5
44
DMF
DME
70
trace
0
70
CH CN
3
70
35
Dioxane
Toluene
DCE
70
0
70
trace
73
100
100
100
100
100
100
100
c
DCE
84
c, d
DCE
78
c
0
DCE
(87)
85 (90)
(14)
0
c
1
DCE
3
c, e
2
3
DCE
3
c, f
DCE
3
a
Reaction conditions: styrene 1a (0.5 mmol), NFSI (0.75 mmol),
TMSN (0.75 mmol), FeCl (0.05 mmol) in solvent (2 mL) in air (1
atm). Isolated yields of 2a. The yields in the parentheses are
determined by NMR using CH Br as an internal standard.
(1 atm). With NFSI (1 mmol) and TMSN (1
. In the
Scheme 2 Fe-catalysed aminoazidation of styrenes with NFSI. Reaction
conditions: see entry 11, Table 1. Isolated yields.
3
2
b
With the optimized conditions established, a variety of styrene
derivatives were investigated for this aminoazidation (Scheme
2
2
c
d
Conducted under N
mmol). Catalyzed by CuCl (0.05 mmol) instead of FeCl
absence of FeCl
2
3
e
f
2
2, 2a-m). Generally, all styrenes underwent this Fe-catalysed
2
.
ligand-free aminoazidation smoothly, affording corresponding
products 2b-j in good yields, and no remarkable differences in
yields were observed between electron-rich methyl-, tert-
butyl- or acetoxyl-substituted products (2b-d) and electron-
deficient fluoro-, chloro- or bromo-substituted styrenes (2e-j).
Moreover, steric hindrance on the benzene ring seemed to
share little impact on the yield, since the yields of para-
substituted 2g and ortho-substituted 2i are comparable.
However, conversion of 4-vinylbiphenyl or 2-vinylnaphthalene
with larger conjugated system was poorer, and the yields of
their aminoazidated products (2k-l) were moderate. In
Our investigation was commenced with the screening of
reaction conditions for this novel iron-catalysed
aminoazidation using styrene 1a as the alkene substrate, and
the results are summarized in Table 1. Initial trial with 10 mol%
o
of FeCl at 70 C in air afforded corresponding aminoazidated
2
product 2a in 44% yield after 15 hours (entry 1). Several
commonly used solvents were screened (entries 2-6), and
most gave no or only trace product 2a under the same
conditions, except for acetonitrile with 35% yield (entry 4),
indicating that DCE is the best solvent. The yield of 2a was
considerably elevated when reaction temperature was
addition,
corresponding product 2m in a slightly dropped yield. When
internal alkenes, β-methylstyrene 1n or 1,2-
dihydronaphthalene 1o), were conducted under the
a
1,1-disubstituted styrene 1m also gave
o
increased to 100 C (entry 7), and could be further promoted
to 84% when this aminoazidation was conducted under N (1
2
(
)
atm), suggesting molecular dioxygen is detrimental to this
reaction (entry 8). Kinetic experiments were then conducted,
(
2
| J. Name., 2012, 00, 1-3
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optimized conditions, the yield of aminoazidated product 2n Then a competition experiment was performed to elucidate
was well maintained, while the yield of 2o generated from the electronic preference on the alkene substrate. An
more rigid substrate 1o declined remarkably. The equimolecular mixture of styrenes 1b and 1e was subjected to
3
diastereoselectivity of 2n and 2o could be readily insufficient loadings of NFSI and TMSN , and the ratio between
1
10
determinated by H-NMR spectra of the crude products, and electron-rich aminoazidated products 2b and electron-
both showed excellent trans-selectivity (94:6 and 97:3, deficient product 2e was approximately 2.85 : 1 (Scheme 4b),
respectively), which is comparable to the Cu-catalysed indicating that this Fe-catalysed aminoazidation could be
1
0
aminoazidation reported by Zhang and Studer.
categorized as an electrophilic radical addition on alkenes,
which is consistent with previously reported copper- or
palladium-catalysed aminative bisfunctionalization of alkene
with NFSI.
Scheme 4 Control experiments.
Scheme 3 Fe-catalysed aminoazidation of alkenes beside styrenes. Reaction
conditions: alkene (0.5 mmol), NFSI (0.75 mmol), TMSN (0.75 mmol),
FeCl (0.05 mmol) and 2,2'-bipyridine (5 mol%) in DCE (2 mL) under N (1 To summarize, we have developed an intermolecular vicinal
Conclusions
1
3
2
2
o
a
b
atm) at 80 C. Isolated yields. Reaction time was prolonged to 6 h. At 100
C, without 2,2'-bipyridine.
aminoazidation of alkene with NFSI and TMSN
3
through iron
o
catalysis. By elevating the reaction temperature, this iron-
Subsequently, the substrate scope of this efficient Fe-catalyzed catalysed aminoazidation on styrene could be achieved in
aminoazidation was expanded to other types of alkene beside absence of ligand, and the alkene scope of this reaction is
styrene (Scheme 3, 2p-u). Assisted by 5 mol% of 2,2’-bipyridine, broader than previous copper catalysis, suggesting that iron
inactivated alkenes such as 1-octene (1q), 1-decene (1r) and catalysis might probably be a promising alternative for diverse
vinylcyclohexane (1p) could provide aminoazidated products aminative bisfunctionalization of alkenes in addition of copper-
2
p-r in moderate yields at lower temperature, while such or palladium-catalysis. Fully revealing the precise mechanistic
0
1
aliphatic alkenes did not react under Cu-catalysed conditions.
picture, as well as further development of other iron-catalysed
Heteroatom-substituted alkenes including N-vinylphthalimide aminative bisfunctionalization of alkene with NFSI, are
1s), n-butyl vinyl ether (1t) and vinyl benzoate (1u) could also undergoing.
undergo this aminoazidation, affording corresponding
(
products 2s-u in moderate to good yields. These results
suggested that the alkene scope of this Fe-catalysed Acknowledgements
1
0
aminoazidation is broader than previous copper catalysis.
This work is supported by the Fundamental Research Funds for
the Central Universities (2016SCU11020). Prof. Hequan Yao
and Dr. Yue Huang from China Pharmaceutical University are
highly acknowledged for the assistance with the HRMS analysis.
Interestingly, the desired aminoazidated product could not be
obtained when this reaction was conducted on 1,1-
diphenylethylene (1v). Instead, an oxidative C-H aminated
product 3v was generated with or without TMSN
3
, indicating
that 1,1-diaryl alkene might undergo hydrogen elimination
more easily than azidation after the addition of disulfonimidyl Notes and references
group.
1
(a) J.-E. Backvall, Acc. Chem. Res., 1983, 16, 335; (b) A.
To gain some insights into mechanistic picture preliminarily,
Minatti, K. Muniz, Chem. Soc. Rev., 2007, 36, 1142; (c) J.-C.
Kizirian, Chem. Rev., 2008, 108, 140; (d) F. Cardona, A. Goti,
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Med. Chem., 2006, 49, 1; (h) M. J. Borrok, L. L. Kiessling, J.
Am. Chem. Soc., 2007, 129, 12780.
1
8
some control experiments were then performed. First, the
addition of TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl)
severely suppressed this aminoazidation. Meanwhile, an
aminooxygenated product 4a was obtained in 16% yield
(Scheme 4a), suggesting that a benzyl radical might probably
be formed after the attack of the disulfonimidyl radical
generated from NFSI, coinciding with copper-catalysed
2
(a) A. O. Chong, K. Oshima, K. B. Sharpless, J. Am. Chem. Soc.,
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aminofluorination of styrenes with NFSI studied by Zhang.
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| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
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Page 9 of 71
Organic & Biomolecular Chemistry
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DOI: 10.1039/C8OB00699G
The iron-catalysed intermolecular vicinal aminoazidation of alkene with NFSI is reported, with
broader alkene scope comparing to previously reported aminoazidation.

Organic & Biomolecular Chemistry
Page 10 of 71
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DOI: 10.1039/C8OB00699G
Electronic Supplementary Information for:
NFSI-participated Intermolecular Aminoazidation of Alkene
through Iron Catalysis
a
a
a
a
a
Bowen Lei, Xiaojiao Wang, Lifang Ma, Yan Li, and Ziyuan Li*
a
Department of Pharmaceutical and Biological Engineering, School of Chemical Engineering, Sichuan
University, No.24 South Section 1, Yihuan Road, Chengdu 610065, China
E-mail: liziyuan@scu.edu.cn; Fax: (+86)28-85405221
Table of Contents
General Remarks
Kinetic Studies
S2
S3-S4
Experimental Procedure and Characterization Data
Control Experiments
S5-S12
S13-S15
S16
References
1
13
H NMR and C NMR Spectra of Products
S17–S62
S1

Page 11 of 71
Organic & Biomolecular Chemistry
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DOI: 10.1039/C8OB00699G
General Remarks
All commercially available compounds were purchased from Sigma-Aldrich, Alfa-Aesar, Acros, J&K
Chemicals, Adamas-beta, Accela ChemBio and Aladdin Chemicals. FeCl was purchased from Alfa-Aesar
99.99% purity, ultra dry, CAS No. 7758-94-3). TMSN was purchased from TCI (>95%, CAS No.
648-54-8). N-Fluorobenzenesulfonimide (NFSI) (98% purity, CAS No. 133745-75-2) and 2,2’-bipyridine
98% purity, CAS No. 366-18-7) were purchased from Accela ChemBio. Unless otherwise noted, materials
2
(
3
4
(
obtained from commercial suppliers were used without further purification. Products were purified by flash
chromatography on silica gel using petroleum ether, ethyl acetate and dichloromethane as the eluents.
1H-NMR spectra were recorded on Bruker AVANCE III-400 spectrometers. Chemical shifts (in ppm) were
referenced with TMS in CDCl
3
(0 ppm). 13C-NMR spectra were obtained by using the same NMR
(δ = 77.00 ppm). High resolution mass spectra were
spectrometers and were calibrated with CDCl
3
obtained from an Agilent 6520B Q-TOF mass spectrometer with electron spray ionization (ESI) as the ion
source.
S2

Organic & Biomolecular Chemistry
Page 12 of 71
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DOI: 10.1039/C8OB00699G
Kinetic Studies
To a reaction tube charged with FeCl
a solution of styrene (1a, 57.5 μL, 0.5 mmol), TMSN
under N (1 atm). The reaction mixture was stirred at 100 C for indicated time in Table S1. After rapidly
2
(6.3 mg, 0.05 mmol) and NFSI (236.5 mg, 0.75 mmol) was added
3
(98.6 μL, 0.75 mmol ) in DCE (2 mL) via a syringe
o
2
cooled by ice, the mixture was diluted with ethyl acetate, filtered through a celite pad, and concentrated in
1
vacuo. The residue was analyzed with H-NMR to determine the yields of 2a through iron-catalysis, using
CH
2
Br as an internal standard. Similarly, the yields of 2a via copper-catalysis, using the same copper
2
catalyst employed by Zhang and Studer,[1] were determined in the same way. Then the yields of 2a via
iron- or copper-catalysis in different times were summarized in Table S1 and Figure S1, accordingly.
Table S1. Detailed Results of Kinetic Studies.
Time
20
40
60
80
100
120
180
300
420
(
min)
FeCl
CuCl
2
39.8
9.7
53.0
13.7
64.1
15.4
72.7
16.3
78.0
15.8
82.5
14.6
89.8
13.6
87.2
11.8
85.6
9.6
Figure S1. Detailed Results of Kinetic Studies.
S3

Page 13 of 71
Organic & Biomolecular Chemistry
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From the data in Table S1 and Figure S1, this aminoazidation catalyzed by FeCl
2
is rem
D
a
O
r
I
k
: 1
a
0
b
.1
l
0
y
39
f
/
ast
erB00699G
C
8
O
than catalyzed by CuCl, which was previously employed by Zhang and Studer,[1] while the yields of 2a
remained very low, no matter how much the reaction time was, when the reaction was catalyzed by CuCl.
Theses results demonstrated that the iron catalyst, which could achieve this reaction rapidly without any
ligand or additive and provide the product in excellent yield after 3 hours, is a competitive alternative to
previously used copper catalyst, which could not effectively realize this reaction in absence of certain
ligands.[1]
S4

Organic & Biomolecular Chemistry
Page 14 of 71
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DOI: 10.1039/C8OB00699G
Experimental Procedure and Characterization Data
Typical Procedure: To a reaction tube charged with FeCl
2
(6.3 mg, 0.05 mmol) and NFSI (236.5 mg, 0.75
mmol) was added a solution of alkene (1a-u, 0.5 mmol), TMSN (98.6 μL, 0.75 mmol) in DCE (2 mL) via
3
o
a syringe under N (1 atm). The reaction mixture was stirred at 100 C for 3 hours. After rapidly cooling by
2
ice, the mixture was diluted with ethyl acetate, filtered through a celite pad, and concentrated in vacuo to
give dark residue, which was then purified by flash chromatography using petroleum ether and ethyl
acetate as the eluent on silical gel to afford aminoazidated product 2a-u.
N-(2-Azido-2-phenylethyl)-N-(phenylsulfonyl)benzenesulfonamide[1] (2a):
The reaction of 0.5 mmol of styrene (1a) with NFSI and TMSN
3
afforded 187.2 mg of
2a (85%) as colorless oil, after flash chromatography on silica gel using petroleum
1
ether and ethyl acetate (15:1, v/v) as the eluent. H NMR (CDCl , 400 MHz): δ = 8.07-8.05 (m, 4H),
3
7
.67-7.63 (m, 2H), 7.56-7.52 (m, 4H), 7.40-7.35 (m, 5H), 5.01 (dd, J = 9.6 Hz, 4.2 Hz, 1H), 4.06 (dd, J = 15.6
Hz, 9.6 Hz, 1H), 3.72 (dd, J = 15.6 Hz, 4.2 Hz, 1H) ppm; 13C NMR (CDCl
3
, 100 MHz): δ = 139.22, 136.44,
1
34.02, 129.12, 129.02, 128.98, 128.57, 127.19, 65.57, 53.18 ppm. HRMS m/z (ESI) calcd for
+
[C
20
H
18
N
4
O
4
S +Na] 465.0662, found 465.0669.
2
N-(2-Azido-2-(p-tolyl)ethyl)-N-(phenylsulfonyl)benzenesulfonamide[1] (2b):
The reaction of 0.5 mmol of p-methylstyrene (1b) with NFSI and TMSN
3
afforded
1
78.1 mg of 2b (78%) as white solid (m.p. 133.4-134.8 oC), after flash
1
chromatography on silica gel using petroleum ether and ethyl acetate (15:1, v/v) as the eluent. H NMR
CDCl , 400 MHz): δ = 8.06-8.04 (m, 4H), 7.66-7.62 (m, 2H), 7.55-7.52 (m, 4H), 7.25 (d, J = 8.1 Hz, 2H),
.20 (d, J = 8.1 Hz, 2H), 4.98 (dd, J = 9.6 Hz, 4.3 Hz, 1H), 4.05 (dd, J = 15.6 Hz, 9.6 Hz, 1H), 3.70 (dd, J = 15.6
(
3
7
13
Hz, 4.3 Hz, 1H), 2.36 (s, 3H) ppm; C NMR (CDCl
3
, 100 MHz): δ = 139.20, 138.95, 133.98, 133.32, 129.75,
+
1
28.94, 128.56, 127.15, 65.32, 53.09, 21.16 ppm. HRMS m/z (ESI) calcd for [C21
H
20
N
4
O
4
S
2
+Na] 479.0818,
S5

Page 15 of 71
Organic & Biomolecular Chemistry
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found 479.0827.
DOI: 10.1039/C8OB00699G
N-(2-Azido-2-(4-(tert-butyl)phenyl)ethyl)-N-(phenylsulfonyl)benzenesulfonamide[1] (2c):
The reaction of 0.5 mmol of p-tert-butylstyrene (1c) with NFSI and TMSN
99.4 mg of 2c (80%) as light yellow oil, after flash chromatography on silica gel
3
afforded
1
1
using petroleum ether and ethyl acetate (15:1, v/v) as the eluent. H NMR (CDCl
.08-8.06 (m, 4H), 7.65-7.62 (m, 2H), 7.55-7.51 (m, 4H), 7.42 (d, J = 8.3 Hz, 2H), 7.29 (d, J = 8.3 Hz, 2H), 4.98
dd, J = 9.8 Hz, 3.9 Hz, 1H), 4.08 (dd, J = 15.6 Hz, 9.8 Hz, 1H), 3.71 (dd, J = 15.6 Hz, 3.9 Hz, 1H), 1.32 (s, 9H)
3
, 400 MHz): δ =
8
(
ppm; 13C NMR (CDCl
3
, 100 MHz): δ = 152.08. 139.25. 133.97, 133.36, 128.93, 128.54, 126.84, 125.96,
+
6
5.30, 53.11, 34.61, 31.21 ppm. HRMS m/z (ESI) calcd for [C24
H
26
N
4
O
4
S
2
+Na] 521.1293, found 521.1290;
+
calcd for [C24
H
26
N
4
O
4
S +K] 537.1027, found 537.1030.
2
4
-(1-Azido-2-(N-(phenylsulfonyl)phenylsulfonamido)ethyl)phenyl acetate[1] (2d):
The reaction of 0.5 mmol of 4-vinylphenyl acetate (1d) with NFSI and TMSN
3
afforded 184.3 mg of 2d (74%) as colorless oil, after flash chromatography on silica
1
gel using petroleum ether and ethyl acetate (12:1 to 8:1, v/v) as the eluent. H NMR (CDCl
3
, 400 MHz): δ
=
8.06-8.04 (m, 4H), 7.66-7.62 (m, 2H), 7.56-7.52 (m, 4H), 7.37 (d, J = 8.6 Hz, 2H), 7.12 (d, J = 8.6 Hz, 2H),
.02 (dd, J = 9.5 Hz, 4.2 Hz, 1H), 4.03 (dd, J = 15.6 Hz, 9.5 Hz, 1H), 3.72 (dd, J = 15.6 Hz, 4.2 Hz, 1H), 2.29 (s,
5
3
1
5
1
3
H) ppm; C NMR (CDCl
3
, 100 MHz): δ = 169.12, 150.97, 139.02, 134.00, 133.91, 128.95, 128.47, 128.25,
+
22.26, 64.99, 53.02, 20.97 ppm. HRMS m/z (ESI) calcd for [C22
H
20
N
4
O
6
S
2
+Na] 523.0716, found
23.0720.
N-(2-Azido-2-(4-fluorophenyl)ethyl)-N-(phenylsulfonyl)benzenesulfonamide[1] (2e):
The reaction of 0.5 mmol of p-fluorostyrene (1e) with NFSI and TMSN afforded
3
o
1
85.3 mg of 2e (81%) as white solid (m.p. 104.7-105.9 C), after flash chromatography
1
on silica gel using petroleum ether and ethyl acetate (15:1, v/v) as the eluent. H NMR (CDCl , 400 MHz):
3
δ = 8.06-8.03 (m, 4H), 7.67-7.63 (m, 2H), 7.56-7.52 (m, 4H), 7.34-7.31 (m, 2H), 7.09-7.04 (m, 2H), 5.01 (dd, J
9.3 Hz, 4.5 Hz, 1H), 4.02 (dd, J = 15.6 Hz, 9.3 Hz, 1H), 3.71 (dd, J = 15.6 Hz, 4.5 Hz, 1H) ppm; 13C NMR
=
(
CDCl , 100 MHz): δ = 162.91 (d, J = 247.0 Hz), 139.12, 134.06, 132.27 (d, J = 3.0 Hz), 129.06, 128.99,
3
1
28.51, 116.09 (d, J = 21.4 Hz), 64.86, 53.16 ppm. HRMS m/z (ESI) calcd for [C20
H
17FN
4
O
4
S
+Na]+
2
S6

Organic & Biomolecular Chemistry
Page 16 of 71
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483.0567, found 483.0569.
DOI: 10.1039/C8OB00699G
N-(2-Azido-2-(3-fluorophenyl)ethyl)-N-(phenylsulfonyl)benzenesulfonamide[1] (2f):
The reaction of 0.5 mmol of m-fluorostyrene (1e) with NFSI and TMSN
90.2 mg of 2f (83%) as colorless oil, after flash chromatography on silica gel using
3
afforded
1
1
petroleum ether and ethyl acetate (15:1 to 12:1, v/v) as the eluent. H NMR (CDCl
3
, 400 MHz): δ =
.07-8.05 (m, 4H), 7.66-7.63 (m, 2H), 7.56-7.52 (m, 4H), 7.38-7.32 (m, 1H), 7.14-7.13 (m, 1H), 7.07-7.02 (m,
H), 5.01 (dd, J = 9.5 Hz, 4.2 Hz, 1H), 4.04 (dd, J = 15.6 Hz, 9.5 Hz, 1H), 3.71 (dd, J = 15.6 Hz, 4.2 Hz, 1H)
8
2
ppm; 13C NMR (CDCl
, 100 MHz): δ = 162.92 (d, J = 246.5 Hz), 139.08, 138.95 (d, J = 7.1 Hz), 134.07,
3
1
6
4
30.74 (d, J = 8.1 Hz), 129.00, 128.48, 122.74 (d, J = 2.9 Hz), 115.95 (d, J = 21.0 Hz), 114.13 (d, J = 22.1 Hz),
+
5.02 (d, J = 1.2 Hz), 53.16 ppm. HRMS m/z (ESI) calcd for [C20
H
17FN
4
O
4
S +Na] 483.0567, found
2
83.0570.
N-(2-Azido-2-(4-chlorophenyl)ethyl)-N-(phenylsulfonyl)benzenesulfonamide[1] (2g):
The reaction of 0.5 mmol of p-chlorostyrene (1g) with NFSI and TMSN
3
afforded
1
88.0 mg of 2g (79%) as white solid (m.p. 144.8-146.0 oC), after flash
1
chromatography on silica gel using petroleum ether and ethyl acetate (15:1, v/v) as the eluent. H NMR
CDCl , 400 MHz): δ = 8.04-8.01 (m, 4H), 7.66-7.62 (m, 2H), 7.55-7.51 (m, 4H), 7.34 (d, J = 8.5 Hz, 2H),
.28 (d, J = 8.5 Hz, 2H), 5.01 (dd, J = 9.1 Hz, 4.8 Hz, 1H), 3.99 (dd, J = 15.6 Hz, 9.1 Hz, 1H), 3.73 (dd, J = 15.6
(
3
7
Hz, 4.8 Hz, 1H) ppm; 13C NMR (CDCl
3
, 100 MHz): δ = 138.99, 134.89, 134.86, 134.04, 129.26, 128.97,
+
1
28.58, 128.45, 64.83, 52.98 ppm. HRMS m/z (ESI) calcd for [C20
H
17ClN
4
O
4
S
2
+Na] 499.0277, found
+
499.0278; calcd for [C20
H
17ClN
4
O
4
S +K] 515.0011, found 515.0017.
2
N-(2-Azido-2-(3-chlorophenyl)ethyl)-N-(phenylsulfonyl)benzenesulfonamide (2h):
The reaction of 0.5 mmol of m-chlorostyrene (1h) with NFSI and TMSN
3
afforded
177.9 mg of 2h (75%) as colorless oil, after flash chromatography on silica gel using
1
petroleum ether and ethyl acetate (15:1, v/v) as the eluent. H NMR (CDCl
3
, 400 MHz): δ = 8.07-8.05 (m,
4
1
H), 7.67-7.63 (m, 2H), 7.56-7.52 (m, 4H), 7.33-7.31 (m, 3H), 7.25-7.23 (m, 1H), 4.99 (dd, J = 9.4 Hz, 4.3 Hz,
1
3
H), 4.03 (dd, J = 15.6 Hz, 9.4 Hz, 1H), 3.71 (dd, J = 15.6 Hz, 4.3 Hz, 1H) ppm; C NMR (CDCl , 100 MHz):
3
δ = 139.06, 138.51, 134.96, 134.08, 130.39, 129.16, 129.00, 128.48, 127.29, 125.25, 64.99, 53.14 ppm. HRMS
S7

Page 17 of 71
Organic & Biomolecular Chemistry
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DOI: 10.1039/C8OB00699G
+
m/z (ESI) calcd for [C20
H
17ClN
4
O
4
S
2
+Na] 499.0272, found 499.0278.
N-(2-Azido-2-(2-chlorophenyl)ethyl)-N-(phenylsulfonyl)benzenesulfonamide (2i):
The reaction of 0.5 mmol of o-chlorostyrene (1i) with NFSI and TMSN
3
afforded 189.4
o
mg of 2i (80%) as white solid (m.p. 133.1-134.5 C), after flash chromatography on silica
1
gel using petroleum ether and ethyl acetate (15:1, v/v) as the eluent. H NMR (CDCl
3
, 400 MHz): δ =
8
1
.15-8.14 (m, 4H), 7.69-7.65 (m, 2H), 7.59-7.55 (m, 4H), 7.52-7.49 (m, 1H), 7.40-7.27 (m, 3H), 5.51 (dd, J =
1
3
0.5 Hz, 3.8 Hz, 1H), 4.05 (dd, J = 15.6 Hz, 10.5 Hz, 1H), 3.69 (dd, J = 15.6 Hz, 3.8 Hz, 1H) ppm; C NMR
3
(CDCl , 100 MHz): δ = 139.17, 134.54, 134.06, 132.92, 130.03, 129.96, 129.02, 128.65, 128.33, 127.70, 61.82,
+
5
1.57 ppm. HRMS m/z (ESI) calcd for [C20
H
17ClN
4
O
4
S
2
+Na] 499.0272, found 499.0276.
N-(2-Azido-2-(4-bromophenyl)ethyl)-N-(phenylsulfonyl)benzenesulfonamide[1] (2j):
The reaction of 0.5 mmol of p-bromostyrene (1j) with NFSI and TMSN
3
afforded
2
14.5 mg of 2j (83%) as white solid (m.p. 122.1-123.7 oC), after flash
1
chromatography on silica gel using petroleum ether and ethyl acetate (15:1, v/v) as the eluent. H NMR
CDCl , 400 MHz): δ = 8.03-8.01 (m, 4H), 7.67-7.63 (m, 2H), 7.56-7.49 (m, 6H), 7.22 (d, J = 8.4 Hz, 2H),
.00 (dd, J = 9.0 Hz, 4.8 Hz, 1H), 3.98 (dd, J = 15.6 Hz, 9.0 Hz, 1H), 3.73 (dd, J = 15.6 Hz, 4.8 Hz, 1H) ppm;
(
3
5
13C NMR (CDCl
, 100 MHz): δ = 139.01, 135.46, 134.08, 132.27, 129.01, 128.92, 128.51, 123.10, 64.95,
3
+
5
2.93 ppm. HRMS m/z (ESI) calcd for [C20
H
17BrN
4
O
4
S
2
+Na] 542.9767, found 542.9776.
N-(2-([1,1'-Biphenyl]-4-yl)-2-azidoethyl)-N-(phenylsulfonyl)benzenesulfonamide[1] (2k):
The reaction of 0.5 mmol of 4-vinyl-1,1’-biphenyl (1k) with NFSI and TMSN
3
o
afforded 153.9 mg of 2k (60%) as light yellow solid (m.p. 132.0-133.7 C), after flash
1
chromatography on silica gel using petroleum ether and ethyl acetate (15:1, v/v) as the eluent. H NMR
3
(CDCl , 400 MHz): δ = 8.07-8.05 (m, 4H), 7.65-7.58 (m, 6H), 7.54-7.50 (m, 4H), 7.47-7.35 (m, 5H), 5.07 (dd,
1
3
J = 9.4 Hz, 4.5 Hz, 1H), 4.08 (dd, J = 15.6 Hz, 9.4 Hz, 1H), 3.79 (dd, J = 15.6 Hz, 4.5 Hz, 1H) ppm; C NMR
3
(CDCl , 100 MHz): δ = 141.95, 140.15, 139.17, 135.31, 134.01, 128.97, 128.87, 128.56, 127.75, 127.71,
+
1
27.67, 127.03, 65.32, 53.06 ppm. HRMS m/z (ESI) calcd for [C26
41.0977.
H
22
N
4
O
4
S
2
+Na] 541.0975, found
5
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Organic & Biomolecular Chemistry
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DOI: 10.1039/C8OB00699G
N-(2-Azido-2-(naphthalen-2-yl)ethyl)-N-(phenylsulfonyl)benzenesulfonamide[1] (2l):
The reaction of 0.5 mmol of 2-vinylnaphthalene (1l) with NFSI and TMSN afforded
3
o
1
05.1 mg of 2l (43%) as light yellow solid (m.p. 125.2-126.8 C), after flash
1
chromatography on silica gel using petroleum ether and ethyl acetate (15:1, v/v) as the eluent. H NMR
CDCl , 400 MHz): δ = 8.01-7.99 (m, 4H), 7.90-7.79 (m, 4H), 7.60-7.42 (m, 9H), 5.21 (dd, J = 8.8 Hz, 5.0 Hz,
H), 4.10 (dd, J = 15.6 Hz, 8.8 Hz, 1H), 3.88 (dd, J = 15.6 Hz, 5.0 Hz, 1H) ppm; C NMR (CDCl , 100 MHz):
(
3
1
3
1
3
δ = 139.03, 133.96, 133.65, 133.42, 133.11, 129.18, 128.88, 128.51, 128.09, 127.74, 127.12, 126.73, 126.66,
+
1
24.22, 65.73, 52.94 ppm. HRMS m/z (ESI) calcd for [C24
H
20
N
4
O
4
S
2
+Na] 515.0818, found 515.0825;
+
calcd for [C24
H
20
N
4
O
4
S
2
+K] 531.0563, found 531.0566.
N-(2-Azido-2-phenylpropyl)-N-(phenylsulfonyl)benzenesulfonamide[1] (2m):
The reaction of 0.5 mmol of prop-1-en-2-ylbenzene (1m) with NFSI and TMSN
3
afforded 144.8 mg of 2m (64%) as colorless oil, after flash chromatography on silica gel
1
using petroleum ether and ethyl acetate (15:1, v/v) as the eluent. H NMR (CDCl
3
, 400 MHz): δ =
8
.11-8.09 (m, 4H), 7.65-7.61 (m, 2H), 7.57-7.53 (m, 4H), 7.44-7.30 (m, 5H), 4.17 (d, J = 15.8 Hz, 1H), 3.99 (d, J
13
=
15.8 Hz, 1H), 1.67 (s, 3H) ppm; C NMR (CDCl
3
, 100 MHz): δ = 141.43, 140.58, 133.73, 128.90, 128.85,
+
1
28.43, 128.27, 125.82, 66.92, 58.85, 21.54 ppm. HRMS m/z (ESI) calcd for [C21
H
20
N
4
O
4
S
2
+Na] 479.0818,
found 479.0823.
N-(1-Azido-1-phenylpropan-2-yl)-N-(phenylsulfonyl)benzenesulfonamide[1] (2n):
The reaction of 0.5 mmol of (E)-prop-1-en-1-ylbenzene (1n) with NFSI and TMSN
3
afforded 173.6 mg of 2n (76%, dr > 94:6) as colorless oil, after flash chromatography on
1
silica gel using petroleum ether and ethyl acetate (15:1, v/v) as the eluent. H NMR (CDCl
3
, 400 MHz): δ
=
7.64-7.61 (m, 4H), 7.57-7.53 (m, 2H), 7.40-7.24 (m, 9H), 5.21 (d, J = 9.7 Hz, 1H), 4.37 (dq, J = 9.7 Hz, 6.7 Hz,
1
1
H), 1.51 (d, J = 6.8, 3H) ppm; 13C NMR (CDCl
3
, 100 MHz): δ = 135.87, 133.69, 129.13, 128.81, 128.73,
+
28.67, 128.41, 127.56, 69.71, 61.48, 17.94 ppm. HRMS m/z (ESI) calcd for [C21
H
20
N
4
O
4
S
2
+Na] 479.0818,
+
found 479.0818; calcd for [C21
H
20
N
4
O
4
S
2
+K] 495.0558, found 495.0559.
N-(1-Azido-1,2,3,4-tetrahydronaphthalen-2-yl)-N-(phenylsulfonyl)benzenesulfonamide[1] (2o):
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Page 19 of 71
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O 3B 00699G
The reaction of 0.5 mmol of 1,2-dihydronaphthalene (1o) with NFSIDO
a
I:
n
1
d
0.10
T
3
MSN
9/C
8
afforded 85.6 mg of 2o (37%, dr > 97:3) as light yellow oil, after flash chromatography
1
on silica gel using petroleum ether and ethyl acetate (15:1, v/v) as the eluent. H NMR (CDCl
3
, 400 MHz):
δ = 8.14-8.12 (m, 4H), 7.70-7.66 (m, 2H), 7.60-7.56 (m, 4H), 7.41 (d, J = 7.5 Hz, 1H), 7.27-7.20 (m, 2H), 7.08
d, J = 7.2 Hz, 1H), 5.38 (d, J = 10.0 Hz, 1H), 4.36-4.29 (m, 1H), 2.82-2.78 (m, 2H), 2.63-2.52 (m, 1H),
(
1
1
4
.89-1.83 (m, 1H) ppm; 13C NMR (CDCl
, 100 MHz): δ = 135.66, 134.08, 134.00, 129.02, 128.69, 128.56,
3
28.04, 127.94, 126.83, 64.97, 62.78, 29.99, 28.44 ppm. HRMS m/z (ESI) calcd for [C22
H
20
N
4
O
4
S
+Na]+
2
91.0818, found 491.0826.
N-(2-Azido-2-cyclohexylethyl)-N-(phenylsulfonyl)benzenesulfonamide (2p):
In presence of 2,2’-bipyridine (3.9 mg, 0.025 mmol), the reaction of 0.5 mmol of vinyl
o
cyclohexane (1p) with NFSI and TMSN
3
at 80 C for 6 hours afforded 104.2 mg of 2p
(47%) as colorless oil, after flash chromatography on silica gel using petroleum ether and ethyl acetate
1
(
15:1, v/v) as the eluent. H NMR (CDCl
3
, 400 MHz): δ = 8.12-8.09 (m, 4H), 7.68-7.65 (m, 2H), 7.59-7.55
(
m, 4H), 3.89 (dd, J = 15.8 Hz, 10.5 Hz, 1H), 3.65-3.61 (m, 2H), 1.77-1.75 (m, 3H), 1.67-1.64 (m, 2H),
1
3
1
6
4
.51-1.43 (m, 1H), 1.26-1.12 (m, 5H) ppm; C NMR (CDCl , 100 MHz): δ = 139.33, 133.97, 129.04, 128.40,
3
7.49, 50.80, 41.10, 29.80, 28.03, 26.00, 25.90, 25.73 ppm. HRMS m/z (ESI) calcd for [C20
H
24
N
4
O
4
S
+K]+
2
87.0871, found 487.0880.
N-(2-Azidooctyl)-N-(phenylsulfonyl)benzenesulfonamide (2q):
In presence of 2,2’-bipyridine (3.9 mg, 0.025 mmol), the reaction of 0.5 mmol of
o
1-octene (1q) with NFSI and TMSN
3
at 80 C afforded 116.0 mg of 2q (52%) as colorless
oil, after flash chromatography on silica gel using petroleum ether and ethyl acetate (15:1, v/v) as the eluent.
1H NMR (CDCl
3
, 400 MHz): δ = 8.10-8.08 (m, 4H), 7.68-7.64 (m, 2H), 7.58-7.55 (m, 4H), 3.86 (dd, J = 15.1
Hz, 9.2 Hz, 1H), 3.75-3.69 (m, 1H), 3.57 (dd, J = 15.1 Hz, 3.9 Hz, 1H), 1.50-1.42 (m, 2H), 1.32-1.23 (m, 8H),
1
3
0
3
.89 (t, J = 6.9 Hz, 3H) ppm; C NMR (CDCl
3
, 100 MHz): δ = 139.40, 134.01, 129.06, 128.41, 62.00, 52.15,
+
2.29, 31.52, 28.86, 25.80, 22.47, 13.99 ppm. HRMS m/z (ESI) calcd for [C20
H
26
N
4
O
4
S
2
+Na] 473.1288,
found 473.1298.
N-(2-Azidodecyl)-N-(phenylsulfonyl)benzenesulfonamide (2r):
S10

Organic & Biomolecular Chemistry
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In presence of 2,2’-bipyridine (3.9 mg, 0.025 mmol), the reaction ofDO0.I:
5
10
m
.10
mol
8OofB00699G
39
/C
o
1-decene (1r) with NFSI and TMSN
3
at 80 C afforded 94.3 mg of 2r (40%) as colorless
oil, after flash chromatography on silica gel using petroleum ether and ethyl acetate (15:1, v/v) as the eluent.
1H NMR (CDCl
3
, 400 MHz): δ = 8.10-8.08 (m, 4H), 7.68-7.64 (m, 2H), 7.58-7.54 (m, 4H), 3.86 (dd, J = 15.1
Hz, 9.3 Hz, 1H), 3.75-3.69 (m, 1H), 3.56 (dd, J = 15.1 Hz, 3.9 Hz, 1H), 1.50-1.43 (m, 2H), 1.32-1.26 (m, 12H),
1
3
0
3
5
.89 (t, J = 6.9 Hz, 3H) ppm; C NMR (CDCl , 100 MHz): δ = 139.31, 133.99, 129.02, 128.35, 61.96, 52.09,
3
2.23, 31.71, 29.25, 29.15, 29.07, 25.79, 22.56, 14.03 ppm. HRMS m/z (ESI) calcd for [C22
H
30
N
4
O
4
S
+Na]+
2
+
01.1606, found 501.1607; calcd for [C22
H
30
N
4
O
4
S
2
+Na] 501.1601, found 501.1607.
N-(2-Azido-2-(1,3-dioxoisoindolin-2-yl)ethyl)-N-(phenylsulfonyl)benzenesulfonamide (2s):
In presence of 2,2’-bipyridine (3.9 mg, 0.025 mmol), the reaction of 0.5 mmol of
o
N-vinylphthalimide (1s) with NFSI and TMSN
3
at 80 C afforded 172.5 mg of 2s (68%)
o
as white solid (m.p. 177.3-178.6 C), after flash chromatography on silica gel using petroleum ether and
1
ethyl acetate (15:1 to 3:1, v/v) as the eluent. H NMR (CDCl
3
, 400 MHz): δ = 8.05-8.03 (m, 4H), 7.90-7.88
(
(
m, 2H), 7.77-7.75 (m, 2H), 7.67-7.63 (m, 2H), 7.57-7.53 (m, 4H), 6.04 (dd, J = 7.3 Hz, 4.9 Hz, 1H), 4.42-4.30
m, 2H) ppm; 13C NMR (CDCl
3
, 100 MHz): δ = 166.97, 138.34, 134.60, 134.29, 131.35, 129.14, 128.62,
+
1
23.91, 65.30, 47.32 ppm. HRMS m/z (ESI) calcd for [C22
H
17
N
5
O
6
S
2
+K] 550.0252, found 550.0258.
N-(2-Azido-2-butoxyethyl)-N-(phenylsulfonyl)benzenesulfonamide (2t):
In presence of 2,2’-bipyridine (3.9 mg, 0.025 mmol), the reaction of 0.5 mmol of
o
1-(vinyloxy)butane (1t) with NFSI and TMSN
3
at 80 C for 6 hours afforded 111.2 mg of
2t (51%) as colorless oil, after flash chromatography on silica gel using petroleum ether and ethyl acetate
1
(
15:1, v/v) as the eluent. H NMR (CDCl
3
, 400 MHz): δ = 8.11-8.09 (m, 4H), 7.69-7.65 (m, 2H), 7.59-7.55
(
m, 4H), 4.81 (t, J = 6.0 Hz, 1H), 3.93 (dd, J = 15.7 Hz, 6.1 Hz, 1H), 3.80 (dd, J = 15.7 Hz, 5.8 Hz, 1H), 3.67 (dt,
J = 9.5 Hz, 6.9 Hz, 1H), 3.40 (dt, J = 9.5 Hz, 6.6 Hz, 1H), 1.50-1.43 (m, 2H), 1.34-1.26 (m, 2H), 0.90 (t, J = 7.3
Hz, 3H) ppm; 13C NMR (CDCl
3
, 100 MHz): δ = 139.17, 134.03, 128.97, 128.55, 90.33, 69.82, 50.54, 31.19,
+
1
9.00, 13.73 ppm. HRMS m/z (ESI) calcd for [C18
H
22
N
4
O
5
S
2
+Na] 461.0924, found 461.0930.
1-Azido-2-(N-(phenylsulfonyl)phenylsulfonamido)ethyl benzoate (2u):
S11

Page 21 of 71
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In presence of 2,2’-bipyridine (3.9 mg, 0.025 mmol), the reaction o
D
f
O
0
I:.510.
m
10
m
39
o
/C
l
8OB00699G
o
f
o
vinyl benzoate (1u) with NFSI and TMSN
3
at 80 C for 6 hours afforded 142.3 mg of
2u (59%) as colorless oil, after flash chromatography on silica gel using petroleum ether and ethyl acetate
1
(
15:1, v/v) as the eluent. H NMR (CDCl
3
, 400 MHz): δ = 8.06-8.02 (m, 6H), 7.62-7.58 (m, 3H), 7.50-7.43
1
3
(
m, 6H), 6.42 (t, J = 6.3 Hz, 1H), 3.80 (dq, J = 15.5 Hz, 6.3 Hz, 2H) ppm; C NMR (CDCl
3
, 100 MHz): δ =
1
65.66, 139.11, 134.14, 133.87, 130.09, 129.13, 128.52, 128.35, 128.24, 83.39, 49.56 ppm. HRMS m/z (ESI)
+
calcd for [C21
H
18
N
4
O
6
S
2
+K] 525.0299, found 525.0309.
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Organic & Biomolecular Chemistry
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DOI: 10.1039/C8OB00699G
Control Experiments
1
) TEMPO-suppressed Control Experiment
Typical Procedure: To a reaction tube charged with FeCl (6.3 mg, 0.05 mmol), NFSI (236.5 mg, 0.75
2
mmol) and TEMPO (156.3 mg, 1 mmol) was added a solution of styrene (1a, 57.5 μL, 0.5 mmol), TMSN
3
(
98.6 μL, 0.75 mmol) in DCE (2 mL) via a syringe under N (1 atm). The reaction mixture was stirred at
2
o
1
00 C for 3 hours. After rapidly cooling by ice, the mixture was diluted with ethyl acetate, filtered through
a celite pad, and concentrated in vacuo to give dark residue, which was then purified by flash
chromatography using petroleum ether and ethyl acetate as the eluent on silical gel to afford aminoazidated
product 2a (15.1 mg, 7%) and TEMPO-captured product 4a (43.4 mg, 16%).
N-(2-Phenyl-2-((2,2,6,6-tetramethylpiperidin-1-yl)oxy)ethyl)-N-(phenylsulfonyl)benzenesulfonamide[2]
(4a):
The reaction of 0.5 mmol of styrene (1a) under standard conditions, adding 1 mmol of
o
TEMPO afforded 43.4 mg of 4a (16%) as white solid (m.p. 132.3-133.7 C), after flash
chromatography on silica gel using petroleum ether and ethyl acetate (20:1 to 15:1, v/v)
1
as the eluent. H NMR (CDCl , 400 MHz): δ = 7.60-7.56 (m, 6H), 7.43-7.39 (m, 4H), 7.36-7.30 (m, 5H), 5.23
3
(
(
dd, J = 11.0 Hz, 4.7 Hz, 1H), 4.39 (dd, J = 14.9 Hz, 11.0 Hz, 1H), 4.03 (dd, J = 14.9 Hz, 4.7 Hz, 1H), 1.51-1.39
m, 5H), 1.27-1.24 (m, 4H), 1.11-0.97 (m, 6H), 0.88-0.70 (m, 3H) ppm; 13C NMR (CDCl
3
, 100 MHz): δ =
1
1
39.90, 138.49, 133.58, 129.28, 128.81, 128.62, 128.12, 127.83, 84.10, 59.95, 50.09, 40.50, 34.90, 34.23, 20.22,
+
7.11 ppm. HRMS m/z (ESI) calcd for [C29
H
36
N
2
O
5
S +H] 557.2138, found 557.2144.
2
2
) Competition Experiment between Electron-rich/-deficient Styrenes
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Page 23 of 71
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To a reaction tube charged with FeCl
2
(6.3 mg, 0.05 mmol) and NFSI (126.1 mg, 0.4 mmo
D
l)OI
w
: 1
a
0
s
.10
a
3
d
9
d
/C
e
8OB00699G
d
a
solution of p-methylstyrene (1b, 32.9 μL, 0.25 mmol), p-fluorostyrene (1e, 29.8 μL, 0.25 mmol), TMSN
3
(
52.6 μL, 0.4 mmol ) in DCE (2 mL) via a syringe under N (1 atm). The reaction mixture was stirred at
2
o
1
00 C for 3 hours. After rapidly cooling by ice, the mixture was diluted with ethyl acetate, filtered through
a celite pad, and concentrated in vacuo to give dark residue, which was then purified by flash
chromatography using petroleum ether and ethyl acetate as the eluent (15:1, v/v) on silical gel to afford
116.0 mg of the combined methyl- and fluoro-aminoazidated product 2b and 2e. The average ratio of 2b/2e
1
was determined by H-NMR as 1 : 0.35, as shown in Figure S2. Herein, this competition reaction afforded
0.188 mmol of 2b and 0.066 mmol of 2e.
1
Figure S2. H-NMR of the competition experiment between styrenes 1b and 1e.
3
) C-H Amination of 1,1-disubstituted Alkenes with NFSI
Typical Procedure: To a reaction tube charged with FeCl
2
(6.3 mg, 0.05 mmol) and NFSI (236.5 mg, 0.75
(98.6 μL, 0.75
(1 atm). The reaction mixture was stirred at
mmol) was added a solution of 1,1-diphenylethylene (1v, 88.3 μL, 0.5 mmol) and TMSN
3
mmol, or 0 μL, 0 mmol) in DCE (2 mL) via a syringe under N
2
S14

Organic & Biomolecular Chemistry
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o
1
00 C for 3 hours. After rapidly cooling by ice, the mixture was diluted with ethyl acetate, f
D
il
O
teI:
r
1
e
0
d
.10th39ro/C
u
8OB00699G
g
h
a celite pad, and concentrated in vacuo to give dark residue, which was then purified by flash
chromatography using petroleum ether and ethyl acetate (15:1, v/v) as the eluent on silical gel to afford C-H
aminated product 3v (117.8 mg, 50% with TMSN
3
, or 128.2 mg, 50% without TMSN ) as white solid (m.p.
3
o
1
70.5-171.9 C).
N-(2,2-Diphenylvinyl)-N-(phenylsulfonyl)benzenesulfonamide[3] (3v):
1H NMR (CDCl
3
, 400 MHz): δ = 7.71-7.69 (m, 4H), 7.58-7.55 (m, 2H), 7.41-7.36 (m, 4H), 7.34-7.20 (m,
1
1
0H), 6.13 (s, 1H) ppm; 13C NMR (CDCl
3
, 100 MHz): δ = 152.25, 139.82, 138.63, 136.73, 133.78, 129.87,
29.07, 128.76, 128.69, 128.64, 128.35, 128.23, 128.13, 116.26 ppm. HRMS m/z (ESI) calcd for
+
[C
26
H
21NO
4
S
2
+Na] 498.0810, found 498.0818.
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DOI: 10.1039/C8OB00699G
References
[
[
[
1] Zhang, B.; Studer, A. Org. Lett. 2014, 16, 1790-1793.
2] Zhang, H.; Song, Y.; Zhao, J.; Zhang, J.; Zhang, Q. Angew. Chem. Int. Ed. 2014, 53, 11079-11083.
3] Weng, S.-S.; Hsieh, K.-Y.; Zeng, Z.-J.; Zhang, J.-W. Tetrahedron Lett. 2017, 58, 670-673.
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S17

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S20