Copper-catalyzed N-arylation of tert-butyl N-sulfonylcarbamates with diaryliodonium salts at room temperature

Article abstract of DOI:10.1016/j.tet.2015.01.032

A new and mild synthetic approach for the synthesis of N-arylsulfonamides under copper-catalyzed conditions at room temperature has been developed. The reaction employs various tert-butyl N-sulfonylcarbamates and diaryliodonium salts to avoid potential genotoxic impurities. A one-pot coupling/Boc-deprotection sequence is also reported to provide mono N-arylsulfonamides in good to excellent yields.

Full text of DOI:10.1016/j.tet.2015.01.032

Accepted Manuscript
Copper-Catalyzed N-Arylation of tert-Butyl N-Sulfonylcarbamates with Diaryliodonium
Salts at Room Temperature
Soo-Yeon Moon, Moonjee Koh, Kris Rathwell, Seo-Hee Jung, Won-Suk Kim
PII:
S0040-4020(15)00075-7
10.1016/j.tet.2015.01.032
TET 26355
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 28 November 2014
Revised Date: 13 January 2015
Accepted Date: 15 January 2015
Please cite this article as: Moon S-Y, Koh M, Rathwell K, Jung S-H, Kim W-S, Copper-Catalyzed
N-Arylation of tert-Butyl N-Sulfonylcarbamates with Diaryliodonium Salts at Room Temperature,
Tetrahedron (2015), doi: 10.1016/j.tet.2015.01.032.
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Graphical Abstract
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Copper-Catalyzed N-Arylation of tert-Butyl
N-Sulfonylcarbamates with Diaryliodonium
Salts at Room Temperature
Soo-Yeon Moon, Moonjee Koh, Kris Rathwell, Seo-Hee Jung and Won-Suk Kim*
Department of Chemistry and Nano Science, Ewha Womans University, Seoul 120-750, Korea
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Tetrahedron
journal homepage: www.elsevier.com
Copper-Catalyzed N-Arylation of tert-Butyl N-Sulfonylcarbamates with
Diaryliodonium Salts at Room Temperature
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3 Soo-Yeon Moon, Moonjee Koh, Kris Rathwell, Seo-Hee Jung and Won-Suk Kim
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Department of Chemistry and Nano Science, Ewha Womans Univeristy, Seoul 120-750, Korea
ARTICLE INFO
ABSTRACT
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Article history:
Received
Received in revised form
Accepted
A new and mild synthetic approach for the synthesis of N-arylsulfonamides under copper-
catalyzed conditions at room temperature has been developed. The reaction employs various
tert-butyl N-sulfonylcarbamates and diaryliodonium salts to avoid potential genotoxic
impurities. A one-pot coupling/Boc deprotection sequence is also reported to provide mono N-
arylsulfonamides in good to excellent yields.
Available online
2014 Elsevier Ltd. All rights reserved.
Keywords:
Copper catalysis
tert-Butyl N-sulfonylcarbamates
Diaryliodonium Salts
Room temperature
Mono N-arylsulfonamides
1
. Introduction
N-Arylsulfonamides are a ubiquitous pharmacophore in many
1
3 important medicinal compounds (Figure 1). Due to their
4 anticancer, antibacterial, anticonvulsant and HIV protease
5 inhibitory activities, these arylsulfonamide units have been
6 readily used in many medicinal chemistry endeavors.
7 functional groups are normally synthesized from the
1
a, 2
These
straightforward reaction of an aromatic amine and a sulfonyl
chloride in the presence of base (Scheme 1, eq 1). Unfortunately,
the reactants used in this simple approach are mutagenic or
genotoxic which can induce genetic mutation or act as
carcinogenic compounds. Thus, alternative synthetic methods
utilizing the metal-catalyzed cross-coupling of sulfonamides with
an appropriate aryl coupling partner have been developed to
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4
avoid potential genotoxic intermediates (Scheme 1. Eq 2) .
Scheme 1. Synthesis of N-Arylsulfonamides
In our efforts to improve upon the current methods for the
preparation of N-arylsulfonamides, we investigated the use of
sulfonyl azides in the Chan-Lam reaction (Scheme 1, eq 3) . This
cross-coupling reaction successfully proceeded to completion in
2 h at room temperature in an open flask without the use of any
base or ligand due to the reactivity of the azide and resultant loss
5
Figure 1. N-Arylsulfonamide-containing drugs
of N driving the reaction. As an extension of this work, we
2
continued our focus on non-mutagenic, stable and non-toxic
—
——

Corresponding authors. Tel.: +82 2 3277; fax: +82 2 3277 2384
E-mail addresses: wonsukk@ewha.ac.kr (W.-S. Kim).

2
Tetrahedron
reactants as coupling partners to prepare NA-arCylCsuElfoPnTamEidDes MAEtNNUinStColRueInPe Twith 10 mol % CuCl at room temperature was
3
using mild conditions.
found to be the optimal conditions (Table 1, entry 14).
Easy to prepare, stable and non-toxic, diaryliodonium salts
have been used successfully as arylating agents since their
discovery. In addition, the use of a Cu(I) catalyst can improve
Table 1
1
2
3
4
5
6
7
8
9
6
Optimization of the N-Arylation of Diphenyliodonium Triflate 1 with tert-
Butyl N-Tosylcarbamate 2
the electrophilicity of diaryliodonium salts via the generation of a
7
reactive aryl-Cu(III) intermediate. Recently, diaryliodonium
8
salts were used to arylate various heteroatomic compounds.
Thus, we hypothesized that the use of diaryliodonium salts would
allow for the facile production of N-arylsulfonamides at room
temperature in the presence of Cu(I) catalyst even though
sulfonamides are relatively unreactive as nucleophiles. Initial
1
1
1
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0 studies with catalytic Cu(I) generated a mixture of mono- and di-
temp.
yield
(%)
entry
Cu cat.
base
solvent
o
time
b
9
(
C)
1 arylated sulfonamides without the reaction going to completion.
2 To prevent the unwanted diarylsulfonamides, we decided to use
3 the Boc protecting group, which can be easily removed under
4 either acidic or basic conditions after cross-coupling. While this
5 work was underway, Wang et al. reported the use of
1
2
3
4
5
6
7
8
9
no catalyst
CuI
3
Et N
3
Et N
3
Et N
3
Et N
3
Et N
3
Et N
3
Et N
3
Et N
3
Et N
3
Et N
3
Et N
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
Toluene
THF
50
24 h
30 min
30 min
30 min
30 min
24 h
6 h
0
50
50
50
50
50
50
50
50
50
25
25
25
25
25
25
50
50
25
25
25
96
97
91
94
82
87
0
CuCl
diaryliodonium salts and 20 mol % of CuCl for the N-arylation of
N-arylsulfonamides, which had been prepared from the
corresponding arylamines and sulfonyl chlorides, to yield N,N’-
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CuBr
CuBr·SMe
CuCl
CuBr
2
8
a
diarylsulfonamides. While they demonstrated the possibility for
N-arylation employing various diaryliodonium salts, this reaction
provided N,N’-diarylsulfonamides. In comparison, our method
generates singly N-arylated sulfonamides similar to those found
2
2
CuO
24 h
24 h
24 h
1 h
1
in pharmaceutically active sulfonamide compounds and allow
CuSO
4
31
72
94
91
92
97
53
92
97
0
for further modification of the sulfonamide moiety as needed.
With these consideration in hand, we report herein a mild and
efficient method for the generation of N-arylsulfonamides from
diaryliodonium salts and tert-butyl N-sulfonylcarbamates at room
temperature.
1
1
0
1
Cu(OAc)
2
CuI
12
13
CuCl
CuCl
CuCl
CuCl
CuCl
CuCl
CuCl
CuCl
CuCl
CuCl
3
Et N
1 h
Et
Et
Et
3
3
3
N
N
N
CH Cl
2 2
1 h
1
4
Toluene
Toluene
Toluene
Toluene
1 h
2
. Results and discussion
Initial optimization was attempted using toluene at 50 C with
c
o
15
16
24 h
2 h
d
triethylamine base in the absence of a Cu(I) catalyst. After 24 h
at these conditions, no cross-coupling was observed between
diphenyliodonium triflate 1 and tert-butyl N-tosylcarbamate 2
3
Et N
1
7
DIPEA
30 min
24 h
24 h
18 h
18 h
(
Table 1, entry 1). When the conditions were repeated in the
18
Pyridine Toluene
presence of 10 mol % CuI, the reaction went to completion in 30
min yielding N-phenyl tert-butyl N-tosylcarbamate 3a in 96%
1
9
Cs
2
CO
3
Toluene
Toluene
Toluene
0
9 yield (Table 1, entry 2). Utilizing CuCl gave a slightly higher
0 97% yield (Table 1, entry 3). Both catalytic CuBr and CuBr-
1 dimethyl sulfide complex gave slightly lower yields of the
2 desired product 3a (Table 1, entries 4-5). Using catalytic Cu(II)
3 salts resulted in prolonged reaction times and lower yields (Table
20
2
K CO3
94
95
2
1
3 4
K PO
a
Reaction conditions: 0.325 mmol of diphenyliodonium triflate, 0.25
mmol of tert-butyl N-tosylcarbamate, 0.50 mmol of base, solvent (0.12 M).
b
c
d
o
o
isolated yield.
5 mol % of CuCl. 0.325 mmol of tert-butyl N-
4 1, entries 6-10). Decreasing the temperature from 50 C to 25 C
5 and using CuI gave the desired product in 94% in only 1 h (Table
6 1, entry 11). We next explored the effects of various solvents.
tosylcarbamate, 0.25 mmol of diphenyliodonium triflate.
7 Utilizing CuCl in CH Cl , THF and toluene at room temperature
2 2
provided the desired product in 1 h in 92%, 91% and 97% yield,
respectively (Table 1, entries 12-14). Additionally, utilizing only
With the optimized conditions in hand, we set out to
determine the scope of this cross-coupling reaction with respect
to the tert-butyl N-sulfonylcarbamate coupling partner (Table 2).
In general, tert-butyl N-arylsulfonylcarbamates furnished the
desired N-arylsulfonamide in excellent yield in a moderate
amount of time. tert-Butyl N-phenyl, p-methoxyphenyl, p-
bromophenyl and p-nitrophenyl sulfonylcarbamates, however,
required more than 10 h reaction time (Table 2, entries 3, 4, 9 and
10) and tert-butyl N-p-methoxyphenyl and p-nitrophenyl
sulfonylcarbamate needed 1.5 equiv. of the diphenyliodonium
triflate 1 in order to reach completion. When tert-butyl N-
alkylsulfonylcarbamates were used, the coupled products 3e and
3f were obtained in excellent yield within 8-12 h (Table 2, entries
5-6). Furthermore, tert-butyl N-heteroarylsulfonylcarbamates
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mol % of the copper catalyst at room temperature resulted in a
prolonged reaction time with a significantly reduced yield (Table
, entry 15). When an excess of tert-butyl N-tosylcarbamate 2
1
was utilized, the desired product 3a was isolated in a slightly
lower 92% yield in 2 h (Table 1, entry 16). Using DIPEA in
o
toluene at 50 C (Table 1, entry 17) matched the 97% yield that
was obtained with Et N. However, when either pyridine or
3
Cs CO was used no product was observed even after 24 h (Table
2
3
1
, entries 18-19). When solid bases like K CO and K PO were
2 3 3 4
used, the product 3a was obtained in a slightly lower yield in 18
(entires 20-21). Thus, for the model reaction of
diphenyliodonium triflate 1 with tert-butyl N-tosylcarbamate 2,
h

3
eu nn tdr ei er sw 1e 1n -t 1 N2 )- .a rylation in excellent yield in 1A0-C24ChE(PTaTbEleD2, MATaNbUle 3S.CRIPT
Cu-Catalyzed N-Arylation of tert-Butyl N-Tosylcarbamate 2 with Various
Diaryliodonium Triflates 5
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Table 2.
Cu-Catalyzed N-Arylation of Diphenyliodonium Triflate 1 with Various tert-
Butyl N-Sulfonylcarbamates 4
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
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a
Reaction conditions: 0.325 mmol of diphenyliodonium triflate, 0.25 mmol
of tert-butyl N-tosylcarbamate, 10 mol % CuCl, 0.50 mmol of Et N, toluene
3
b
(0.12 M). isolated yield.
a
Reaction conditions: 0.325 mmol of diphenyliodonium triflate, 0.25 mmol
3
of tert-butyl N-sulfonylcarbamate, 10 mol % CuCl, 0.50 mmol of Et N,
b
c
toluene (0.12 M). isolated yield. 1.5 equiv. of diphenyliodonium triflate.
d
2
.5 equiv. of diphenyliodonium triflate.
Next, we investigated the use of various diaryliodonium
triflates. Symmetric diaryliodonium triflates gave rise to their
coupled products in yields ranging from 87-97% (Table 3, entries
1
-9). The bulky mesityl or 2,4,6-triethylphenyl groups, used to
selectively transfer the other aryl group in unsymmetric iodonium
1
0
Scheme 2. Large Scale Synthesis
salts, were also utilized. The symmetrical mesityl iodonium
triflate was too bulky to undergo aryl transfer resulting in no
product observed after 24 h (Table 3, entry 9). Unsymmetric
mesityl or 2,4,6-triethylphenyl iodonium triflates were used to
successfully transfer aryl and heteroaryl groups to tert-butyl N-
Encouraged by these cross-coupling results, our attention
finally turned to a one-pot coupling/Boc-deprotection sequence
utilizing aqueous trifluoroacetic acid. As described in Table 4,
diaryliodonium triflates were reacted with tert-butyl N-
sulfonylcarbamates, and, upon completion of the cross-coupling
4 tosylcarbamate 2 (Table 3, entries 10-12). Particularly, the 3-
5 thienyl and 2-bromopyridine moieties were coupled with tert-
6 butyl-N-tosylcarbamate 2 at room temperature in 94% and 61%
7 yield and in 16 and 12 h, respectively (Table 3, entries 11-12). To
o
reaction, water and TFA were added at 0 C to synthesize mono
N-arylsulfonamides. After 1 h under the deprotection conditions,
the singly arylated N-phenyl tosylsulfonamide 12a was isolated
in 85% yield (Table 4, entry 1). In a similar manner, tert-butyl N-
sulfonylcarbamates containing an aryl, alkyl or a heteroaryl
group were reacted with diaryliodonium triflates giving rise to
mono N-arylsulfonamides in yields ranging from 83-94% (Table
8 further demonstrate the flexibility of copper catalyzed N-
9 arylation, the cross-coupling reactions were then conducted on a
0 large scale (5.0 mmol), furnishing the desired products in
1 excellent yields (Scheme 2).
2
3
4
5

4
4
Tetrahedron
ACCEPTED MANUSCRIPT
, entries 2-8).
Table 4.
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One-Pot N-Arylation and Boc Deprotection of Various tert-Butyl N-
Sulfonylcarbamates 4 with Various Diaryliodonium Triflates 5
1
1
1
1
1
1
1
1
1
1
2
2
2
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Scheme 3. Plausible Mechanism
4
4
. Experimental
.1. General information
Unless otherwise indicated, all chemical reagents were
purchased from Sigma-Aldrich, Alfa Aesar, and TCI and were
1
1
used without further purification. All diarylisodonium salts and
1
2
tert-butyl N-sulfonylcarbamates were prepared by the reported
procedures. All reactions were carried out in oven-dried
glassware equipped with a magnetic stir bar. Reactions were
a
Reaction conditions: 1.30 mmol of diaryliodonium triflate, 1.00 mmol of monitored by thin layer chromatography (TLC) with 0.25-mm E.
tert-butyl N-sulfonylcarbamate, 10 mol % CuCl, 0.50 mmol of Et
3
N, toluene Merck pre-coated silica gel plates (Kieselgel 60F254, Merck).
Products were detected by viewing under a UV light, by staining
with an anisaldehyde solution composed of acetic acid, sulfuric
acid, and MeOH, or by staining with a KMnO4 solution
b
(0.12 M). isolated yield.
We propose the following mechanism, similar to other reported
copper catalyzed arylations with diaryliodonium salts, for this
composed of potassium carbonate, sodium hydroxide, and water.
Flash column chromatography was performed on Merck 60 silica
gel (70-230 mesh). Yields refer to chromatographically and
spectroscopically pure compounds unless otherwise noted. H
and C spectra were recorded on a Bruker AM-300 or Varian
7b, 8b
cross-coupling procedure (Scheme 3).
Oxidation of Cu(I) salt
1
A with iodonium triflate would give rise to the aryl-Cu(III)
species B. Next, coordination of the oxygen lone pairs of tert-
butyl-N-sulfonylcarbamate with this active copper species would
form a tetracoordinate Cu(III)-complex C. After the extraction of
13
Unity-Inova 500 MHz spectrometer. Chemical shifts are reported
1
as  values relative to internal SiMe or chloroform ( 0.00 for H
4
a proton from C by the base utilized (cf. Et N, DIPEA),
13
13
3
and  77.0 for C) or benzene ( 128.0 for C). IR spectra were
measured as neat oils on a Varian Scimitar 800 FT-IR
spectrometer. High resolution spectra were obtained at Sogang
University’s Organic Chemistry Research Center or the Korea
Basic Science Institute Mass Spectrometry Service Center.
rearrangement would afford Cu(III)-complex D. Finally,
reductive elimination would yield the coupled product E and
regenerate the Cu(I) catalyst allowing the catalytic cycle to
continue.
3. Conclusions
4
(
.2. General procedure I for copper-catalyzed N-arylation
Tables 1-3, Scheme 2)
In conclusion, we have described a new synthetic method for
the preparation of N-arylsulfonamides employing tert-butyl N-
sulfonylcarbamates and diaryliodonium salts. The reaction diaryliodonium salt (0.325 mmol), CuCl (10 mol %),
A 10 mL round bottom flask was charged with a
requires 10 mol % of CuCl catalyst and Et N as a base at room triethylamine (0.50 mmol) and the corresponding tert-butyl N-
3
temperature. The scope of this method has been explored sulfonylcarbamate (0.25 mmol). Toluene (2 mL) was then added
employing different tert-butyl N-sulfonylcarbamates and to the flask. The reaction mixture was stirred at room
diaryliodonium salts. Furthermore, a one-pot coupling/Boc- temperature. After completion of the reaction, as monitored by
deprotection sequence utilizing aqueous trifluoroacetic acid was TLC analysis, the solvent was removed in vacuo and the residue
investigated to successfully furnish mono N-arylsulfonamides in was purified by flash column chromatography on silica gel to
good to excellent yields.
obtain the desired product.
4
.2.1. tert-butyl phenyl(tosyl)carbamate (3a).

5
General procedure
I
was used empAloyCinCg EtPerTt-bEuDtyl MANGUenSerCalRpIrPocTedure
I was used employing tert-butyl
tosylcarbamate (0.068 g, 0.25 mmol) and diphenyliodonium
triflate (0.140 g, 0.325 mmol), and the reaction was complete in 1
h. Flash chromatography on silica gel using hexane/ethyl acetate
methylsulfonylcarbamate (0.049 g, 0.25 mmol) and
diphenyliodonium triflate (0.140 g, 0.325 mmol), and the
reaction was complete in 8 h. Flash chromatography on silica gel
using hexane/ethyl acetate (7:1) provided pure 3e (0.062 g, 0.23
1
2
3
4
5
6
7
8
9
0
1
2
(
7:1) provided pure 3a (0.084 g, 0.24 mmol, 97%) as a white
1
o
solid. R 0.47 (hexane/ethyl acetate = 3:1); H NMR (300 MHz,
mmol, 91%) as a white solid. mp: 83-85 C; Rf 0.27
f
CDCl )  7.87 (d, J = 8.1 Hz, 2H), 7.48-7.37 (m, 3H), 7.34 (d, J
(hexane/ethyl acetate = 3:1); IR (neat) 3015, 2982, 2939, 1732,
1596, 1492, 1356, 1148, 967, 838, 694, 547 cm ; H NMR (300
3
13
-1 1
=
8.1 Hz, 2H), 7.29-7.20 (m, 2H), 2.46 (s, 3H), 1.34 (s, 9H);
C
NMR (75 MHz, CDCl )  150.9, 144.4, 136.7, 136.4, 129.6,
MHz, CDCl )  7.45-7.37 (m, 3H), 7.27-7.21 (m, 2H), 3.42 (s,
3
3
1
3
1
29.3, 129.0, 128.9, 128.6, 84.3, 27.8, 21.6; Data is consistent
3H), 1.46 (s, 9H); C NMR (75 MHz, CDCl )  151.5, 135.6,
3
1
3
with that reported in the literature.
129.3, 129.1, 129.05, 84.7, 41.6, 27.8; HRMS-FAB: m/z
+
+
2
94.0772 [(M+Na) ; calcd for C H NNaO S : 294.0770].
12 17 4
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
4
.2.2 tert-butyl naphthalene-2-ylsulfonyl(phenyl)carbamate (3b).
General procedure was used employing tert-butyl
4
.2.6. tert-butyl cyclopropylsulfonyl(phenyl)carbamate (3f).
General procedure was used employing tert-butyl
I
3 naphthalen-2-ylsulfonylcarbamate (0.077 g, 0.25 mmol) and
4 diphenyliodonium triflate (0.140 g, 0.325 mmol), and the
5 reaction was complete in 4 h. Flash chromatography on silica gel
I
cyclopropylsulfonylcarbamate (0.055 g, 0.25 mmol) and
diphenyliodonium triflate (0.140 g, 0.325 mmol), and the
reaction was complete in 12 h. Flash chromatography on silica
6 using hexane/ethyl acetate (7:1) provided pure 3b (0.092 g, 0.24
o
7 mmol, 96%) as a white solid. mp: 126-128 C; R
0.44
gel using hexane/ethyl acetate (7:1) provided pure 3f (0.071 g,
f
o
8 (hexane/ethyl acetate = 3:1); IR (neat) 3059, 2977, 1734, 1352,
0.24 mmol, 96%) as a white solid. mp: 75-76 C; R
0.34
f
-
1 1
1
8
3

1
292, 1150, 1073, 814, 695 cm ; H NMR (300 MHz, CDCl ) 
(hexane/ethyl acetate = 3:1); IR (neat) 2982, 1733, 1490, 1361,
9
0
1
2
3
4
5
6
7
8
9
0
3
-1 1
.59 (s, 1H), 8.02-7.88 (m, 4H), 7.72-7.57 (m, 2H), 7.45-7.38 (m,
1293, 1145, 1074, 970, 885, 711, 586 cm ; H NMR (300 MHz,
CDCl )  7.46-7.33 (m, 3H), 7.28-7.22 (m, 2H), 3.36-3.25 (m,
1
3
H), 7.36-7.26 (m, 2H), 1.31 (s, 9H); C NMR (75 MHz, CDCl3)
150.8, 136.4, 136.3, 135.1, 131.7, 130.5, 129.7, 129.3, 129.2,
29.1, 129.0, 128.9, 127.9, 127.6, 123.1, 84.5, 27.7; HRMS-
3
1
3
1H), 1.47 (s, 9H), 1.36-1.29 (m, 2H), 1.18-1.09 (m, 2H);
C
NMR (75 MHz, CDCl )  151.6, 136.2, 129.4, 129.0, 128.8,
3
+
+
+
FAB: m/z 406.1084 [(M+Na) ; calcd for C H NNaO S :
84.3, 31.7, 27.8, 6.0; HRMS-FAB: m/z 298.1107 [(M+Na) ;
calcd for C H NO S : 298.1108].
2
1
21
4
+
4
06.1083].
1
4
20
4
4
.2.3. tert-butyl phenyl(phenylsulfonyl)carbamate (3c).
General procedure was used employing tert-butyl
4.2.7. tert-butyl (4-fluorophenyl)sulfonyl(phenyl)carbamate (3g).
I
General procedure I was used employing tert-butyl (4-
fluorophenyl)sulfonylcarbamate (0.069 g, 0.25 mmol) and
diphenyliodonium triflate (0.140 g, 0.325 mmol), and the
reaction was complete in 6 h. Flash chromatography on silica gel
using hexane/ethyl acetate (7:1) provided pure 3g (0.084 g, 0.24
phenylsulfonylcarbamate (0.064 g, 0.25 mmol) and
1 diphenyliodonium triflate (0.140 g, 0.325 mmol), and the
2 reaction was complete in 10 h. Flash chromatography on silica
3 gel using hexane/ethyl acetate (7:1) provided pure 3c (0.080 g,
4 0.24 mmol, 96%) as a white solid. mp: 67-68 C; R 0.43
5 (hexane/ethyl acetate = 3:1); IR (neat) 3065, 2981, 1734, 1598,
o
o
mmol, 96%) as a white solid. mp: 80-82 C; Rf 0.55
f
(hexane/ethyl acetate = 3:1); IR (neat) 2982, 1734, 1591, 1494,
-
1
1
-1
1
6 1790, 1368, 1151, 1091, 970, 812, 696, 580 cm ; H NMR (300
7 MHz, CDCl )  8.00 (d, J = 7.5 Hz, 2H), 7.68-7.60 (m, 1H),
8 7.58-7.50 (m, 2H), 7.46-7.38 (m, 3H), 7.29-7.25 (m, 2H), 1.32 (s,
1370, 1151, 968, 841, 695, 579 cm ; H NMR (300 MHz,
CDCl )  8.09-7.96 (m, 2H), 7.47-7.37 (m, 3H), 7.29-7.20 (m,
4H), 1.34 (s, 9H); C NMR (100 MHz, CDCl
3
3
1
3
)  165.5 (d, J =
3
1
3
9 9H); C NMR (75 MHz, CDCl
)  150.7, 139.6, 136.2, 133.4,
104 Hz), 150.7, 136.2, 135.5, 131.4 (d, J = 7.6 Hz), 129.5, 129.1,
129.06, 115.9 (d, J = 17.8 Hz), 84.6, 27.7; HRMS-FAB: m/z
3
1
3
29.6, 129.0, 128.97, 128.6, 128.4, 84.5, 27.7; HRMS-FAB: m/z
56.0927 [(M+Na) ; calcd for C H NNaO S : 356.0927].
0
1
2
3
4
5
6
7
8
9
0
1
+
+
+
+
374.0833 [(M+Na) ; calcd for C H FNNaO S : 374.0833].
17 19
4
17 18 4
4
.2.4. tert-butyl (4-methoxyphenyl)sulfonyl(phenyl)carbamate
4.2.8. tert-butyl (4-chlorophenyl)sulfonyl(phenyl)carbamate (3h).
(3d).
General procedure I was used employing tert-butyl (4-
chlorophenyl)sulfonylcarbamate (0.073 g, 0.25 mmol) and
diphenyliodonium triflate (0.140 g, 0.325 mmol), and the
reaction was complete in 4 h. Flash chromatography on silica gel
General procedure I was used employing tert-butyl (4-
methoxyphenyl)sulfonylcarbamate (0.072 g, 0.25 mmol) and
diphenyliodonium triflate (0.161 g, 0.375 mmol), and the
reaction was complete in 10 h. Flash chromatography on silica
gel using hexane/ethyl acetate (7:1) provided pure 3d (0.088 g,
using hexane/ethyl acetate (7:1) provided pure 3h (0.088 g, 0.24
o
mmol, 96%) as a white solid. mp: 102-103 C; R 0.61
f
0
.24 mmol, 97%) as a colorless oil.; R 0.30 (hexane/ethyl acetate
(hexane/ethyl acetate = 3:1); IR (neat) 2982, 1733, 1584, 1491,
f
-
1 1
2 = 3:1); IR (neat) 2981, 1733, 1596, 1498, 1368, 1263, 1150, 1090,
1371, 1150, 1092, 839, 759, 694, 576 cm ; H NMR (300 MHz,
-
1
1
3 839, 677, 581 cm ; H NMR (300 MHz, CDCl )  7.92 (d, J =
CDCl )  7.93 (d, J = 8.8 Hz, 2H), 7.52 (d, J = 8.7 Hz, 2H), 7.46-
3
3
1
3
4 8.7 Hz, 2H), 7.46-7.38 (m, 3H), 7.27-7.21 (m, 2H), 7.00 (d, J =
7.38 (m, 3H), 7.26-7.18 (m, 2H), 1.34 (s, 9H); C NMR (75
1
3
5 9.0 Hz, 2H), 3.89 (s, 3H), 1.35 (s, 9H); C NMR (75 MHz,
6 CDCl )  163.5, 151.0, 136.6, 131.1, 130.9, 129.6, 129.0, 128.9,
7 113.8, 84.2, 55.6, 27.8; HRMS-FAB: m/z 364.1213 [(M+Na) ;
8 calcd for C18
9
MHz, C D )  151.1, 139.8, 138.9, 137.1, 130.7, 130.1, 129.3,
6
6
+
129.1, 129.0, 84.0, 27.7; HRMS-FAB: m/z 390.0536 [(M+Na) ;
+
3
+
calcd for C17H18ClNNaO S : 390.0537].
4
+
H22NO
S : 364.1213].
5
0
4.2.9. tert-butyl (4-bromophenyl)sulfonyl(phenyl)carbamate (3i).
1 4.2.5. tert-butyl methylsulfonyl(phenyl)carbamate (3e).
2
3
4
5

6
Tetrahedron
General procedure I was used employiAngCtCerEt-bPuTtylE(D4- MA4.N2.1U3.SteCrt-RbuItPylTp-tolyl(tosyl)carbamate (5a).
bromophenyl)sulfonylcarbamate (0.084 g, 0.25 mmol) and
diphenyliodonium triflate (0.140 g, 0.325 mmol), and the
reaction was complete in 10 h. Flash chromatography on silica
General procedure
I
was used employing tert-butyl
tosylcarbamate (0.068 g, 0.25 mmol) and di-p-tolyliodonium
triflate (0.149 g, 0.325 mmol), and the reaction was complete in 6
h. Flash chromatography on silica gel using hexane/ethyl acetate
1
2
3
4
5
6
7
8
9
0
1
2
3
4
gel using hexane/ethyl acetate (7:1) provided pure 3i (0.098 g,
o
0
.24 mmol, 95%) as a white solid. mp: 108-110 C; R 0.61
f
(7:1) provided pure 5a (0.086 g, 0.24 mmol, 95%) as a white
(hexane/ethyl acetate = 3:1); IR (neat) 2981, 1736, 1574, 1491,
o
-
1
1
solid. mp: 132-134 C; R
0.56 (hexane/ethyl acetate = 3:1); IR
f
1
391, 1370, 1290, 1148, 745, 602 cm ; H NMR (300 MHz,
(
neat) 2982, 2929, 1733, 1511, 1368, 1290, 1151, 971, 841, 669
CDCl )  7.86 (d, J = 8.4 Hz, 2H), 7.69 (d, J = 8.4 Hz, 2H), 7.47-
-1
1
3
1
3
cm ; H NMR (300 MHz, CDCl )  7.86 (d, J = 8.3 Hz, 2H),
7.33 (d, J = 7.7 Hz, 2H), 7.22 (d, J = 7.7 Hz, 2H), 7.13 (d, J = 8.3
3
7
.38 (m, 3H), 7.25-7.18 (m, 2H), 1.34 (s, 9H); C NMR (75
MHz, C D )  151.1, 139.4, 137.2, 132.0, 130.7, 130.1, 129.2,
13
6
6
+
Hz, 2H), 2.46 (s, 3H), 2.38 (s, 3H), 1.34 (s, 9H); C NMR (75
1
29.0, 128.5, 84.0, 27.7; HRMS-FAB: m/z 412.0212 [(M+Na) ;
+
MHz, CDCl )  151.0, 144.3, 139.0, 136.8, 133.8, 129.8, 129.3,
129.25, 128.5, 84.3, 27.8, 21.6, 21.2; HRMS-FAB: m/z 384.1241
[(M+Na) ; calcd for C19H23NNaO S : 384.1240].
3
calcd for C H BrNO S : 412.0213].
1
7
19
4
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
+
+
4
4
.2.10. tert-butyl (4-nitrophenyl)sulfonyl(phenyl)carbamate (3j).
General procedure I was used employing tert-butyl (4-
4.2.14. tert-butyl (4-(tert-butyl)phenyl)(tosyl)carbamate (5b).
General procedure was used employing tert-butyl
tosylcarbamate (0.068 g, 0.25 mmol) and bis(4-(tert-
butyl)phenyl)iodonium triflate (0.176 g, 0.325 mmol), and the
reaction was complete in 4 h. Flash chromatography on silica gel
5 nitrophenyl)sulfonylcarbamate (0.076 g, 0.25 mmol) and
6 diphenyliodonium triflate (0.161 g, 0.375 mmol), and the
7 reaction was complete in 24 h. Flash chromatography on silica
I
8 gel using hexane/ethyl acetate (7:1) provided pure 3j (0.089 g,
o
0
.235 mmol, 94%) as a white solid. mp: 146-148 C; R 0.46
9
0
1
2
3
4
5
6
7
8
9
0
f
using hexane/ethyl acetate (7:1) provided pure 5b (0.089 g, 0.22
(hexane/ethyl acetate = 3:1); IR (neat) 3117, 2975, 1734, 1611,
o
-
1
1
mmol, 88%) as a white solid. mp: 156-158 C; R
f
0.63
1
491, 1361, 1286, 1151, 1090, 747, 695, 568 cm ; H NMR (300
(
hexane/ethyl acetate = 3:1); IR (neat) 2966, 1734, 1368, 1151,
MHz, CDCl )  8.40 (d, J = 9.3 Hz, 2H), 8.20 (d, J = 8.7 Hz,
2
NMR (75 MHz, C D )  151.0, 150.4, 145.1, 136.7, 130.1, 130.0,
1
-1 1
3
1
3
1091, 665, 591 cm ; H NMR (300 MHz, CDCl
3
)  7.87 (d, J =
.1 Hz, 2H), 7.43 (d, J = 8.4 Hz, 2H), 7.31 (d, J = 8.1 Hz, 2H),
.18 (d, J = 8.4 Hz, 2H), 2.47 (s, 3H), 1.35 (s, 9H), 1.34 (s, 9H);
H), 7.50-7.41 (m, 3H), 7.25-7.17 (m, 2H), 1.34 (s, 9H);
C
8
7
6
6
29.4, 129.3, 123.8, 84.5, 27.6; HRMS-FAB: m/z 401.0778
13
+
+
C NMR (75 MHz, CDCl
29.3. 129.0, 128.5, 126.1, 84.4, 34.7, 31.3, 27.8, 21.6; HRMS-
3
)  151.9, 151.1, 144.3, 137.0, 133.6,
[
(M+Na) ; calcd for C H N NaO S : 401.0778].
17 18 2 6
1
+
+
FAB: m/z 426.1709 [(M+Na) ; calcd for C H NNaO S :
2
2
29
4
426.1710].
4
.2.11. tert-butyl phenyl(thiophen-2-ylsulfonyl)carbamate (3k).
General procedure I was used employing tert-butyl thiophen-
1 2-ylsulfonylcarbamate
(0.066
g,
0.25
mmol)
and
4.2.15. tert-butyl (4-methoxyphenyl)(tosyl)carbamate (5c).
General procedure was used employing tert-butyl
2 diphenyliodonium triflate (0.140 g, 0.325 mmol), and the
3 reaction was complete in 10 h. Flash chromatography on silica
4 gel using hexane/ethyl acetate (7:1) provided pure 3k (0.083 g,
5 0.245 mmol, 98%) as a white oil.; R 0.50 (hexane/ethyl acetate =
6 3:1); IR (neat) 3105, 2924, 2854, 1733, 1596, 1372, 1290, 1148,
I
tosylcarbamate (0.068 g, 0.25 mmol) and bis(4-
methoxyphenyl)iodonium triflate (0.159 g, 0.325 mmol), and the
reaction was complete in 12 h. Flash chromatography on silica
gel using hexane/ethyl acetate (7:1) provided pure 5c (0.091 g,
f
-
1 1
7 914, 742, 593 cm ; H NMR (300 MHz, CDCl )  7.80 (dd, J =
3
0
=
.24 mmol, 96%) as a white solid. R 0.43 (hexane/ethyl acetate
f
1
8 3.8 and 1.3 Hz, 1H), 7.71 (dd, J = 5.0 and 1.3 Hz, 1H), 7.46-7.38
3:1); H NMR (300 MHz, CDCl )  7.86 (d, J = 8.4 Hz, 2H),
3
9 (m, 3H), 7.27-7.20 (m, 2H), 7.14 (dd, J = 6.3 and 4.9 Hz, 1H),
1
3
7.33 (d, J = 8.1 Hz, 2H), 7.16 (dd, J = 6.9 and 2.1 Hz, 2H), 6.92
1
1
.40 (s, 9H); C NMR (75 MHz, C D )  150.9, 140.2, 137.0,
13
0
1
2
3
4
5
6
7
8
9
0
1
6
6
(
d, J = 8.7 Hz, 2H), 3.81 (s, 3H), 2.45 (s, 3H), 1.34 (s, 9H);
NMR (75 MHz, CDCl )  159.7, 151.0, 144.3, 136.7, 130.6,
29.2, 128.9, 128.4, 114.2, 84.2, 55.3, 27.7, 21.5; Data is
C
34.9, 132.8, 129.8, 128.8, 128.6, 126.4, 83.6, 27.4; HRMS-
+
+
3
FAB: m/z 340.0672 [(M+Na) ; calcd for C H NO S :
3
15 18
4 2
1
40.0672].
14
consistent with that reported in the literature.
4
.2.12. tert-butyl benzofuran-2-ylsulfonyl(phenyl)carbamate (3l).
General procedure was used employing tert-butyl
4
.2.16. tert-butyl tosyl(4-trifluoromethyl)phenyl)carbamate (5d).
General procedure was used employing tert-butyl
I
I
benzofuran-2-ylsulfonylcarbamate (0.074 g, 0.25 mmol) and
diphenyliodonium triflate (0.269 g, 0.625 mmol), and the
reaction was complete in 24 h. Flash chromatography on silica
tosylcarbamate (0.068 g, 0.25 mmol) and bis(4-
trifluoromethyl)phenyl)iodonium triflate (0.184 g, 0.325 mmol),
(
and the reaction was complete in 8 h. Flash chromatography on
gel using hexane/dichloromathane (1:1) provided pure 3l (0.085
o
silica gel using hexane/ethyl acetate (7:1) provided pure 5d
2 g, 0.23 mmol, 91%) as a white solid. mp: 116-118 C; R 0.26
3 (hexane/ethyl acetate = 3:1); IR (neat) 3120, 2984, 2931, 1738,
f
o
(
0.090 g, 0.22 mmol, 87%) as a white solid. mp: 136-138 C; R
f
-
1
1
0.59 (hexane/ethyl acetate = 3:1); IR (neat) 2984, 2931, 1738,
4 1548, 1490, 1374, 1291, 1144, 974, 838, 756, 565 cm ; H NMR
-1 1
1
612, 1326, 1169, 1020, 812, 766, 579 cm ; H NMR (300 MHz,
CDCl )  7.86 (d, J = 8.3 Hz, 2H), 7.69 (d, J = 8.3 Hz, 2H), 7.37
t, J = 8.3 Hz, 4H), 2.47 (s, 3H), 1.35 (s, 9H); C NMR (75
MHz, CDCl )  150.4, 144.9, 139.6, 139.59, 136.3, 130.9 (q, J =
33 Hz), 130.3, 129.5, 128.5, 126.2 (q, J = 3.8 Hz), 85.1, 27.7,
5 (300 MHz, CDCl )  7.74 (d, J = 7.8 Hz, 1H), 7.66-7.36 (m, 9H),
3
1
3
3
6 1.35 (s, 9H); C NMR (75 MHz, CDCl )  155.6, 150.3, 149.1,
3
13
(
7 135.6, 129.9, 129.3, 129.2, 128.2, 125.7, 124.4, 123.1, 114.8,
+
3
8 112.3, 85.2, 27.7; HRMS-FAB: m/z 396.0877 [(M+Na) ; calcd
9 for C19
+
H
19NNaO
S : 396.0876].
+
5
2
1.6; HRMS-FAB: m/z 438.0957 [(M+Na) ; calcd for
0
1
2
3
4
5
+
C H F NNaO : 438.0957].
1
9
20
3
4

7
4
.2.17. tert-butyl (4-fluorophenyl)(tosyl)carbamAatCe (C5eE). PTED MA13N0.U5, S1C35R.4,IP1T29.7, 129.4, 128.6, 84.8, 52.3, 27.8, 21.7;
+
+
HRMS-FAB: m/z 428.1138 [(M+Na) ; calcd for C H NNaO S :
2
0
23
6
General procedure
I
was used employing tert-butyl
4
28.1138].
tosylcarbamate (0.068 g, 0.25 mmol) and bis(4-
fluorophenyl)iodonium triflate (0.152 g, 0.325 mmol), and the
reaction was complete in 6 h. Flash chromatography on silica gel
using hexane/ethyl acetate (7:1) provided pure 5e (0.088 g, 0.24
1
2
3
4
5
6
7
8
9
4
.2.21. tert-butyl thiophen-3-yl(tosyl)carbamate (5j).
General procedure was used employing tert-butyl
o
mmol, 96%) as a white solid. mp: 104-106 C; Rf 0.56
I
(
hexane/ethyl acetate = 3:1); IR (neat) 3449, 2986, 1733, 1598,
tosylcarbamate (0.068 g, 0.25 mmol) and mesityl(thiophen-3-
yl)iodonium triflate (0.155 g, 0.325 mmol), and the reaction was
complete in 16 h. Flash chromatography on silica gel using
-
1
1
1505, 1373, 1093, 975, 842, 671 cm ; H NMR (300 MHz,
CDCl )  7.85 (d, J = 8.4 Hz, 2H), 7.35 (d, J = 8.0 Hz, 2H), 7.27-
7.19 (m, 2H), 7.15-7.06 (s, 2H), 2.46 (s, 3H), 1.35 (s, 9H);
3
1
3
C
hexane/ethyl acetate (7:1) provided pure 5j (0.083 g, 0.235
o
NMR (75 MHz, CDCl )  162.6 (d, J = 248 Hz), 150.8, 144.6,
mmol, 94%) as a white solid. mp: 115-117 C; R
0.52
3
f
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
0 136.5, 132.4 (d, J = 3.6 Hz), 131.4 (d, J = 8.8 Hz), 129.4, 128.5,
1 116.0 (d, J = 23 Hz), 84.6, 27.8, 21.6; HRMS-FAB: m/z
2 388.0989 [(M+Na) ; calcd for C18
3
(hexane/ethyl acetate = 3:1); IR (neat) 3108, 2976, 2360, 1734,
-
1 1
1527, 1369, 1148, 812, 636 cm ; H NMR (300 MHz, CDCl ) 
3
+
+
H20FNNaO
S : 388.0989].
7.85 (d, J = 8.0 Hz, 2H), 7.36-7.24 (m, 4H), 6.96 (dd, J = 5.0 and
4
1
3
1.1 Hz, 1H), 2.45 (s, 3H), 1.35 (s, 9H); C NMR (100 MHz,
CDCl )  150.6, 144.5, 136.5, 133.3, 129.3, 128.4, 127.2, 124.8,
124.3, 84.5, 27.8, 21.6; HRMS-FAB: m/z 376.0647 [(M+Na) ;
4
3
+
5 4.2.18. tert-butyl (4-chlorophenyl)(tosyl)carbamate (5f).
+
6
calcd for C16H19NNaO S : 376.0648].
4 2
General procedure
I
was used employing tert-butyl
7
8
9
0
1
2
3
4
5
6
7
tosylcarbamate (0.068 g, 0.25 mmol) and bis(4-
chlorophenyl)iodonium triflate (0.162 g, 0.325 mmol), and the
reaction was complete in 10 h. Flash chromatography on silica
gel using hexane/ethyl acetate (7:1) provided pure 5f (0.088 g,
0
4.2.22. tert-butyl (6-bromopyridin-3-yl)(tosyl)carbamate (5k).
General procedure was used employing tert-butyl
I
o
.23 mmol, 92%) as a white solid. mp: 132-133 C; R 0.59
tosylcarbamate (0.068 g, 0.25 mmol) and (6-bromopyridin-3-
yl)(2,4,6-triethylphenyl)iodonium triflate (0.193 g, 0.325 mmol),
and the reaction was complete in 12 h. Flash chromatography on
f
(hexane/ethyl acetate = 3:1); IR (neat) 3455, 2980, 1733, 1597,
-
1 1
1
489, 1373, 1250, 1091, 973, 813, 665 cm ; H NMR (300 MHz,
CDCl )  7.85 (d, J = 8.0 Hz, 2H), 7.43-7.30 (m, 4H), 7.18 (d, J
=
C D )  151.0, 144.3, 137.6, 136.0, 135.0, 131.6, 129.4 (2C),
1
silica gel using hexane/ethyl acetate (7:1) provided pure 5k
3
1
3
o
8.4 Hz, 2H), 2.46 (s, 3H), 1.35 (s, 9H); C NMR (75 MHz,
(0.065 g, 0.15 mmol, 61%) as a white solid. mp: 166-168 C; R
f
6
6
0.48 (hexane/ethyl acetate = 3:1); IR (neat) 2976, 2360, 1735,
+
-1
1
29.2, 83.9, 27.7, 21.2; HRMS-FAB: m/z 404.0694 [(M+Na) ;
1370, 1285, 1149, 1090, 664, 582 cm ; H NMR (300 MHz,
CDCl
+
8 calcd for C H ClNNaO S : 404.0694].
1
8
20
4
3
)  8.16 (d, J = 2.2 Hz, 1H), 7.83 (d, J = 8.1 Hz, 2H), 7.58
d, J = 8.7 Hz, 1H), 7.50 (dd, J = 8.7 and 2.7 Hz, 1H), 7.37 (d, J
9
0
(
1
3
=
8.1 Hz, 2H), 2.48 (s, 3H), 1.37 (s, 9H); C NMR (100 MHz,
1 4.2.19. tert-butyl (4-bromophenyl)(tosyl)carbamate (5g).
CDCl )  150.2, 150.0, 145.3, 142.0, 139.8, 135.8, 133.1, 129.6,
3
2
128.6, 128.5, 85.6, 27.8, 21.7; HRMS-FAB: m/z 449.0141
General procedure
I
was used employing tert-butyl
+
+
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
[(M+Na) ; calcd for C H BrN NaO S : 449.0141].
17 19 2 4
tosylcarbamate (0.068 g, 0.25 mmol) and bis(4-
bromophenyl)iodonium triflate (0.191 g, 0.325 mmol), and the
reaction was complete in 6 h. Flash chromatography on silica gel
using hexane/ethyl acetate (7:1) provided pure 5g (0.102 g, 0.24
4.2.23.
tert-butyl
(4-bromophenyl)sulfonyl(4-
o
fluorophenyl)carbamate (8).
mmol, 96%) as a white solid. mp: 148-150 C; Rf 0.59
(hexane/ethyl acetate = 3:1); IR (neat) 2987, 2931, 1739, 1595,
General procedure I was used employing tert-butyl (4-
bromophenyl)sulfonylcarbamate (1.681 g, 5.00 mmol) and bis(4-
fluorophenyl)iodonium triflate (3.030 g, 6.50 mmol), and the
reaction was complete in 10 h. Flash chromatography on silica
-1
1
1
487, 1284, 1173, 1071, 838, 730, 664, 580 cm ; H NMR (300
MHz, CDCl )  7.84 (d, J = 8.0 Hz, 2H), 7.55 (d, J = 8.9 Hz,
3
2
3
1
H), 7.34 (d, J = 8.5 Hz, 2H), 7.12 (d, J = 8.5 Hz, 2H), 2.47 (s,
13
H), 1.35 (s, 9H); C NMR (75 MHz, CDCl )  150.5, 144.7,
gel using hexane/ethyl acetate (10:1) provided pure 8 (2.086 g,
3
o
36.4, 135.5, 132.3, 131.3, 129.4, 128.6, 123.1, 84.8, 27.8, 21.7;
4.85 mmol, 97%) as a white solid. mp: 128-129 C; R 0.62
f
+
HRMS-FAB:
C H BrNNaO S : 448.0189].
m/z
448.0189
[(M+Na) ;
calcd
for
(hexane/ethyl acetate = 4:1); IR (neat) 3092, 2981, 2939, 1736,
+
-1
1
1
8
20
4
1574, 1506, 1471, 1370, 1147, 1087, 744, 619, 569 cm ; H
NMR (300 MHz, CDCl )  7.84 (d, J = 8.7 Hz, 2H), 7.70 (d, J =
3
13
8
.4 Hz, 2H), 7.25-7.03 (m, 4H), 1.35 (s, 9H); C NMR (75 MHz,
4
.2.20.
methyl
4-(N-tert-butoxycarbonyl)-4-
CDCl )  162.7 (d, J = 248 Hz), 150.5, 138.3, 132.1, 132.0, 131.3
3
methylphenylsulfonamido)benzoate (5i).
(d, J = 8.8 Hz), 130.1, 128.9, 116.2 (d, J = 23 Hz), 85.0, 27.8;
+
HRMS-FAB:
m/z
430.0123
[(M+H) ;
calcd
for
General procedure
I
was used employing tert-butyl
+
C H BrFNO S : 430.0124].
1
7
18
4
tosylcarbamate (0.068 g, 0.25 mmol) and mesityl(4-
methoxycarbonyl)phenyl)iodonium triflate (0.172 g, 0.325
mmol), and the reaction was complete in h. Flash
(
6
4
.2.24.
tert-butyl
(4-chlorophenyl)sulfonyl(4-(tert-
chromatography on silica gel using hexane/ethyl acetate (7:1)
provided pure 5i (0.092 g, 0.23 mmol, 91%) as a white solid. mp:
1
1
butyl)phenyl)carbamate (11).
o
40-142 C; R 0.41 (hexane/ethyl acetate = 3:1); IR (neat) 2983,
General procedure I was used employing tert-butyl (4-
chlorophenyl)sulfonylcarbamate (1.459 g, 5.00 mmol) and bis(4-
(tert-butyl)phenyl)iodonium triflate (3.525 g, 6.50 mmol), and
the reaction was complete in 4 h. Flash chromatography on silica
gel using hexane/ethyl acetate (10:1) provided pure 11 (2.077 g,
f
-1
1
729, 1605, 1370, 1281, 1150, 702, 661, 548 cm ; H NMR (300
MHz, CDCl )  8.10 (d, J = 8.4 Hz, 2H), 7.86 (d, J = 8.4 Hz,
3
2
H), 7.39-7.26 (m, 4H), 3.94 (s, 3H), 2.47 (s, 3H), 1.34 (s, 9H);
13
C NMR (75 MHz, CDCl )  166.2, 150.4, 144.8, 140.5, 136.4,
3

8
Tetrahedron
o
4
.90 mmol, 98%) as a white solid. mp: 156A-1C58CEC;PRTE0.D73 MANTUheSoCneR-pIoPt Tprocedure was used employing tert-butyl (4-
f
(hexane/ethyl acetate = 4:1); IR (neat) 2967, 2871, 1734, 1476,
bromophenyl)sulfonylcarbamate (0.292 g, 1.00 mmol) and
diphenyliodonium triflate (0.559 g, 1.30 mmol). Flash
chromatography on silica gel using hexane/ethyl acetate (5:1)
provided pure 12d (0.088 g, 0.83 mmol, 83%) as a white solid.;
-
1 1
1
367, 1171, 1090, 973, 757, 626, 582 cm ; H NMR (300 MHz,
CDCl )  7.93 (d, J = 8.4 Hz, 2H), 7.52 (d, J = 8.4 Hz, 2H), 7.43
1
2
3
4
5
6
7
8
9
0
1
3
(d, J = 8.4 Hz, 2H), 7.16 (d, J = 8.7 Hz, 2H),1.35 (s, 9H), 1.33 (s,
1
3
1
9
1
H); C NMR (75 MHz, CDCl )  152.1, 150.8, 139.9, 138.2,
33.2, 129.9, 128.9, 128.8, 126.1, 84.6, 34.6, 31.1, 27.7; HRMS-
R 0.62 (dichloromethane); H NMR (300 MHz, CDCl )  7.65
3
f
3
(d, J = 8.6 Hz, 2H), 7.53 (d, J = 8.7 Hz, 2H), 7.49 (br, 1H), 7.28-
7.19 (m, 2H), 7.15-7.07 (m, 3H); C NMR (75 MHz, CDCl ) 
137.7, 136.0, 132.3, 129.4, 128.7, 128.1, 125.6, 121.7; Data is
+
+
13
FAB: m/z 446.1168 [(M+Na) ; calcd for C H ClNNaO S :
2
1
26
4
3
4
46.1169].
1
4
consistent with that reported in the literature.
4
.3. One-pot procedure for the preparation of mono N-
arylsulfonamide (Table 4)
4.3.5. N-(4-fluorophenyl)-4-methylbenzenesulfonamide (12e).
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
Upon completion of General procedure I, as determined by
The one-pot procedure was used employing tert-butyl
tosylcarbamate (0.271 g, 1.00 mmol) and bis(4-
fluorophenyl)iodonium triflate (0.606 g, 1.30 mmol). Flash
chromatography on silica gel using hexane/ethyl acetate (5:1)
o
2 TLC, the reaction mixture (1.00 mmol scale) was cooled to 0 C.
3 Cold trifluoroacetic acid/water (9/1 mL) was slowly added. The
4 reaction was stirred 1 h at 0 C at which time the reaction was
5 diluted with toluene. All volatiles were removed with a rotary
6 evaporator, and the product isolated by silica gel chromatography
7 using the solvent system indicated.
o
provided pure 12e (0.249 g, 0.94 mmol, 94%) as a white solid.;
1
R
0.45 (hexane/ethyl acetate = 2:1); H NMR (300 MHz, CDCl
)
f
3
 7.60 (d, J = 8.3 Hz, 2H), 7.23 (d, J = 7.9 Hz, 2H), 7.06-6.98 (m,
1
3
8
2H), 6.97-6.88 (m, 2H), 6.51 (br, 1H), 2.39 (s, 3H); C NMR (75
MHz, CDCl ) 160.6 (d, J = 244 Hz), 144.0, 135.8, 132.2 (d, J =
9
3
0 4.3.1. 4-methyl-N-phenylbenzenesulfonamide (12a).
1
2
.5 Hz), 129.7, 127.3, 124.9 (d, J = 8.3 Hz), 116.1 (d, J = 22 Hz),
1.6; Data is consistent with that reported in the literature.
15
1
2
3
4
5
6
The one-pot procedure was used employing tert-butyl
tosylcarbamate (0.271 g, 1.00 mmol) and diphenyliodonium
triflate (0.559 g, 1.30 mmol). Flash chromatography on silica gel
using hexane/ethyl acetate (5:1) provided pure 12a (0.210 g, 0.85
mmol, 85%) as a white solid. R 0.59 (hexane/ethyl acetate =
4
.3.6. N-phenylmethanesulfonamide (12f).
The one-pot procedure was used employing tert-butyl
methylcarbamate (0.195 g, 1.00 mmol) and diphenyliodonium
triflate (0.559 g, 1.30 mmol). Flash chromatography on silica gel
f
1
2
7
:1); H NMR (300 MHz, CDCl )  7.67 (d, J = 8.4 Hz, 2H),
3
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
.29-7.21 (m, 4H), 7.12-7.06 (m, 3H), 6.91 (br, 1H), 2.37 (s, 3H);
1
3
C NMR (75 MHz, CDCl )  143.9, 136.5, 136.0, 129.6, 129.3,
using hexane/ethyl acetate (5:1) provided pure 12f (0.156 g, 0.91
3
1
1
27.2, 125.3, 121.5, 21.5; Data is consistent with that reported in
mmol, 91%) as a white solid. R 0.20 (dichloromethane); H
f
5
the literature.
NMR (300 MHz, CDCl )  7.39-7.33 (m, 2H), 7.26-7.16 (m,
3
1
3
3H), 6.96 (s, 1H), 3.02 (s, 3H); C NMR (75 MHz, CDCl ) 
3
136.7, 129.7, 125.4, 120.8, 39.2; Data is consistent with that
5
4
.3.2. 4-methoxy-N-phenylbenzenesulfonamide (12b).
reported in the literature.
The one-pot procedure was used employing tert-butyl (4-
methoxyphenyl)sulfonylcarbamate (0.287 g, 1.00 mmol) and
diphenyliodonium triflate (0.645 g, 1.50 mmol). Flash
chromatography on silica gel using hexane/ethyl acetate (5:1)
provided pure 12b (0.245 g, 0.93 mmol, 93%) as a white solid. R
0
4.3.7. N-phenylthiophene-2-sulfonamide (12g).
The one-pot procedure was used employing tert-butyl
thiophen-2-ylsulfonylcarbamate (0.263 g, 1.00 mmol) and
diphenyliodonium triflate (0.559 g, 1.30 mmol). Flash
chromatography on silica gel using hexane/ethyl acetate (5:1)
provided pure 12g (0.225 g, 0.94 mmol, 94%) as a colorless oil.
f
1
.61 (dichloromethane); H NMR (300 MHz, CDCl )  7.76 (d, J
9.0 Hz, 2H), 7.61 (br, 1H), 7.25-7.01 (m, 5H), 6.84 (d, J = 9.0
3
=
13
Hz, 2H), 3.76 (s, 3H); C NMR (75 MHz, CDCl )  163.0,
1
consistent with that reported in the literature.
3
36.7, 130.3, 129.4, 129.2, 124.9, 121.2, 114.1, 55.4; Data is
R 0.43 (hexane/ethyl acetate = 2:1); IR (neat) 3241, 3091, 2825,
f
5
-1
1
1599, 1498, 1404, 1335, 1229, 1153, 1092, 928, 589 cm ; H
NMR (300 MHz, CDCl )  7.53 (dd, J = 5.1 and 1.2 Hz, 1H),
3
7
.49 (dd, J = 3.7 and 1.2 Hz, 1H), 7.33-7.25 (m, 2H), 7.20-7.10
13
4
.3.3. 4-chloro-N-phenylbenzenesulfonamide (12c).
(m, 3H), 7.03-6.97 (m, 1H), 6.77 (br, 1H); C NMR (75 MHz,
CDCl ) 139.3, 136.0, 132.9, 132.4, 129.4, 127.3, 125.9, 122.0;
3
The one-pot procedure was used employing tert-butyl (4-
+
+
HRMS-FAB: m/z 261.9966 [(M+Na) ; calcd for C H NNaO S :
1
0
9
2 2
chlorophenyl)sulfonylcarbamate (0.292 g, 1.00 mmol) and
diphenyliodonium triflate (0.559 g, 1.30 mmol). Flash
chromatography on silica gel using hexane/ethyl acetate (5:1)
2
61.9967].
provided pure 12c (0.249 g, 0.89 mmol, 89%) as a white solid.;
1
4.3.8. 4-methyl-N-(thiophen-3-yl)benzenesulfonamide (12h).
R 0.62 (dichloromethane); H NMR (300 MHz, CDCl )  7.72
f
3
(d, J = 8.7 Hz, 2H), 7.39 (d, J = 8.7 Hz, 2H), 7.28-7.20 (m, 2H),
The one-pot procedure was used employing tert-butyl
tosylcarbamate (0.271 g, 1.00 mmol) and mesityl(thiophen-3-
yl)iodonium triflate (0.622 g, 1.30 mmol). Flash chromatography
on silica gel using hexane/ethyl acetate (5:1) provided pure 12h
1
3
7
1
.18-7.04 (m, 4H); C NMR (75 MHz, CDCl )  139.6, 137.3,
3
36.0, 129.4, 129.3, 128.7, 125.8, 121.8; Data is consistent with
5
that reported in the literature.
(
0.228 g, 0.90 mmol, 90%) as a white solid. R 0.45 (hexane/ethyl
f
1
acetate = 2:1); H NMR (300 MHz, CDCl )  7.67 (d, J = 8.0 Hz,
2H), 7.23 (d, J = 8.0 Hz, 2H), 7.20-7.13 (m, 1H), 7.04 (br, 1H),
6
3
4
.3.4. 4-bromo-N-phenylbenzenesulfonamide (12d).
13
.90-6.81 (m, 2H), 2.39 (s, 3H); C NMR (75 MHz, CDCl3)

9
Process Res. Dev. 2010, 14, 960-976. (c) Skipper, P. L.; Kim, M. Y.;
1
43.9, 135.9, 134.2, 129.6, 127.2, 125.6, 123.3,A11C3.C9,E21P.5T; EDaDta MANUSCRIPT
5
Sun, H.-L. P.; Wogan, G. N.; Tannenbaum, S. R. Carcinogenesis 2010,
1, 50-58.
is consistent with that reported in the literature.
3
4
.
For selective examples, see: (a) Lam, P. Y. S.; Vincent, G.; Clark, C. G.;
Deudon, S.; Jadhav, P. K. Tetrahedron Lett. 2001, 42, 3415-3418. (b)
Yin, J.; Buchwald, S. L. J. Am. Chem. Soc. 2002, 124, 6043-6048. (c) He,
H.; Wu, Y.-J. Tetrahedron Lett. 2003, 44, 3385-3386. (d) Hicks, J. D.;
Hyde, A. M.; Cuezva, A. M.; Buchwald, S. L. J. Am. Chem. Soc. 2009,
131, 16720-16734. (e) Shekhar, S.; Dunn, T. B.; Kotecki, B. J.;
Montavon, D. K.; Cullen, S. C. J. Org. Chem. 2011, 76, 4552-4563. (f)
Rosen, B. R.; Ruble, J. C.; Beauchamp, T. J.; Navarro, A. Org. Lett. 2011,
1
2
3
4
5
6
7
8
9
4
.4. N,N-diphenyl-p-toluenesulfonamide (12aa).
10 mL round bottom flask was charged with
A
a
diphenyliodonium triflate (0.140 g, 0.325 mmol), CuI (10 mol
), triethylamine (0.50 mmol) and the corresponding p-
%
toluenesulfonamide (0.043 g, 0.25 mmol). Toluene (2 mL) was
then added to the flask. The reaction mixture was stirred at 50 C.
After 24 h complete consumption of diphenyliodonium triflate
was observed by TLC analysis. The solvent was removed in
1
3, 2564-2567.
o
5
.
Moon, S.-Y.; Nam, J.; Rathwell, K.; Kim, W.-S. Org. Lett. 2014, 16,
338-341.
6. For selective examples, see: (a) Hartmann, C.; Meyer, V. Ber. Dtsch.
Chem. Ges. 1894, 27, 426-429. (b) Varvoglis, A. Synthesis, 1984, 709-
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
0 vacuo and the residue was purified by flash chromatography on
1 silica gel using hexane/ethyl acetate (15:1) provided pure 12aa
2 (0.041 g, 0.13 mmol, 51%) as a white solid. R 0.65 (hexane/ethyl
3 acetate = 2:1); H NMR (300 MHz, CDCl )  7.58 (d, J = 8.1 Hz,
7
9
26. (c) Merritt, E. A.; Olofsson, B. Angew. Chem. Int. Ed. 2009, 48,
052-9070. (d) Yusubov, M. S.; Maskaev, A. V.; Zhdankin, V. V.
f
ARKIVOC 2011, 370-409. (e) Wang. Y.; Chen, C.; Peng, J.; Li. M.
Angew. Chem., Int. Ed, 2013, 52, 5323-5327. (f) Ichiishi, N.; Canty, A.
J.; Yates, B. F.; Sanford, M. S. Org. Lett. 2013, 15, 5134-5137. (g)
Iyanaga, M.; Aihara, Y.; Chatani, N. J. Org. Chem. 2014, 79, 11933-
11939.
For reviews on high-valent organometallic copper complexes, see: (a)
Hickman, A. J.; Sanford, M. S. Nature 2012, 484, 177-185. (b) Casitas,
A.; Ribas, X. Chem. Sci. 2013, 4, 2301-2318.
1
3
1
3
4 2H), 7.35-7.21 (m, 12H), 2.42 (s, 3H); C NMR (75 MHz,
5 CDCl )  143.5, 141.5, 137.5, 129.5, 129.2, 128.3, 127.7, 127.3,
6 21.5; Data is consistent with that reported in the literature. 12a
7 (0.012 g, 0.05 mmol, 19%) as a white solid. R 0.59 (hexane/ethyl
)  7.67 (d, J = 8.4 Hz,
H), 7.29-7.21 (m, 4H), 7.12-7.06 (m, 3H), 6.91 (br, 1H), 2.37 (s,
3
1
7
7
.
f
1
8 acetate = 2:1); H NMR (300 MHz, CDCl
3
2
3
1
8. (a) Geng, X.; Mao, S.; Chen, L.; Yu, J.; Han, J.; Hua, J.; Wang, L.
Tetrahedron Lett. 2014, 55, 3856-3859. (b) Fañanás-Mastral, M; Feringa,
B. L. J. Am. Chem. Soc. 2014, 136, 9894-9897.
9. Initial attempt using 4-toluenesulfonamide and diphenyliodonium triflate.
see:
9
0
1
2
3
4
5
6
7
1
3
H); C NMR (75 MHz, CDCl )  143.9, 136.5, 136.0, 129.6,
3
29.3, 127.2, 125.3, 121.5, 21.5; Data is consistent with that
5
reported in the literature.
Acknowledgments
This research was supported by the Basic Science Research
8 Program through the National Research Foundation of Korea
9 (NRF) (NRF-2012R1A1A1006123) and the New & Renewable
0 Energy of the Korea Institute of Energy Technology Evaluation
1 and Planning (KETEP) grant (No. 20133030000210).
2
3
4
5
6
10. (a) Phipps, R. J.; Gaunt, M. J. Science, 2009, 323, 1593-1597. (b)
Kalayani, D.; Deprez, N. R.; Desai, L. V.; Sanford, M. S. J. Am. Chem.
Soc. 2005, 127, 7330-7331. (c) Kuriyama, M.; Hamaguchi, N.; Onomura,
O. Chem. - Eur. J. 2012, 18, 1591-1594. (d) Malmgren, J.; Santoro, S.;
Jalalian, N.; Himo, F.; Olofsson, B. Chem. Eur. J. 2013, 19, 10334-
10342. (e) Collins, B. S. L.; Suero, M. G.; Gaunt, M. J. Angew. Chem. Int.
Ed. 2013, 52, 5799-5802.
1. (a) Bielawski, M; Olofsson, B. Chem. Commun. 2007, 2521-2523. (b)
Bielawski, M. Zhu, M.; Olofsson, B. Adv. Synth. Catal. 2007, 349, 2610-
2618. (c) Bielawski, M.; Olofsson, B. Org. Synth. 2009, 86, 308-314.
References and notes
1
1
.
(a) For a list of N-arylsulfonamide-containing drugs. see: (a) Scozzafava,
A; Owa, T.; Mastrolorenzo, A.; Supuran, C. T. Curr. Med. Chem. 2003,
10, 925-953. (b) Smith, D. A.; Jones, R. M. Curr. Opin. Drug Discovery
Dev. 2008, 11, 72-79.
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
12. Neustadt, B. R. Tetrahedron Lett. 1994, 35, 379-380.
13. Vellemäe, E.; Lebedev, O.; Mäeorg, U. Tetrahedron Lett. 2008, 49,
1
373-1375.
2
.
(a) Supuran, C. T.; Casini, A.; Scozzafava, A. Med. Res. Rev. 2003, 5,
14. Ankner, T.; Hilmersson, G. Org. Lett. 2009, 11, 503-506.
15. Gowda, B. T.; Shetty, M.; Jayalakshmi, K. L. A: Physical Science, 2004,
59, 239-249.
16. Teo, T.-C.; Yong, F.-F. Synlett, 2011, 6, 837-843.
7. Nandi, P.; Redko, M. Y.; Petersen, K.; Dye, J. L.; Lefenfeld, M.; Vogt, P.
5
35-558. (b) Siddiqui, N.; Pandeya, S. N.; Khan, S. A.; Stables, J.; Rana,
A.; Alam, M.; Arshad, M. F.; Bhat, M. A. Bioorg. Med. Chem. Lett.
2007, 17, 255-259. (c) Basanagouda, M.; Shivashankar, K.; Kulkarni, M.
V.; Rasal, V. P.; Patel, H.; Mutha, S. S.; Mohite, A. A. Eur. J. Med.
Chem. 2010, 45, 1151-1157.
(a) Pierson, D. A.; Olsen, B. A.; Ribbins, D. K.; DeVries, K. M.; Varie,
D. L. Org. Process Res. Dev. 2009, 13, 285-291. (b) Snodin, D. J. Org.
1
F.; Jackson, J. E. Org. Lett. 2008, 10, 5441-5444.
3
.

ACCEPTED MANUSCRIPT
Supporting Information
Copper-Catalyzed N-Arylation of tert-Butyl N-
Sulfonylcarbamates with Diaryliodonium Salts at Room
Temperature
Soo-Yeon Moon, Moonjee Koh, Kris Rathwell, Seo-Hee Jung and Won-Suk Kim*
Department of Chemistry and Nano Science, Ewha Womans University,
Seoul 120-750, South Korea
wonsukk@ewha.ac.kr
Table of Contents:
-
-
General Methods and Experimental Procedures
S2-S19
1
13
H and C NMR Spectra
S20-S85

ACCEPTED MANUSCRIPT
Experimental
I. Materials and Methods
Unless otherwise indicated, all chemical reagents were purchased from Sigma-Aldrich,
1
Alfa Aesar, and TCI and were used without further purification. All diaryliodonium salts and
2
tert-butyl N-sulfonylcarbamates were prepared by the reported procedures. All reactions
were carried out in oven-dried glassware equipped with a magnetic stir bar. Reactions were
monitored by thin layer chromatography (TLC) with 0.25-mm E. Merck pre-coated silica gel
plates (Kieselgel 60F , Merck). Products were detected by viewing under a UV light, by
2
54
staining with an anisaldehyde solution composed of acetic acid, sulfuric acid, and MeOH, or
by staining with a KMnO solution composed of potassium carbonate, sodium hydroxide, and
4
water. Flash column chromatography was performed on Merck 60 silica gel (70-230 mesh).
Yields refer to chromatographically and spectroscopically pure compounds unless otherwise
1
13
noted. H and C spectra were recorded on a Bruker AM-300 or Varian Unity-Inova 500
MHz spectrometer. Chemical shifts are reported as values relative to internal SiMe or
4
1
13
13
chloroform ( 0.00 for H and 77.0 for C) or benzene ( 128.0 for C). IR spectra were
measured as neat oils on a Varian Scimitar 800 FT-IR spectrometer. High resolution spectra
were obtained at Sogang University’s Organic Chemistry Research Center or the Korea Basic
Science Institute Mass Spectrometry Service Center.
II. Experimental Section
General procedure I for copper-catalyzed N-arylation (Table 1-3, scheme 2)
A 10 mL round bottom flask was charged with a diaryliodonium salt (0.325 mmol), CuCl
(10 mol %), triethylamine (0.50 mmol) and the corresponding tert-butyl N-sulfonylcarbamate
(0.25 mmol). Toluene (0.12 M) was then added to the flask. The reaction mixture was stirred
at room temperature. After completion of the reaction, as monitored by TLC analysis, the
S2

ACCEPTED MANUSCRIPT
solvent was removed in vacuo and the residue was purified by flash column chromatography
on silica gel to obtain the desired product.
One-pot procedure for the production of mono N-arylsulfonamides
Upon completion of General procedure I, as determined by TLC, the reaction mixture
o
(
1.00 mmol scale) was cooled to 0 C. Cold trifluoroacetic acid/water (9/1 mL) was slowly
o
added. The reaction was stirred 1 h at 0 C at which time the reaction was diluted with
toluene. All volatiles were removed with a rotary evaporator, and the product isolated by
silica gel chromatography using the solvent system indicated.
tert-butyl phenyl(tosyl)carbamate (3a). General procedure I was used employing tert-butyl
tosylcarbamate (0.068 g, 0.25 mmol) and diphenyliodonium triflate (0.140 g, 0.325 mmol),
and the reaction was complete in 1 h. Flash chromatography on silica gel using hexane/ethyl
acetate (7:1) provided pure 3a (0.084 g, 0.24 mmol, 97%) as a white solid. R 0.47
f
1
(
hexane/ethyl acetate = 3:1); H NMR (300 MHz, CDCl ) 7.87 (d, J = 8.1 Hz, 2H), 7.48-
3
13
7
.37 (m, 3H), 7.34 (d, J = 8.1 Hz, 2H), 7.29-7.20 (m, 2H), 2.46 (s, 3H), 1.34 (s, 9H); C
NMR (75 MHz, CDCl ) 150.9, 144.4, 136.7, 136.4, 129.6, 129.3, 129.0, 128.9, 128.6, 84.3,
3
1
2
7.8, 21.6; Data is consistent with that reported in the literature.
tert-butyl naphthalene-2-ylsulfonyl(phenyl)carbamate (3b). General procedure I was used
employing tert-butyl naphthalen-2-ylsulfonylcarbamate (0.077 g, 0.25 mmol) and
diphenyliodonium triflate (0.140 g, 0.325 mmol), and the reaction was complete in 4 h. Flash
chromatography on silica gel using hexane/ethyl acetate (7:1) provided pure 3b (0.092 g, 0.24
1
Vellemäe, E.; Lebedev, O.; Mäeorg, U. Tetrahedron Lett. 2008, 49, 1373-1375.
S3

ACCEPTED MANUSCRIPT
o
mmol, 96%) as a white solid. mp: 126-128 C; R 0.44 (hexane/ethyl acetate = 3:1); IR (neat)
f
-
1 1
3
8
1
1
059, 2977, 1734, 1352, 1292, 1150, 1073, 814, 695 cm ; H NMR (300 MHz, CDCl )
3
.59 (s, 1H), 8.02-7.88 (m, 4H), 7.72-7.57 (m, 2H), 7.45-7.38 (m, 3H), 7.36-7.26 (m, 2H),
1
3
.31 (s, 9H); C NMR (75 MHz, CDCl ) 150.8, 136.4, 136.3, 135.1, 131.7, 130.5, 129.7,
3
29.3, 129.2, 129.1, 129.0, 128.9, 127.9, 127.6, 123.1, 84.5, 27.7; HRMS-FAB: m/z 406.1084
+
+
[
(M+Na) ; calcd for C H NNaO S : 406.1083].
21 21 4
tert-butyl phenyl(phenylsulfonyl)carbamate (3c). General procedure I was used employing
tert-butyl phenylsulfonylcarbamate (0.064 g, 0.25 mmol) and diphenyliodonium triflate
(0.140 g, 0.325 mmol), and the reaction was complete in 10 h. Flash chromatography on
silica gel using hexane/ethyl acetate (7:1) provided pure 3c (0.080 g, 0.24 mmol, 96%) as a
o
white solid. mp: 67-68 C; R 0.43 (hexane/ethyl acetate = 3:1); IR (neat) 3065, 2981, 1734,
f
-1 1
1
598, 1790, 1368, 1151, 1091, 970, 812, 696, 580 cm ; H NMR (300 MHz, CDCl ) 8.00
3
(d, J = 7.5 Hz, 2H), 7.68-7.60 (m, 1H), 7.58-7.50 (m, 2H), 7.46-7.38 (m, 3H), 7.29-7.25 (m,
1
3
2
1
H), 1.32 (s, 9H); C NMR (75 MHz, CDCl ) 150.7, 139.6, 136.2, 133.4, 129.6, 129.0,
3
+
28.97, 128.6, 128.4, 84.5, 27.7; HRMS-FAB: m/z 356.0927 [(M+Na) ; calcd for
+
C H NNaO S : 356.0927].
17
19
4
tert-butyl (4-methoxyphenyl)sulfonyl(phenyl)carbamate (3d). General procedure I was used
employing tert-butyl (4-methoxyphenyl)sulfonylcarbamate (0.072 g, 0.25 mmol) and
diphenyliodonium triflate (0.161 g, 0.375 mmol), and the reaction was complete in 10 h.
Flash chromatography on silica gel using hexane/ethyl acetate (7:1) provided pure 3d (0.088
g, 0.24 mmol, 97%) as a colorless oil.; R 0.30 (hexane/ethyl acetate = 3:1); IR (neat) 2981,
f
-1 1
1
733, 1596, 1498, 1368, 1263, 1150, 1090, 839, 677, 581 cm ; H NMR (300 MHz, CDCl )
3
S4

ACCEPTED MANUSCRIPT
7
.92 (d, J = 8.7 Hz, 2H), 7.46-7.38 (m, 3H), 7.27-7.21 (m, 2H), 7.00 (d, J = 9.0 Hz, 2H),
1
3
3
1
.89 (s, 3H), 1.35 (s, 9H); C NMR (75 MHz, CDCl
)
163.5, 151.0, 136.6, 131.1, 130.9,
3
+
29.6, 129.0, 128.9, 113.8, 84.2, 55.6, 27.8; HRMS-FAB: m/z 364.1213 [(M+Na) ; calcd for
+
C H NO S : 364.1213].
18
22
5
tert-butyl methylsulfonyl(phenyl)carbamate (3e). General procedure I was used employing
tert-butyl methylsulfonylcarbamate (0.049 g, 0.25 mmol) and diphenyliodonium triflate
(0.140 g, 0.325 mmol), and the reaction was complete in 8 h. Flash chromatography on silica
gel using hexane/ethyl acetate (7:1) provided pure 3e (0.062 g, 0.23 mmol, 91%) as a white
o
solid. mp: 83-85 C; R 0.27 (hexane/ethyl acetate = 3:1); IR (neat) 3015, 2982, 2939, 1732,
f
-1 1
1
596, 1492, 1356, 1148, 967, 838, 694, 547 cm ; H NMR (300 MHz, CDCl ) 7.45-7.37
3
1
3
(
m, 3H), 7.27-7.21 (m, 2H), 3.42 (s, 3H), 1.46 (s, 9H); C NMR (75 MHz, CDCl ) 151.5,
3
+
1
35.6, 129.3, 129.1, 129.05, 84.7, 41.6, 27.8; HRMS-FAB: m/z 294.0772 [(M+Na) ; calcd for
+
C H NNaO S : 294.0770].
12
17
4
tert-butyl cyclopropylsulfonyl(phenyl)carbamate (3f). General procedure I was used
employing tert-butyl cyclopropylsulfonylcarbamate (0.055 g, 0.25 mmol) and
diphenyliodonium triflate (0.140 g, 0.325 mmol), and the reaction was complete in 12 h.
Flash chromatography on silica gel using hexane/ethyl acetate (7:1) provided pure 3f (0.071
o
g, 0.24 mmol, 96%) as a white solid. mp: 75-76 C; R 0.34 (hexane/ethyl acetate = 3:1); IR
f
-1 1
(
neat) 2982, 1733, 1490, 1361, 1293, 1145, 1074, 970, 885, 711, 586 cm ; H NMR (300
MHz, CDCl ) 7.46-7.33 (m, 3H), 7.28-7.22 (m, 2H), 3.36-3.25 (m, 1H), 1.47 (s, 9H), 1.36-
3
1
3
1
.29 (m, 2H), 1.18-1.09 (m, 2H); C NMR (75 MHz, CDCl ) 151.6, 136.2, 129.4, 129.0,
3
S5

ACCEPTED MANUSCRIPT
+
+
1
2
28.8, 84.3, 31.7, 27.8, 6.0; HRMS-FAB: m/z 298.1107 [(M+Na) ; calcd for C H NO S :
14 20 4
98.1108].
tert-butyl (4-fluorophenyl)sulfonyl(phenyl)carbamate (3g). General procedure I was used
employing tert-butyl (4-fluorophenyl)sulfonylcarbamate (0.069 g, 0.25 mmol) and
diphenyliodonium triflate (0.140 g, 0.325 mmol), and the reaction was complete in 6 h. Flash
chromatography on silica gel using hexane/ethyl acetate (7:1) provided pure 3g (0.084 g, 0.24
o
mmol, 96%) as a white solid. mp: 80-82 C; R 0.55 (hexane/ethyl acetate = 3:1); IR (neat)
f
-
1 1
2
8
982, 1734, 1591, 1494, 1370, 1151, 968, 841, 695, 579 cm ; H NMR (300 MHz, CDCl )
3
13
.09-7.96 (m, 2H), 7.47-7.37 (m, 3H), 7.29-7.20 (m, 4H), 1.34 (s, 9H); C NMR (100 MHz,
CDCl3) 165.5 (d, J = 104 Hz), 150.7, 136.2, 135.5, 131.4 (d, J = 7.6 Hz), 129.5, 129.1,
+
1
29.06, 115.9 (d, J = 17.8 Hz), 84.6, 27.7; HRMS-FAB: m/z 374.0833 [(M+Na) ; calcd for
+
C H FNNaO S : 374.0833].
17
18
4
tert-butyl (4-chlorophenyl)sulfonyl(phenyl)carbamate (3h). General procedure I was used
employing tert-butyl (4-chlorophenyl)sulfonylcarbamate (0.073 g, 0.25 mmol) and
diphenyliodonium triflate (0.140 g, 0.325 mmol), and the reaction was complete in 4 h. Flash
chromatography on silica gel using hexane/ethyl acetate (7:1) provided pure 3h (0.088 g, 0.24
o
mmol, 96%) as a white solid. mp: 102-103 C; R 0.61 (hexane/ethyl acetate = 3:1); IR (neat)
f
-1 1
2
982, 1733, 1584, 1491, 1371, 1150, 1092, 839, 759, 694, 576 cm ; H NMR (300 MHz,
CDCl ) 7.93 (d, J = 8.8 Hz, 2H), 7.52 (d, J = 8.7 Hz, 2H), 7.46-7.38 (m, 3H), 7.26-7.18 (m,
3
1
3
2
H), 1.34 (s, 9H); C NMR (75 MHz, C D ) 151.1, 139.8, 138.9, 137.1, 130.7, 130.1,
6
6
S6

ACCEPTED MANUSCRIPT
+
1
29.3, 129.1, 129.0, 84.0, 27.7; HRMS-FAB: m/z 390.0536 [(M+Na) ; calcd for
+
C H ClNNaO S : 390.0537].
17
18
4
tert-butyl (4-bromophenyl)sulfonyl(phenyl)carbamate (3i). General procedure I was used
employing tert-butyl (4-bromophenyl)sulfonylcarbamate (0.084 g, 0.25 mmol) and
diphenyliodonium triflate (0.140 g, 0.325 mmol), and the reaction was complete in 10 h.
Flash chromatography on silica gel using hexane/ethyl acetate (7:1) provided pure 3i (0.098
o
g, 0.24 mmol, 95%) as a white solid. mp: 108-110 C; R 0.61 (hexane/ethyl acetate = 3:1);
f
-1 1
IR (neat) 2981, 1736, 1574, 1491, 1391, 1370, 1290, 1148, 745, 602 cm ; H NMR (300
MHz, CDCl ) 7.86 (d, J = 8.4 Hz, 2H), 7.69 (d, J = 8.4 Hz, 2H), 7.47-7.38 (m, 3H), 7.25-
3
1
3
7
1
.18 (m, 2H), 1.34 (s, 9H); C NMR (75 MHz, C D ) 151.1, 139.4, 137.2, 132.0, 130.7,
6 6
+
30.1, 129.2, 129.0, 128.5, 84.0, 27.7; HRMS-FAB: m/z 412.0212 [(M+Na) ; calcd for
+
C H BrNO S : 412.0213].
17
19
4
tert-butyl (4-nitrophenyl)sulfonyl(phenyl)carbamate (3j). General procedure I was used
employing tert-butyl (4-nitrophenyl)sulfonylcarbamate (0.076 g, 0.25 mmol) and
diphenyliodonium triflate (0.161 g, 0.375 mmol), and the reaction was complete in 24 h.
Flash chromatography on silica gel using hexane/ethyl acetate (7:1) provided pure 3j (0.089
o
g, 0.235 mmol, 94%) as a white solid. mp: 146-148 C; R 0.46 (hexane/ethyl acetate = 3:1);
f
-1
1
IR (neat) 3117, 2975, 1734, 1611, 1491, 1361, 1286, 1151, 1090, 747, 695, 568 cm ; H
NMR (300 MHz, CDCl ) 8.40 (d, J = 9.3 Hz, 2H), 8.20 (d, J = 8.7 Hz, 2H), 7.50-7.41 (m,
3
13
3
H), 7.25-7.17 (m, 2H), 1.34 (s, 9H); C NMR (75 MHz, C D ) 151.0, 150.4, 145.1, 136.7,
6 6
S7

ACCEPTED MANUSCRIPT
+
1
30.1, 130.0, 129.4, 129.3, 123.8, 84.5, 27.6; HRMS-FAB : m/z 401.0778 [(M+Na) ; calcd
+
for C H N NaO S : 401.0778].
1
7
18
2
6
tert-butyl phenyl(thiophen-2-ylsulfonyl)carbamate (3k). General procedure I was used
employing tert-butyl thiophen-2-ylsulfonylcarbamate (0.066 g, 0.25 mmol) and
diphenyliodonium triflate (0.140 g, 0.325 mmol), and the reaction was complete in 10 h.
Flash chromatography on silica gel using hexane/ethyl acetate (7:1) provided pure 3k (0.083
g, 0.245 mmol, 98%) as a white oil.; R 0.50 (hexane/ethyl acetate = 3:1); IR (neat) 3105,
f
-
1 1
2
7
3
924, 2854, 1733, 1596, 1372, 1290, 1148, 914, 742, 593 cm ; H NMR (300 MHz, CDCl )
3
7
.80 (dd, J = 3.8 and 1.3 Hz, 1H), 7.71 (dd, J = 5.0 and 1.3 Hz, 1H), 7.46-7.38 (m, 3H),
1
3
.27-7.20 (m, 2H), 7.14 (dd, J = 6.3 and 4.9 Hz, 1H), 1.40 (s, 9H); C NMR (75 MHz, C D )
6
6
1
50.9, 140.2, 137.0, 134.9, 132.8, 129.8, 128.8, 128.6, 126.4, 83.6, 27.4; HRMS-FAB: m/z
+
+
40.0672 [(M+Na) ; calcd for C H NO S : 340.0672].
1
5
18
4 2
tert-butyl benzofuran-2-ylsulfonyl(phenyl)carbamate (3l). General procedure I was used
employing tert-butyl benzofuran-2-ylsulfonylcarbamate (0.074 g, 0.25 mmol) and
diphenyliodonium triflate (0.269 g, 0.625 mmol), and the reaction was complete in 24 h.
Flash chromatography on silica gel using hexane/dichloromathane (1:1) provided pure 3l
o
(
0.085 g, 0.23 mmol, 91%) as a white solid. mp: 116-118 C; R 0.26 (hexane/ethyl acetate =
f
3
:1); IR (neat) 3120, 2984, 2931, 1738, 1548, 1490, 1374, 1291, 1144, 974, 838, 756, 565
-1 1
cm ; H NMR (300 MHz, CDCl ) 7.74 (d, J = 7.8 Hz, 1H), 7.66-7.36 (m, 9H), 1.35 (s,
3
1
3
9
H); C NMR (75 MHz, CDCl ) 155.6, 150.3, 149.1, 135.6, 129.9, 129.3, 129.2, 128.2,
3
S8

ACCEPTED MANUSCRIPT
+
1
25.7, 124.4, 123.1, 114.8, 112.3, 85.2, 27.7; HRMS-FAB: m/z 396.0877 [(M+Na) ; calcd for
+
C H NNaO S : 396.0876].
19
19
5
tert-butyl p-tolyl(tosyl)carbamate (5a). General procedure I was used employing tert-butyl
tosylcarbamate (0.068 g, 0.25 mmol) and di-p-tolyliodonium triflate (0.149 g, 0.325 mmol),
and the reaction was complete in 6 h. Flash chromatography on silica gel using hexane/ethyl
o
acetate (7:1) provided pure 5a (0.086 g, 0.24 mmol, 95%) as a white solid. mp: 132-134 C;
R 0.56 (hexane/ethyl acetate = 3:1); IR (neat) 2982, 2929, 1733, 1511, 1368, 1290, 1151,
f
-1 1
9
71, 841, 669 cm ; H NMR (300 MHz, CDCl ) 7.86 (d, J = 8.3 Hz, 2H), 7.33 (d, J = 7.7
3
Hz, 2H), 7.22 (d, J = 7.7 Hz, 2H), 7.13 (d, J = 8.3 Hz, 2H), 2.46 (s, 3H), 2.38 (s, 3H), 1.34 (s,
1
3
9
H); C NMR (75 MHz, CDCl ) 151.0, 144.3, 139.0, 136.8, 133.8, 129.8, 129.3, 129.25,
3
+
1
28.5, 84.3, 27.8, 21.6, 21.2; HRMS-FAB: m/z 384.1241 [(M+Na) ; calcd for
+
C H NNaO S : 384.1240].
19
23
4
tert-butyl (4-(tert-butyl)phenyl)(tosyl)carbamate (5b). General procedure I was used
employing tert-butyl tosylcarbamate (0.068 g, 0.25 mmol) and bis(4-(tert-
butyl)phenyl)iodonium triflate (0.176 g, 0.325 mmol), and the reaction was complete in 4 h.
Flash chromatography on silica gel using hexane/ethyl acetate (7:1) provided pure 5b (0.089
o
g, 0.22 mmol, 88%) as a white solid. mp: 156-158 C; R 0.63 (hexane/ethyl acetate = 3:1);
f
-1 1
IR (neat) 2966, 1734, 1368, 1151, 1091, 665, 591 cm ; H NMR (300 MHz, CDCl ) 7.87
3
(d, J = 8.1 Hz, 2H), 7.43 (d, J = 8.4 Hz, 2H), 7.31 (d, J = 8.1 Hz, 2H), 7.18 (d, J = 8.4 Hz,
1
3
2
H), 2.47 (s, 3H), 1.35 (s, 9H), 1.34 (s, 9H); C NMR (75 MHz, CDCl ) 151.9, 151.1,
3
S9

ACCEPTED MANUSCRIPT
1
4
44.3, 137.0, 133.6, 129.3. 129.0, 128.5, 126.1, 84.4, 34.7, 31.3, 27.8, 21.6; HRMS-FAB: m/z
+
+
26.1709 [(M+Na) ; calcd for C H NNaO S : 426.1710].
2
2
29
4
tert-butyl (4-methoxyphenyl)(tosyl)carbamate (5c). General procedure I was used employing
tert-butyl tosylcarbamate (0.068 g, 0.25 mmol) and bis(4-methoxyphenyl)iodonium triflate
(0.159 g, 0.325 mmol), and the reaction was complete in 12 h. Flash chromatography on
silica gel using hexane/ethyl acetate (7:1) provided pure 5c (0.091 g, 0.24 mmol, 96%) as a
1
white solid. R 0.43 (hexane/ethyl acetate = 3:1); H NMR (300 MHz, CDCl ) 7.86 (d, J =
f
3
8
2
1
.4 Hz, 2H), 7.33 (d, J = 8.1 Hz, 2H), 7.16 (dd, J = 6.9 and 2.1 Hz, 2H), 6.92 (d, J = 8.7 Hz,
1
3
H), 3.81 (s, 3H), 2.45 (s, 3H), 1.34 (s, 9H); C NMR (75 MHz, CDCl ) 159.7, 151.0,
3
44.3, 136.7, 130.6, 129.2, 128.9, 128.4, 114.2, 84.2, 55.3, 27.7, 21.5; Data is consistent with
2
that reported in the literature.
tert-butyl tosyl(4-trifluoromethyl)phenyl)carbamate (5d). General procedure I was used
employing tert-butyl
tosylcarbamate (0.068 g, 0.25 mmol) and bis(4-
(trifluoromethyl)phenyl)iodonium triflate (0.184 g, 0.325 mmol), and the reaction was
complete in 8 h. Flash chromatography on silica gel using hexane/ethyl acetate (7:1) provided
o
pure 5d (0.090 g, 0.22 mmol, 87%) as a white solid. mp: 136-138 C; R 0.59 (hexane/ethyl
f
-1 1
acetate = 3:1); IR (neat) 2984, 2931, 1738, 1612, 1326, 1169, 1020, 812, 766, 579 cm ; H
NMR (300 MHz, CDCl ) 7.86 (d, J = 8.3 Hz, 2H), 7.69 (d, J = 8.3 Hz, 2H), 7.37 (t, J = 8.3
3
1
3
Hz, 4H), 2.47 (s, 3H), 1.35 (s, 9H); C NMR (75 MHz, CDCl3) 150.4, 144.9, 139.6,
2
Ankner, T.; Hilmersson, G. Org. Lett. 2009, 11, 503-506
S10

ACCEPTED MANUSCRIPT
1
2
39.59, 136.3, 130.9 (q, J = 33 Hz), 130.3, 129.5, 128.5, 126.2 (q, J = 3.8 Hz), 85.1, 27.7,
+
+
1.6; HRMS-FAB: m/z 438.0957 [(M+Na) ; calcd for C H F NNaO : 438.0957].
1
9
20
3
4
tert-butyl (4-fluorophenyl)(tosyl)carbamate (5e). General procedure I was used employing
tert-butyl tosylcarbamate (0.068 g, 0.25 mmol) and bis(4-fluorophenyl)iodonium triflate
(0.152 g, 0.325 mmol), and the reaction was complete in 6 h. Flash chromatography on silica
gel using hexane/ethyl acetate (7:1) provided pure 5e (0.088 g, 0.24 mmol, 96%) as a white
o
solid. mp: 104-106 C; R 0.56 (hexane/ethyl acetate = 3:1); IR (neat) 3449, 2986, 1733, 1598,
f
-
1 1
1
2
505, 1373, 1093, 975, 842, 671 cm ; H NMR (300 MHz, CDCl ) 7.85 (d, J = 8.4 Hz,
3
H), 7.35 (d, J = 8.0 Hz, 2H), 7.27-7.19 (m, 2H), 7.15-7.06 (s, 2H), 2.46 (s, 3H), 1.35 (s, 9H);
C NMR (75 MHz, CDCl3) 162.6 (d, J = 248 Hz), 150.8, 144.6, 136.5, 132.4 (d, J = 3.6
1
3
Hz), 131.4 (d, J = 8.8 Hz), 129.4, 128.5, 116.0 (d, J = 23 Hz), 84.6, 27.8, 21.6; HRMS-FAB:
+
+
m/z 388.0989 [(M+Na) ; calcd for C H FNNaO S : 388.0989].
1
8
20
4
tert-butyl (4-chlorophenyl)(tosyl)carbamate (5f). General procedure I was used employing
tert-butyl tosylcarbamate (0.068 g, 0.25 mmol) and bis(4-chlorophenyl)iodonium triflate
(0.162 g, 0.325 mmol), and the reaction was complete in 10 h. Flash chromatography on
silica gel using hexane/ethyl acetate (7:1) provided pure 5f (0.088 g, 0.23 mmol, 92%) as a
o
white solid. mp: 132-133 C; R 0.59 (hexane/ethyl acetate = 3:1); IR (neat) 3455, 2980, 1733,
f
-1 1
1
597, 1489, 1373, 1250, 1091, 973, 813, 665 cm ; H NMR (300 MHz, CDCl ) 7.85 (d, J
3
1
3
=
8.0 Hz, 2H), 7.43-7.30 (m, 4H), 7.18 (d, J = 8.4 Hz, 2H), 2.46 (s, 3H), 1.35 (s, 9H); C
NMR (75 MHz, C D ) 151.0, 144.3, 137.6, 136.0, 135.0, 131.6, 129.4 (2C), 129.2, 83.9,
6
6
+
+
2
7.7, 21.2; HRMS-FAB: m/z 404.0694 [(M+Na) ; calcd for C H ClNNaO S : 404.0694].
18 20 4
S11

ACCEPTED MANUSCRIPT
tert-butyl (4-bromophenyl)(tosyl)carbamate (5g). General procedure I was used employing
tert-butyl tosylcarbamate (0.068 g, 0.25 mmol) and bis(4-bromophenyl)iodonium triflate
(0.191 g, 0.325 mmol), and the reaction was complete in 6 h. Flash chromatography on silica
gel using hexane/ethyl acetate (7:1) provided pure 5g (0.102 g, 0.24 mmol, 96%) as a white
o
solid. mp: 148-150 C; R 0.59 (hexane/ethyl acetate = 3:1); IR (neat) 2987, 2931, 1739, 1595,
f
-1 1
1
487, 1284, 1173, 1071, 838, 730, 664, 580 cm ; H NMR (300 MHz, CDCl ) 7.84 (d, J =
3
8
.0 Hz, 2H), 7.55 (d, J = 8.9 Hz, 2H), 7.34 (d, J = 8.5 Hz, 2H), 7.12 (d, J = 8.5 Hz, 2H), 2.47
1
3
(
s, 3H), 1.35 (s, 9H); C NMR (75 MHz, CDCl ) 150.5, 144.7, 136.4, 135.5, 132.3, 131.3,
3
+
1
29.4, 128.6, 123.1, 84.8, 27.8, 21.7; HRMS-FAB: m/z 448.0189 [(M+Na) ; calcd for
+
C H BrNNaO S : 448.0189].
18
20
4
methyl 4-(N-tert-butoxycarbonyl)-4-methylphenylsulfonamido)benzoate (5i). General
procedure I was used employing tert-butyl tosylcarbamate (0.068 g, 0.25 mmol) and
mesityl(4-(methoxycarbonyl)phenyl)iodonium triflate (0.172 g, 0.325 mmol), and the
reaction was complete in 6 h. Flash chromatography on silica gel using hexane/ethyl acetate
o
(
7:1) provided pure 5i (0.092 g, 0.23 mmol, 91%) as a white solid. mp: 140-142 C; R 0.41
f
(hexane/ethyl acetate = 3:1); IR (neat) 2983, 1729, 1605, 1370, 1281, 1150, 702, 661, 548
-1 1
cm ; H NMR (300 MHz, CDCl ) 8.10 (d, J = 8.4 Hz, 2H), 7.86 (d, J = 8.4 Hz, 2H), 7.39-
3
1
3
7
.26 (m, 4H), 3.94 (s, 3H), 2.47 (s, 3H), 1.34 (s, 9H); C NMR (75 MHz, CDCl ) 166.2,
3
1
50.4, 144.8, 140.5, 136.4, 130.5, 135.4, 129.7, 129.4, 128.6, 84.8, 52.3, 27.8, 21.7; HRMS-
+
+
FAB: m/z 428.1138 [(M+Na) ; calcd for C H NNaO S : 428.1138].
2
0
23
6
S12

ACCEPTED MANUSCRIPT
tert-butyl thiophen-3-yl(tosyl)carbamate (5j). General procedure I was used employing tert-
butyl tosylcarbamate (0.068 g, 0.25 mmol) and mesityl(thiophen-3-yl)iodonium triflate
(0.155 g, 0.325 mmol), and the reaction was complete in 16 h. Flash chromatography on
silica gel using hexane/ethyl acetate (7:1) provided pure 5j (0.083 g, 0.235 mmol, 94%) as a
o
white solid. mp: 115-117 C; R 0.52 (hexane/ethyl acetate = 3:1); IR (neat) 3108, 2976, 2360,
f
-
1 1
1
2
734, 1527, 1369, 1148, 812, 636 cm ; H NMR (300 MHz, CDCl ) 7.85 (d, J = 8.0 Hz,
3
1
3
H), 7.36-7.24 (m, 4H), 6.96 (dd, J = 5.0 and 1.1 Hz, 1H), 2.45 (s, 3H), 1.35 (s, 9H); C
NMR (100 MHz, CDCl3) 150.6, 144.5, 136.5, 133.3, 129.3, 128.4, 127.2, 124.8, 124.3,
+
+
8
4.5, 27.8, 21.6; HRMS-FAB: m/z 376.0647 [(M+Na) ; calcd for C H NNaO S :
16 19 4 2
3
76.0648].
tert-butyl (6-bromopyridin-3-yl)(tosyl)carbamate (5k). General procedure I was used
employing tert-butyl tosylcarbamate (0.068 g, 0.25 mmol) and (6-bromopyridin-3-yl)(2,4,6-
triethylphenyl)iodonium triflate (0.193 g, 0.325 mmol), and the reaction was complete in 12
h. Flash chromatography on silica gel using hexane/ethyl acetate (7:1) provided pure 5k
o
(
0.065 g, 0.15 mmol, 61%) as a white solid. mp: 166-168 C; R 0.48 (hexane/ethyl acetate =
f
-1
1
3
:1); IR (neat) 2976, 2360, 1735, 1370, 1285, 1149, 1090, 664, 582 cm ; H NMR (300
MHz, CDCl ) 8.16 (d, J = 2.2 Hz, 1H), 7.83 (d, J = 8.1 Hz, 2H), 7.58 (d, J = 8.7 Hz, 1H),
3
1
3
7
.50 (dd, J = 8.7 and 2.7 Hz, 1H), 7.37 (d, J = 8.1 Hz, 2H), 2.48 (s, 3H), 1.37 (s, 9H); C
NMR (100 MHz, CDCl3) 150.2, 150.0, 145.3, 142.0, 139.8, 135.8, 133.1, 129.6, 128.6,
+
+
1
4
28.5, 85.6, 27.8, 21.7; HRMS-FAB: m/z 449.0141 [(M+Na) ; calcd for C H BrN NaO S :
17 19 2 4
49.0141].
S13

ACCEPTED MANUSCRIPT
tert-butyl (4-bromophenyl)sulfonyl(4-fluorophenyl)carbamate (8). General procedure I was
used employing tert-butyl (4-bromophenyl)sulfonylcarbamate (1.681 g, 5.00 mmol) and
bis(4-fluorophenyl)iodonium triflate (3.030 g, 6.50 mmol), and the reaction was complete in
1
0 h. Flash chromatography on silica gel using hexane/ethyl acetate (10:1) provided pure 8
o
(
2.086 g, 4.85 mmol, 97%) as a white solid. mp: 128-129 C; R 0.62 (hexane/ethyl acetate =
f
4
:1); IR (neat) 3092, 2981, 2939, 1736, 1574, 1506, 1471, 1370, 1147, 1087, 744, 619, 569
-1 1
cm ; H NMR (300 MHz, CDCl ) 7.84 (d, J = 8.7 Hz, 2H), 7.70 (d, J = 8.4 Hz, 2H), 7.25-
3
1
3
7
.03 (m, 4H), 1.35 (s, 9H); C NMR (75 MHz, CDCl ) 162.7 (d, J = 248 Hz), 150.5, 138.3,
3
1
32.1, 132.0, 131.3 (d, J = 8.8 Hz), 130.1, 128.9, 116.2 (d, J = 23 Hz), 85.0, 27.8; HRMS-
+
+
FAB: m/z 430.0123 [(M+H) ; calcd for C H BrFNO S : 430.0124].
1
7
18
4
tert-butyl (4-chlorophenyl)sulfonyl(4-(tert-butyl)phenyl)carbamate (11). General procedure
I was used employing tert-butyl (4-chlorophenyl)sulfonylcarbamate (1.459 g, 5.00 mmol)
and bis(4-(tert-butyl)phenyl)iodonium triflate (3.525 g, 6.50 mmol), and the reaction was
complete in 4 h. Flash chromatography on silica gel using hexane/ethyl acetate (10:1)
o
provided pure 11 (2.077 g, 4.90 mmol, 98%) as a white solid. mp: 156-158 C; R 0.73
f
(hexane/ethyl acetate = 4:1); IR (neat) 2967, 2871, 1734, 1476, 1367, 1171, 1090, 973, 757,
-
1 1
6
2
26, 582 cm ; H NMR (300 MHz, CDCl ) 7.93 (d, J = 8.4 Hz, 2H), 7.52 (d, J = 8.4 Hz,
3
1
3
H), 7.43 (d, J = 8.4 Hz, 2H), 7.16 (d, J = 8.7 Hz, 2H), 1.35 (s, 9H), 1.33 (s, 9H); C NMR
(
75 MHz, CDCl ) 152.1, 150.8, 139.9, 138.2, 133.2, 129.9, 128.9, 128.8, 126.1, 84.6, 34.6,
3
+
+
3
1.1, 27.7; HRMS-FAB: m/z 446.1168 [(M+Na) ; calcd for C H ClNNaO S : 446.1169].
21 26 4
S14

ACCEPTED MANUSCRIPT
One-pot procedure for the production of mono N-arylsulfonamide (Table 4)
Upon completion of General procedure I, as determined by TLC, the reaction mixture
o
(
1.00 mmol scale) was cooled to 0 C. Cold trifluoroacetic acid/water (9/1 mL) was slowly
o
added. The reaction was stirred 1 h at 0 C at which time the reaction was diluted with
toluene. All volatiles were removed with a rotary evaporator, and the product isolated by
silica gel chromatography using the solvent system indicated.
4
-methyl-N-phenylbenzenesulfonamide (12a). The one-pot procedure was used employing
tert-butyl tosylcarbamate (0.271 g, 1.00 mmol) and diphenyliodonium triflate (0.559 g, 1.30
mmol). Flash chromatography on silica gel using hexane/ethyl acetate (5:1) provided pure
1
1
2a (0.210 g, 0.85 mmol, 85%) as a white solid. R 0.59 (hexane/ethyl acetate = 2:1); H
f
NMR (300 MHz, CDCl3) 7.67 (d, J = 8.4 Hz, 2H), 7.29-7.21 (m, 4H), 7.12-7.06 (m, 3H),
1
3
6
1
.91 (br, 1H), 2.37 (s, 3H); C NMR (75 MHz, CDCl ) 143.9, 136.5, 136.0, 129.6, 129.3,
3
3
27.2, 125.3, 121.5, 21.5; Data is consistent with that reported in the literature.
4
-methoxy-N-phenylbenzenesulfonamide (12b). The one-pot procedure was used employing
tert-butyl (4-methoxyphenyl)sulfonylcarbamate (0.287 g, 1.00 mmol) and diphenyliodonium
triflate (0.645 g, 1.50 mmol). Flash chromatography on silica gel using hexane/ethyl acetate
(
5:1) provided pure 12b (0.245 g, 0.93 mmol, 93%) as a white solid. R 0.61
f
1
(
dichloromethane); H NMR (300 MHz, CDCl ) 7.76 (d, J = 9.0 Hz, 2H), 7.61 (br, 1H),
3
1
3
7
.25-7.01 (m, 5H), 6.84 (d, J = 9.0 Hz, 2H), 3.76 (s, 3H); C NMR (75 MHz, CDCl )
3
3
Moon, S. –Y.; Nam, J.; Rathwell, K.; Kim, W. –S. Org. Lett. 2014, 16, 338-341
S15

ACCEPTED MANUSCRIPT
1
63.0, 136.7, 130.3, 129.4, 129.2, 124.9, 121.2, 114.1, 55.4; Data is consistent with that
3
reported in the literature.
4
-chloro-N-phenylbenzenesulfonamide (12c). The one-pot procedure was used employing
tert-butyl (4-chlorophenyl)sulfonylcarbamate (0.292 g, 1.00 mmol) and diphenyliodonium
triflate (0.559 g, 1.30 mmol). Flash chromatography on silica gel using hexane/ethyl acetate
(
5:1) provided pure 12c (0.249 g, 0.89 mmol, 89%) as a white solid.; R 0.62
f
1
(
dichloromethane); H NMR (300 MHz, CDCl ) 7.72 (d, J = 8.7 Hz, 2H), 7.39 (d, J = 8.7
3
1
3
Hz, 2H), 7.28-7.20 (m, 2H), 7.18-7.04 (m, 4H); C NMR (75 MHz, CDCl ) 139.6, 137.3,
3
1
36.0, 129.4, 129.3, 128.7, 125.8, 121.8; Data is consistent with that reported in the
3
literature.
4
-bromo-N-phenylbenzenesulfonamide (12d). The one-pot procedure was used employing
tert-butyl (4-bromophenyl)sulfonylcarbamate (0.292 g, 1.00 mmol) and diphenyliodonium
triflate (0.559 g, 1.30 mmol). Flash chromatography on silica gel using hexane/ethyl acetate
(
5:1) provided pure 12d (0.088 g, 0.83 mmol, 83%) as a white solid.; R 0.62
f
1
(
dichloromethane); H NMR (300 MHz, CDCl ) 7.65 (d, J = 8.6 Hz, 2H), 7.53 (d, J = 8.7
3
1
3
Hz, 2H), 7.49 (br, 1H), 7.28-7.19 (m, 2H), 7.15-7.07 (m, 3H); C NMR (75 MHz, CDCl )
3
1
37.7, 136.0, 132.3, 129.4, 128.7, 128.1, 125.6, 121.7; Data is consistent with that reported in
4
the literature.
4
Gowda, B.T.; Shetty, M; Jayalakshmi, K. L. A: Physical Science, 2004, 59, 239-249.
S16

ACCEPTED MANUSCRIPT
N-(4-fluorophenyl)-4-methylbenzenesulfonamide (12e). The one-pot procedure was used
employing tert-butyl tosylcarbamate (0.271 g, 1.00 mmol) and bis(4-fluorophenyl)iodonium
triflate (0.606 g, 1.30 mmol). Flash chromatography on silica gel using hexane/ethyl acetate
(
5:1) provided pure 12e (0.249 g, 0.94 mmol, 94%) as a white solid.; R 0.45 (hexane/ethyl
f
1
acetate = 2:1); H NMR (300 MHz, CDCl ) 7.60 (d, J = 8.3 Hz, 2H), 7.23 (d, J = 7.9 Hz,
3
1
3
2
H), 7.06-6.98 (m, 2H), 6.97-6.88 (m, 2H), 6.51 (br, 1H), 2.39 (s, 3H); C NMR (75 MHz,
CDCl ) 160.6 (d, J = 244 Hz), 144.0, 135.8, 132.2 (d, J = 1.5 Hz), 129.7, 127.3, 124.9 (d, J =
3
5
8
.3 Hz), 116.1 (d, J = 22 Hz), 21.6; Data is consistent with that reported in the literature.
N-phenylmethanesulfonamide (12f). The one-pot procedure was used employing tert-butyl
methylcarbamate (0.195 g, 1.00 mmol) and diphenyliodonium triflate (0.559 g, 1.30 mmol).
Flash chromatography on silica gel using hexane/ethyl acetate (5:1) provided pure 12f (0.156
1
g, 0.91 mmol, 91%) as a white solid. R 0.20 (dichloromethane); H NMR (300 MHz, CDCl )
f
3
1
3
7
.39-7.33 (m, 2H), 7.26-7.16 (m, 3H), 6.96 (s, 1H), 3.02 (s, 3H); C NMR (75 MHz,
CDCl3) 136.7, 129.7, 125.4, 120.8, 39.2; Data is consistent with that reported in the
3
literature.
N-phenylthiophene-2-sulfonamide (12g). The one-pot procedure was used employing tert-
butyl thiophen-2-ylsulfonylcarbamate (0.263 g, 1.00 mmol) and diphenyliodonium triflate
5
Teo, Y. –C.; Yong, F. –F. Synlett, 2011, 6, 837-843.
S17

ACCEPTED MANUSCRIPT
(0.559 g, 1.30 mmol). Flash chromatography on silica gel using hexane/ethyl acetate (5:1)
provided pure 12g (0.225 g, 0.94 mmol, 94%) as a colorless oil. R 0.43 (hexane/ethyl acetate
f
-1
=
2:1); IR (neat) 3241, 3091, 2825, 1599, 1498, 1404, 1335, 1229, 1153, 1092, 928, 589 cm ;
1
H NMR (300 MHz, CDCl3) 7.53 (dd, J = 5.1 and 1.2 Hz, 1H), 7.49 (dd, J = 3.7 and 1.2
1
3
Hz, 1H), 7.33-7.25 (m, 2H), 7.20-7.10 (m, 3H), 7.03-6.97 (m, 1H), 6.77 (br, 1H); C NMR
(
75 MHz, CDCl ) 139.3, 136.0, 132.9, 132.4, 129.4, 127.3, 125.9, 122.0; HRMS-FAB: m/z
3
+
+
2
61.9966 [(M+Na) ; calcd for C H NNaO S : 261.9967].
10 9 2 2
4
-methyl-N-(thiophen-3-yl)benzenesulfonamide (12h). The one-pot procedure was used
employing tert-butyl tosylcarbamate (0.271 g, 1.00 mmol) and mesityl(thiophen-3-
yl)iodonium triflate (0.622 g, 1.30 mmol). Flash chromatography on silica gel using
hexane/ethyl acetate (5:1) provided pure 12h (0.228 g, 0.90 mmol, 90%) as a white solid. Rf
1
0
7
.45 (hexane/ethyl acetate = 2:1); H NMR (300 MHz, CDCl ) 7.67 (d, J = 8.0 Hz, 2H),
3
.23 (d, J = 8.0 Hz, 2H), 7.20-7.13 (m, 1H), 7.04 (br, 1H), 6.90-6.81 (m, 2H), 2.39 (s, 3H);
1
3
C NMR (75 MHz, CDCl ) 143.9, 135.9, 134.2, 129.6, 127.2, 125.6, 123.3, 113.9, 21.5;
3
3
Data is consistent with that reported in the literature.
N,N-diphenyl-p-toluenesulfonamide (12aa). A 10 mL round bottom flask was charged with
a diphenyliodonium triflate (0.140 g, 0.325 mmol), CuI (10 mol %), triethylamine (0.50
mmol) and the corresponding p-toluenesulfonamide (0.043 g, 0.25 mmol). Toluene (2 mL)
o
was then added to the flask. The reaction mixture was stirred at 50 C. After 24 h complete
consumption of diphenyliodonium triflate was observed by TLC analysis. The solvent was
removed in vacuo and the residue was purified by flash chromatography on silica gel using
S18

ACCEPTED MANUSCRIPT
hexane/ethyl acetate (15:1) provided pure 12aa (0.041 g, 0.13 mmol, 51%) as a white solid.
1
R 0.65 (hexane/ethyl acetate = 2:1); H NMR (300 MHz, CDCl ) 7.58 (d, J = 8.1 Hz, 2H),
f
3
1
3
7
.35-7.21 (m, 12H), 2.42 (s, 3H); C NMR (75 MHz, CDCl ) 143.5, 141.5, 137.5, 129.5,
3
6
1
29.2, 128.3, 127.7, 127.3, 21.5; Data is consistent with that reported in the literature. 12a
1
(
(
(
0.012 g, 0.05 mmol, 19%) as a white solid. R 0.59 (hexane/ethyl acetate = 2:1); H NMR
f
300 MHz, CDCl3) 7.67 (d, J = 8.4 Hz, 2H), 7.29-7.21 (m, 4H), 7.12-7.06 (m, 3H), 6.91
13
br, 1H), 2.37 (s, 3H); C NMR (75 MHz, CDCl ) 143.9, 136.5, 136.0, 129.6, 129.3, 127.2,
3
3
1
25.3, 121.5, 21.5; Data is consistent with that reported in the literature.
6
Nandi, P.; Redko, M. Y.; Petersen, K.; Dye, J. L.; Lefenfeld, M.; Vogt, P. F.; Jackson, J. E. Org. Lett. 2008, 10,
5
441-5444.
S19