The: N -alkylation of sulfonamides with alcohols in water catalyzed by a water-soluble metal-ligand bifunctional iridium complex [Cp?Ir(biimH2)(H2O)][OTf]2

Article abstract of DOI:10.1039/c9nj02542a

The iridium complex [Cp?Ir(biimH₂)(H₂O)][OTf]₂ (Cp? = η⁵-pentamethylcyclopentadienyl, biimH₂ = 2,2′-biimidazole) was synthesized and developed as a new-type of water-soluble metal-ligand bifunctional catalyst for the N-alkylation of poorly nucleophilic sulfonamides with alcohols in water. In the presence of catalyst (1 mol%) and Cs₂CO₃ (0.1 equiv.), a series of desirable products was obtained in 74-91% yields under microwave irradiation. Mechanistic experiments revealed that the presence of NH units in the imidazole ligand is crucially important for the catalytic activity of the iridium complex. Notably, this research would facilitate the process of water-soluble metal-ligand bifunctional catalysis for the hydrogen autotransfer process.

Full text of DOI:10.1039/c9nj02542a

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Jason B. Benedict et al.
The role of atropisomers on the photo-reactivity and fatigue of
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The N-alkylation of sulfonamides with alcohols in water catalyzed
by a water-soluble metal-ligand bifunctional iridium complex
[Cp*Ir(biimH2)(H2O)][OTf]2
Received 00th January 20xx,
Accepted 00th January 20xx
Yao Ai,a Pengcheng Liu,a Ran Liang,a Yan Liu,a and Feng Li*a,b
DOI: 10.1039/x0xx00000x
The iridium complex [Cp*Ir(biimH2)(H2O)][OTf]2 (Cp* = η5-pentamethylcyclopentadienyl, biimH2 = 2,2’-biimidazole) was
synthesized and developed as a new-type of water-soluble metal-ligand bifunctional catalyst for the N-alkylation of poor
nucleophilic sulfonamides with alcohols in water. In the presence of catalyst (1 mol %) and Cs2CO3 (0.1 equiv), a series of
desirable products were obtained in 74-91% yields under microwave irradiation. Mechanistic experiment revealed that the
presence of NH units in the imidazole ligand is crucially important for the catalytic activity of iridium complex. Notably, this
research would facilitate the process of water-soluble metal-ligand bifunctional catalysts for hydrogen autotransfer
process.
www.rsc.org/
[M]
Introduction
R
OH
R
Nuc
The N-alkylation of amines presents one of the most
fundamental and important C-N bond-forming reactions in
organic synthesis.1 Traditionally, such transformations were
performed with alkyl halides as alkylating agents in the
presence of stoichiometric bases. In recent years, much
attention has been directed to the N-alkylation of amines with
alcohols as alkylating agents based on the so-called hydrogen
autotransfer process or hydrogen-borrowing strategy,2 using
ruthenium,3 iridium,4 palladium,5 nickel,6 cobalt,7 iron8 and
manganese catalysts.9 In this process, alcohols are first
dehydrogenated to form aldehydes, followed by the
condensation of the resulting aldehydes with amines afforded
imine intermediates, which are hydrogenated by the metal
hydride species generated in the step of the dehydrogenation
of alcohols to give the final N-alkylated products (Scheme 1).
This methodology is attractive because of high atom efficiency
and the formation of water as the only by-product. Despite
significant advance, most of reactions have to be performed in
[M]
[M-H]
R
R
O
Nuc
Nuc
H2O
Scheme 1. Transition metal-catalyzed N-alkylation of amines with alcohols.
important.10 However, the transition metal-catalyzed N-
alkylation of amines with alcohols to N-alkylated amines in
water remained rarely unexplored and only a few examples
have been reported to date (Scheme 2). Fujita, Yamaguchi and
co-workers demonstrated the N-alkylation of ammonia,
aromatic and aliphatic amines with alcohols in water catalyzed
by a water-soluble iridium complex [Cp*Ir(NH3)3]11 Williams
and co-workers reported also the N-alkylation of aromatic and
aliphatic amines with alcohols in water catalyzed by
organic solvents or using several equiv. of alcohols as solvents, [Cp*IrI2]2.12 However, when poor nucleophilic sulfonamides
were used as substrates, this catalytic system required a
stoichiometric amount of base and the products were
obtained in only low to moderate yields (25%-74%).13-14
Recently, we demonstrated the N-alkylation of sulfonamides
with alcohols in water catalyzed by a water-soluble Cp*Ir
complex bearing a functional 6,6’-dihydroxy-2,2’-bipyridine
which results in the production of a large amount of auxiliary
waste and environmental pollution.
Because water is cheap, safe and environmentally benign
compared with various organic solvents, the development of
catalytic transformations in water has becoming increasingly
ligand [Cp*Ir(6,6’-(OH)2bpy)(H2O)][OTf]2.15,16
A mechanistic
a.School of Chemical Engineering, Nanjing University of Science & Technology,
Nanjing 210094, P. R. China. Fax: (+)86-25-84431939; E-mail: fengli@njust.edu.cn
b.State Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian
116024, P. R. China
investigation revealed that protic hydrogens of OH units in the
bpy ligand are crucially important for the catalytic activity.15 As
a part of our continuing interest in the development of
iridium-catalyzed environmentally friendly reactions,15,17 we
herein wish to describe our effort towards the synthesis of a
Electronic Supplementary Information (ESI) available: 1H NMR and 13C NMR spectra
of all products. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
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I2
[OTf]2
[OTf]2
Table 1. N-alkylation of p-methylbenzenesulfonamide (1a) with benzyl alcohol
2a) under various conditions.a
View Article Online
DOI: 10.1039/C9NJ02542A
HO
(
I
I
I
Ir H2O
OH
Ir H2O
N
Ir
H3N
H3N
Ir
Ir
N
N
Cat. (1 mol %)
NH3
O
O
O O
N
I
Base (0.1 equiv)
S
S
N
NH2
OH
N
+
N
H
H
H
MW, H2O, Temp.
Me
Me
1a
2a
3aa
Fujita, Yamaguchi, 2010
This time
Willamis, 2010
Li, 2014
Entry
Base
Temp. [oC]
Yield [%][b]
Cat.
9
97 (91%[c]
)
Cs2CO3
Cs2CO3
1
2
3
4
5
cat. 1
cat. 2
cat. 1
cat. 1
cat. 1
cat. 1
130
130
130
130
120
110
110
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
7
47
40
71
32
25
Scheme 2. Organometallic catalysts for the N-alkylation of amines with alcohols in
K2CO3
water.
Na2CO3
Cs2CO3
Cs2CO3
Cs2CO3
6
7
water-soluble Cp*Ir complex bearing a functional biimidazole
[Cp*Ir(biimH2)(H2O)][OTf]2 (biimH2 = 2,2’-imidazole) that
contains protic hydrogens and a tautomerism structure like
hydroxypyridine. Furthermore, such complex was developed
[Cp*Ir(biimH2)Cl]Cl
-
Cs2CO3
8
100
n.d.
a Reactions conditions: 1a (1 mmol), 2a (1.2 mmol), [Cp*Ir(biimH2)(H2O)][OTf]2 (1
as a new-type of water-soluble metal-ligand bifunctional mol %), Cs2CO3 (0.1 equiv), H2O (1 mL), MW, 130 oC, 2 h. Isolated yield.
b
c
2 (2
catalyst for the N-alkylation of sulfonamides with alcohols in
water.
mmol), Cs2CO3 (0.2 equiv).
product 3aa was obtained in 25% yield (Table 1, entry 7). No
reaction took place in the presence of Cs2CO3 alone (Table 1,
entry 8).
Results and discussion
With the established catalytic system in hand, we
investigated the scope of reaction with respect of alcohols and
these results are summarized in Table 2. Reactions of benzylic
alcohols bearing an electron-donating substituent, such as
methyl and p-methoxy groups, gave the desired products 3ab-
3ad in 82-84% yields (Table 2, entries 1-3). Similarly, benzylic
alcohols bearing an electron-withdrawing group, such as m-
methoxy or a halide atom (fluorine, chlorine and bromine),
were successfully converted to the corresponding products
3ae-3ai in 81-91% yields (Table 2, entries 4-8). Stronger
electron-withdrawing substituents, such as trifluoromethyl and
trifluoromethoxy groups, were also tolerated and the
corresponding products 3aj and 3ak were obtained in 80% and
88%, respectively (Table 2, entries 9-10). Transformations of 1-
naphthalenemethanol proceeded smoothly to afford the
desired product 3al in 84% yield (Table 2, entry 11). In the case
of aliphatic alcohols, such as 1-butanol, 1-hexanol and cyclic
alcohol, the corresponding products 3am-3ao were obtained
in 74-78% yields (Table 2, entries 12-14).
Water-soluble Cp*Ir complexes employed in this work were
synthesized outlined in Scheme 3. The reaction of
o
[Cp*Ir(biimH2)Cl]Cl and AgOTf (2.2 equiv) carried out at 60 C
in H2O for 12 h to give the product [Cp*Ir(biimH2)H2O][OTf]2 in
59% yield.1 This complex could also be prepared in 65% yield
8
through the reaction of [Cp*Ir(H2O)3][OTf]2 with 2,2’-
biimidazole (1.2 equiv) in water at 60 oC for 12 h. The
analogous
complex
[Cp*Ir(biimMe2)H2O][OTf]2
was
synthesized in 61% yield by the later method. These two
complexes are very stable to air and moisture.
Cl
[OTf]2
[OTf]2
Ir Cl
N
Ir H2O
N
AgOTf
2,2'-biimidazole
N
N
Ir
N
H2O, 60 o
C
H2O
H2O
H2O, 60 o
C
N
OH2
N
R
N
R
R
R
cat. 1, R = H
cat. 2, R = Me
Scheme
3.
The
synthesis
of
water-soluble
iridium
complexes
The scope of reaction with respect to sulfonamides was
[Cp*Ir(biimR2)(H2O)][OTf]2 (R = H, Me).
then evaluated (Table
benzenesulfonamides bearing
3). The N-alkylation of
an electron-donating
We next investigated their catalytic activity for the N-
substituent, such as methyl and methoxy groups, afforded the
desired products 3ba and 3ca with 80% and 87% yields,
respectively (Table 3, entries 1-2). When benzenesulfonamides
bearing a halide atom or a more serious electron-withdrawing
substituent were served, reactions gave the corresponding
products 3da-3ha in 84-90% yields (Table 3, entries 3-7).
Benzenesulfonamide and naphthalenesulfonamide were also
proven to be suitable substrates and the desired products 3ia
and 3ja were obtained with 83% and 85% yields, respectively
alkylation of p-methylbenzenesulfonamide (1a) with benzyl
alcohol
(2a
)
in
water.
In
the
presence
of
[Cp*Ir(biimH2)H2O][OTf]2 (cat.
1
) (1 mol %) and Cs2CO3 (0.1
equiv), the reaction was performed at 130 °C for 2 h in a
focused, single mode microwave synthesizer (Discover CEM,
USA, 300 W) to afford the desired product 3aa in 97% yield
(Table 1, entry 1). Using [Cp*Ir(biimMe2)H2O][OTf]2 (cat.
2) as
an alternative catalyst, only 7% yield was obtained (Table 1,
entry 2). Apparently, NH units in the ligand have a significant (Table 3, entries 8-9). Apart from aromatic sulfonamides,
aliphatic ones, including phenylmethyl, methyl and cyclopropyl
groups, were successfully converted into the desired products
On the basis of experimental results, a plausible mechanism
was proposed to account for the present N-alkylation of
sulfonamides with alcohols in water catalyzed by
effect on the catalytic activity of Cp*Ir complex. cat.
1 was
chosen as the catalyst for further research. Attempts to use
K2CO3 and Na2CO3 as alternative bases, and decrease the
reaction temperature resulted in relatively low yields (Table 1,
entries 3-6). When [Cp*Ir(biimH2)Cl]Cl was utilized, the
2 | J. Name., 2012, 00, 1-3
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Table 2. N-alkylation with respect of alcohols in watera
Table 3. N-alkylation with respect of sulfonamides in watera
View Article Online
DOI: 10.1039/C9NJ02542A
O
O
cat. 1 (1 mol %)
Cs2CO3 (0.1 equiv)
cat. 1 (1 mol %)
O
S
O
O
O
S
O
O
Cs2CO3 (0.1 equiv)
S
OH
N
R
NH2
R
N
S
+
R
OH
+
H
MW, H2O, 130 oC, 2 h
MW, H2O, 130 oC, 2 h
Product
R
NH2
H
Me
Me
1a
2
3
1
2a
Sulfonamide
Me
3
Alcohol
Me
Product
Yield (%)b
Entry
Yield (%)b
Entry
Me
O
O
Me
O O
O
O
S
OH
N
S
S
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
H
1
83
NH2
N
H
Me
Me
Me
Me
1
2
80
2b
2c
2d
2e
3ab
1b
3ba
O
O
O
S
O
O O
S
S
OH
OH
N
H
2
3
4
82
84
82
NH2
N
Me
Me
H
87
84
3ac
MeO
MeO
O
O
1c
3ca
S
O
O
O O
N
H
S
S
NH2
N
MeO
MeO
OMe
OMe
H
3
3ad
F
F
O
O
1d
3da
S
OH
OH
N
H
O
O
O O
S
S
NH2
N
3ae
H
4
85
87
O
O
Cl
Cl
Br
S
1e
3ea
N
H
O
S
O
O O
5
86
F
Me
F
S
NH2
N
H
2f
3af
5
6
7
8
Cl
Cl
O
O
Br
S
1f
3fa
OH
OH
N
H
6
7
81
90
O
S
O
O O
Me
Me
S
2g
2h
3ag
NH2
N
H
O
O
90
88
83
S
F3C
F3C
N
H
1g
3ga
Cl
Cl
O
S
O
O O
3ah
S
NH2
N
H
O
O
S
F3CO
F3CO
OH
OH
OH
N
H
8
9
91
1h
3ha
Br
Me
Me
Me
Br
O
S
O
O O
2i
3ai
S
O
O
NH2
N
H
S
N
H
80
88
1i
3ia
F3C
CF3
2j
3aj
O
O
O O
O
O
S
S
NH2
NH2
N
H
S
N
H
9
85
78
10
F3CO
OCF3
1j
3ja
2k
3ak
O
O
O O
S
O
O
S
10
N
H
S
OH
OH
N
H
11
12
84
Me
Me
Me
1k
3ka
2l
3al
O
O
O O
O
O
S
S
S
Me
NH2
Me
N
H
N
H
11
12
76
83
76c
1l
3la
2m
3am
O
S
O
O O
S
O
O
S
NH2
N
H
N
H
13
14
78c
OH
OH
1m
3ma
2n
2o
3an
a Reactions conditions:
1 (1 mmol), 2a (1.2 mmol), [Cp*Ir(biimH2)(H2O)][OTf]2 (1
O
O
S
mol %), Cs2CO3 (0.1 equiv), H2O (1 mL), MW, 130 oC, 2 h. b Isolated yield.
N
H
74c
Me
3ao
[Cp*Ir(biimH2)(H2O)][OTf]2 (Scheme 4). The initial step of the
reaction involved the formation of unsaturated species
the deprotonation through the reaction
A
by
of
a Reactions conditions: 1a (1 mmol),
mol %), Cs2CO3 (0.1 equiv), H2O (1 mL), MW, 130 oC, 2 h. b Isolated yield.
2
(1.2 mmol), [Cp*Ir(biimH2)(H2O)][OTf]2 (1
c
2 (2
[Cp*Ir(biimH2)(H2O)][OTf]2 and Cs2CO3, and the dissociation
through the elimination of water. Accompanied by the
activation of alcohols, the ligand accepted a proton to give
mmol), Cs2CO3 (0.2 equiv).
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O
O
Cat. (1 mol %)
Cs2CO3 (0.1 equiv)
alkoxy iridium species
elimination to give iridium hydride species
B
, which then underwent ß-hydrogen
and aldehydes.
O
S
O
View Article Online
S
N
OH
DOI: 10.1039/C9NJ02542A
C
H
+
N
MW, H2O, 130 oC, 2 h
Me
Ph
The condensation between the resulting aldehydes and
sulfonamides occurred to give unsaturated sulfonimine
intermediates. Furthermore, the simultaneous transfer of the
hydride on iridium and the proton on the bisimidazole ligand
Me
4
2a
3a
a
[OTf]2
[OTf]2
of species
which resulted in the liberation of N-alkylated products and
the regeneration of catalytic active species Similar
C to the C=N bond of sulfonimine intermediates,
Ir H2O
N
Ir H2O
N
N
N
N
N
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
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31
32
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43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
A
.
N
N
H
Me
H
Me
mechanism for the simultaneous delivery of hydride and
proton to ketones or imines was proposed in metal-ligand
bifunctional catalysts, such as Shvo’s catalyst,19 and Noyori-
Ikariya catalysts.20
cat. 1, 80% yield
cat. 2, 0% yield
Scheme 5. The hydrogen transfer between a sulfonimine and an alcohol.
[OTf]2
Conclusion
Ir H2O
N
We have synthesized
a
water-soluble iridium complex
N
N
[Cp*Ir(biimH2)(H2O)][OTf]2 and developed it as a new-type of metal-
ligand bifunctional catalyst for the N-alkylation of poor nucleophilic
sulfonamides with alcohols in water. In the presence of catalyst (1
mol %) and Cs2CO3 (0.1 equiv), a series of desirable products were
obtained in 74-90% yields under microwave irradiation. Mechanistic
experiment revealed that the presence of NH units in the imidazole
ligand is crucially important for the catalytic activity of iridium
complex. Notably, this research would facilitate the process of
water-soluble metal-ligand bifunctional catalysts for hydrogen
autotransfer process.
N
H
H
-2HOTf, -H2O
base
O
O
S
R2
OH
R1
N
R2
Ir
H
N
N
N
N
A
H
R2
H
Ir
Experimental Section
O
S
R1
Ir
O
N
R2
N
O
N
N
N
N
N
N
General Experimental Details. High-resolution mass spectra (HRMS)
were obtained on Thermo Scientific LTQ Orbitrap XL spectrometer
and are reported as m/z (relative intensity). Accurate masses are
reported for the molecular ion. Melting points were measured on a
X-6 micro-melting apparatus. Proton nuclear magnetic resonance
(1H NMR) spectra were recorded at 500 MHz using a Bruker Avance
500 spectrometer. Chemical shifts are reported in delta (δ) units,
parts per million (ppm) downfield from trimethylsilane or ppm
relative to the center of the singlet at 7.26 ppm for CDCl3 and 2.50
ppm for DMSO-d6. Coupling constants J values are reported in Hertz
(Hz), and the splitting patterns were designated as follows: s, singlet;
d, doublet; t, triplet; m, multiplet; b, broad. Carbon-13 nuclear
magnetic resonance (13C NMR) spectra were recorded at 125 MHz
using a Bruker Avance 500 spectrometer. Chemical shifts are
reported in delta (δ) units, ppm relative to the center of the triplet
at 77.0 ppm for CDCl3 and 39.5 ppm for DMSO-d6. 13C NMR spectra
were routinely run with broadband decoupling. All reactions were
run under an atmosphere of nitrogen, unless otherwise indicated.
Analytical thin-layer chromatography (TLC) was carried out using
0.2-mm commercial silica gel plates.
N
H
H
C
B
R2
O
+
H2O
O
O
Ir
H
S
N
R1
NH2
N
N
N
: vacant site
R1, R2 = Aryl or aliphatic group
H
C
Scheme 4. The proposed reaction mechanism.
To support the proposed reaction mechanism, the catalytic
hydrogen transfer of a sulfonimine with an alcohol as a
hydrogen source in water was investigated (Scheme 5). In the
[Cp*Ir(biimH2)(Cl)]18 and [Cp*Ir(H2O)3][OTf]2 were synthesized by
21
the according to previous reports.
presence of cat.
1 (1 mol %) and Cs2CO3 (0.1 equiv), the
reaction of (E)-N-benzylidene-4-methylbenzenesulfonamide
(4), which is synthesized by the condensation between p-
methylbenzenesulfonamide and benzaldehyde, with 2a
proceeded for 2 h in water at 130 oC under microwave
irradiation to afford the product 3aa in 80% yield, although the
Procedure for the synthesis of [Cp*Ir(biimH2)(H2O)][OTf]2. Method
1: To an oven-dried Schlenk tube were added [Cp*Ir(biimH2)(Cl)] (67
mg, 0.126 mmol), AgOTf (71 mg, 0.277 mmol) and H2O (3 mL), and
the mixture was heated at 60 oC for 12 h. The reaction mixture was
allowed to cool to ambient temperature. Then, the precipitate was
hydration of a part of starting materials occurred. Using cat. 2
as an alternative catalyst, all starting materials were hydrated
and none of 3aa was found under same conditions.
filtered, and the filtrate was concentrated in vacuo to afford the
product. Yellow solid, 59% yield (58 mg). H NMR (500 MHz, D2O) δ
1
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7.61-7.50 (m, 4ꢀH), 1.76 (s, 15ꢀH); 13C NMR (125 MHz, D2O) δ 140.6, 2H), 6.77 (d, J = 8.0 Hz, 2H), 4.85 (br s, 1H), 4.03 (d, JV=iew5.A9rtiHclez,O2nHlin)e,
126.9, 121.4, 87.3, 8.2; 19F NMR (470 MHz, D2O) δ -80.7; HRMS (ESI) 3.76 (s, 3H), 2.43 (s, 3H); 13C NMR (125 MHz, CDCl ) δ 159.2, 143.3,
DOI: 10.31039/C9NJ02542A
m/z calcd for C16H20N4Ir [M-(OTf)2-H2O-H]+ 461.13117, found 136.8, 129.6, 129.2, 128.3, 127.1, 113.9, 55.2, 46.7, 21.5.
461.13113
N-(4-Fluorobenzyl)-4-methylbenzenesulfonamide (3af).25 White
solid, 86% yield (240 mg); mp 93-94 oC; H NMR (500 MHz, CDCl3) δ
1
Method 2: To an oven-dried Schlenk tube were added
[Cp*Ir(H2O)3][OTf]2 (86 mg, 0.126 mmol), 2,2’-Biimidazole (20 mg,
0.150 mmol) and H2O (3 mL), and the mixture was heated at 60 C
for 12 h. The reaction mixture was allowed to cool to ambient
temperature. Then, the precipitate was filtered, and the filtrate was
concentrated in vacuo to afford the product in 65% yield (64 mg).
7.72 (d, J = 7.8 Hz, 2H), 7.28 (d, J = 7.7 Hz, 2ꢀH), 7.15 (dd, J = 8.2 Hz
and 5.6 Hz, 2ꢀH), 6.92 (t, J = 8.4 Hz, 2ꢀH), 4.91 (br s, 1ꢀH), 4.07 (s, 2ꢀH),
2.42 (s, 3ꢀH); 13C NMR (125 MHz, CDCl3) δ 162.3 (d, JC-F = 246.7 Hz),
143.5, 136.8, 132.2, 129.7, 129.6 (d, JC-F = 8.2 Hz), 127.1 , 115.4 (d,
JC-F = 21.6 Hz), 46.4, 21.5.
o
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
N-(2-Chlorobenzyl)-4-methylbenzenesulfonamide (3ag).26 White
solid, 81% yield (239 mg); mp 66-67 oC; 1H NMR (500 MHz, CDCl3) δ
7.70 (d, J = 8.4 Hz, 2H), 7.24-7.31 (m, 4H), 7.14-7.21 (m, 2H), 5.00 (s,
2H), 4.23 (d, J = 6.1 Hz, 2H), 2.41 (s, 3H); 13C NMR (125 MHz, CDCl3)
δ 143.4, 136.9, 133.9, 133.3, 130.3, 129.6, 129.4,129.2, 127.1, 45.1,
21.5.
Procedure for the synthesis of [Cp*Ir(biimMe2)(H2O)][OTf]2. To an
oven-dried Schlenk tube were added [Cp*Ir(H2O)3][OTf]2 (86 mg,
0.126 mmol), 1-methyl-2-(1-methylimidazol-2-yl)imidazole (24 mg,
o
0.148 mmol) and H2O (3 mL), and the mixture was heated at 60 C
for 12 h. The reaction mixture was allowed to cool to ambient
temperature. Then, the precipitate was filtered, and the filtrate was
concentrated in vacuo to afford the product in 61% yield (62 mg).
1H NMR (500 MHz, D2O) δ 7.59 (s, 2ꢀH), 7.48 (s, 2ꢀH), 4.24 (s, 6ꢀH),
1.76 (s, 15ꢀH); 13C NMR (125 MHz, D2O) δ 141.5, 127.9, 127.3, 87.5,
37.9, 8.2; 19F NMR (470 MHz, D2O) δ -80.7; HRMS (ESI) m/z calcd for
C18H24N4Ir [M-(OTf)2-H2O-H]+ 489.16247, found 489.16257.
N-(4-Chlorobenzyl)-4-methylbenzenesulfonamide (3ah).14b White
solid, 90% yield (266 mg); mp 103-105 oC; 1H NMR (500 MHz, CDCl3)
δ 7.72 (d, J = 7.6 Hz, 2H), 7.29 (d, J = 7.3 Hz, 2H), 7.22 (d, J = 7.5 Hz,
2H), 7.13 (d, J = 7.2 Hz, 2H), 5.20 (br s, 1ꢀH), 4.07 (s, 2H), 2.44 (s, 3H);
13C NMR (125 MHz, CDCl3) δ 143.7, 136.8, 134.8, 133.8, 129.8, 129.2,
128.8, 127.1, 46.6, 21.5.
General procedure for the N-alkylation of sulfonamides with
alcohols in water catalyzed by Cp*Ir(biimH2)(H2O)][OTf]2.
N-(4-Bromobenzyl)-4-methylbenzenesulfonamide (3ai).27 White
solid, 91% yield (310 mg); mp 118-119 oC; 1H NMR (500 MHz, CDCl3)
δ 7.70 (d, J = 7.4 Hz, 2H), 7.35 (d, J = 7.8 Hz, 2H), 7.27 (d, J = 7.4 Hz,
2H), 7.05 (d, J = 7.7 Hz, 2H), 5.24 (br s, 1H), 4.05 (s, 2H), 2.43 (s, 3H);
13C NMR (125 MHz, CDCl3) δ 143.5, 136.7, 135.4, 131.5, 129.6, 129.5,
127.0, 121.6, 46.4, 21.4.
sulfonamides
(1
mmol),
alcohols
(1.2
mmol),
[Cp*Ir(biimH2)(H2O)][OTf]2 (7.8 mg, 0.01 mmol, 1 mol %), Cs2CO3 (33
mg, 0.1 mmol, 0.1 equiv) and water (1 mL) were added to a
microwave vial containing a stirrer bar. The vial was then placed in a
focused, single-mode microwave synthesizer (Discover CEM, USA)
at 130 C for 2 h (300 W, sealed reaction vessel), and was then
o
cooled to ambient temperature. The reaction mixture was
concentrated under vacuum and purified by flash column
chromatography with hexanes/ethyl acetate to afford the
corresponding product.
N-[4-(Trifluoromethyl)benzyl]-4-methylbenzenesulfonamide
1
(3aj).14h White solid, 80% yield (263 mg); mp 136-137 oC; H NMR
(500 MHz, DMSO-d6) δ 8.22 (br s, 1ꢀH), 7.66 (d, J = 8.2 Hz, 2H), 7.62
(d, J = 8.1 Hz, 2H), 7.45 (d, J = 7.9 Hz, 2H), 7.35 (d, J = 7.9 Hz, 2H),
4.07 (s, 2H), 2.37 (s, 3H); 13C NMR (125 MHz, DMSO-d6) δ 143.6,
138.8, 130.5, 129.2, 128.7 (q, JC-F = 31.9 Hz), 127.5, 127.2, 126.3,
126.0, 125.2 (q, JC-F = 272.2 Hz), 46.5, 21.8.
N-Benzyl-4-methylbenzenesulfonamide (3aa).14b White solid, 91%
1
yield (238 mg); mp 113-114 oC; H NMR (500 MHz, CDCl3) δ 7.74 (d,
J = 8.4 Hz, 2H), 7.29-7.24 (m, 5H), 7.19-7.18 (m, 2H), 4.09 (d, J = 6.0
Hz, 2H), 2.42 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 143.4, 136.8,
136.3, 129.7, 128.6, 127.8, 127.8, 127.1, 47.1, 21.4.
N-[4-(Trifluoromethoxy)benzyl]-4-methylbenzenesulfonamide
1
(3ak).15 White solid, 88% yield (305 mg); mp 85-86 oC; H NMR (500
MHz, DMSO) δ 8.15 (br s, 1ꢀH), 7.64 (d, J = 8.2 Hz, 2ꢀH), 7.34 (d, J =
8.2 Hz, 4ꢀH), 7.25 (d, J = 8.7 Hz, 2H), 3.99 (ds, 2ꢀH), 2.36 (s, 3ꢀH); 13C
NMR (125 MHz, DMSO) δ 148.3, 143.6, 138.8, 138.2, 130.5, 130.4,
127.5, 121.8, 121.2 (q, JC-F = 255.3 Hz), 46.4, 21.8.
N-(2-Methylbenzyl)-4-methylbenzenesulfonamide (3ab).22 White
solid, 83% yield (229 mg); mp 119-120 oC; 1H NMR (500 MHz, CDCl3)
δ 7.74 (d, J = 8.2 Hz, 2H), 7.28 (d, J = 8.1 Hz, 2H), 7.15 (t, J = 7.0 Hz,
1H), 7.11-7.06 (m, 3H), 4.06 (s, 2H), 2.43 (s, 3H), 2.23 (s, 3H); 13C
NMR (125 MHz, CDCl3) δ 143.4, 136.6, 133.9, 130.5, 129.7, 128.8,
128.1,127.1, 126.1, 45.3, 21.4, 18.7.
4-Methyl-N-(naphthalen-2-ylmethyl)benzenesulfonamide (3al).14a
White solid, 84% yield (262 mg); mp 145-146 oC; 1H NMR (500 MHz,
CDCl3) δ 7.88-7.75 (m, 5H), 7.47 (s, 1H), 7.32-7.27 (m, 4H), 4.52 (s,
2H), 2.43(s, 3H); 13C NMR (125 MHz, CDCl3) δ 143.5, 136.5, 133.7,
131.3, 131.1, 129.7, 129.0, 128.7. 127.2, 126.9, 126.7, 126.0, 125.2,
123.2, 45.4, 21.5.
N-(3-Methoxybenzyl)-4-methylbenzenesulfonamide
(3ac).14b
1
White solid, 82% yield, (239 mg); mp 83-84 oC; H NMR (500 MHz,
CDCl3) δ 7.74 (s, 2H), 7.28-7.16 (m, 3H), 6.76-6.71 (m, 3H), 4.99 (br s,
1H), 4.07 (s, 2H), 3.72 (s, 3H), 2.42 (s, 3H); 13C NMR (125 MHz, CDCl3)
δ 159.7, 143.4, 137.8, 136.8, 129.7, 129.6, 127.1, 120.0, 113.6,
113.0, 55.1, 47.1, 21.4.
N-Hexyl-4-methylbenzenesulfonamide (3am).14b White solid, 76%
yield (194 mg); mp 62-63 oC; 1H NMR (500 MHz, CDCl3) δ 7.75 (d, J =
8.3 Hz, 2H), 7.31 (d, J = 7.9 Hz, 2H), 4.54 (br s, 1ꢀH), 2.92 (q, J = 6.8
Hz, 2H), 2.43 (s, 3H), 1.47-1.41 (m, 2H), 1.26-1.19 (m, 6H), 0.84 (t, J
= 6.9 Hz, 3H); 13C NMR (125 MHz, CDCl3) δ 143.3, 137.0, 129.6,
127.1, 43.2, 31.2, 29.5, 26.1, 22.4, 21.5, 13.9.
N-(4-Methylbenzyl)-4-methylbenzenesulfonamide (3ad).23 White
1
solid, 82% yield (226 mg); mp 90-91 oC; H NMR (500 MHz, CDCl3) δ
7.74 (d, J = 7.7 Hz, 2H), 7.29 (d, J = 7.8 Hz, 2H), 7.06 (s, 4H), 4.85 (br
s, 1H), 4.05 (s, 2H), 2.43 (s, 3H), 2.30 (s, 3H); 13C NMR (125 MHz,
CDCl3) δ 143.8, 143.2, 139.5, 136.6, 129.8, 128.5, 127.5, 127.0, 46.4,
44.4, 21.5.
N-isopentyl-4-methylbenzenesulfonamide (3an).27 Oil, 78% yield
(187 mg); H NMR (500 MHz, CDCl3) δ 7.75 (d, J = 8.4 Hz, 2H), 7.30
1
(d, J = 8.3 Hz, 2H), 4.78 (br s, 1H), 2.92 (q, J = 7.4 Hz, 2H), 2.43 (s, 3H),
1.53-1.61 (m, 1H), 1.31-1.35 (m, 2H), 0.81 (d, J = 6.7 Hz, 6H); 13C
NMR (125 MHz, CDCl3) δ 143.3, 137.0, 129.6, 127.1, 43.2, 31.2, 29.5,
26.1, 22.4, 21.5, 13.9.
N-(4-Methoxybenzyl)-4-methylbenzenesulfonamide (3ae).24 White
solid, 84% yield (245 mg); mp 120-121 oC; 1H NMR (500 MHz, CDCl3)
δ 7.73 (d, J = 7.7 Hz, 2H), 7.29 (d, J = 7.7 Hz, 2H), 7.09 (d, J = 8.0 Hz,
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N-(Cyclohexylmethyl)-4-methylbenzenesulfonamide
(3ao).14a N-Benzyl(phenyl)methanesulfonamide (3ka).30 White solid, 78%
View Article Online
1
1
White solid, 74% yield (198 mg); mp 80-81 oC; H NMR (500 MHz, yield (204 mg); mp 147-148 oC; H NMR (5D00OIM: 10H.z10, 3C9D/CC9l3N) Jδ0275.4328A-
CDCl3) δ 7.75 (d, J = 8.1 Hz, 2H), 7.30 (d, J = 7.9 Hz, 2H), 4.91 (br s, 7.26 (m, 10H), 4.19 (s, 2H), 4.13 (s, 2H); 13C NMR (125 MHz, CDCl3) δ
1ꢀH), 2.73 (d, J = 5.9 Hz, 2H), 2.42 (s, 3H), 1.67-1.60 (m, 5H), 1.40- 136.8, 130.6, 129.1, 128.8, 128.0, 59.3, 47.6.
1.38 (m, 1ꢀH), 1.17-1.07 (m, 3H), 0.88-0.80 (m, 2H); 13C NMR (125
MHz, CDCl3) δ 143.1, 137.0, 129.6, 127.0, 49.3, 37.6, 30.5, 26.2, 25.6, N-Benzylmethanesulfonamide (3la).30 White solid, 76% yield (141
21.4.
1
mg); mp 58-59 oC; H NMR (500 MHz,CDCl3) δ 7.37-7.30 (m, 5H),
4.30 (s, 2H), 2.84 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 136.7, 128.8,
N-Benzyl-2-methylbenzenesulfonamide (3ba).14h White solid, 80% 128.0, 127.9, 47.1, 40.0.
yield (209 mg); mp 57-58 oC; 1H NMR (500 MHz, CDCl3) δ 7.99 (d, J =
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
7.6 Hz, 1H), 7.46 (t, J = 7.3 Hz, 1H), 7.34-7.24 (m, 5H), 7.16-7.15 (m, N-Benzylcyclopropanesulfonamide (3ma).14b White solid, 83% yield
2H), 4.79 (br s, 1H), 4.11 (d, J = 5.9 Hz, 2H), 2.61 (s, 3H); 13C NMR (176 mg); mp 54-55 oC; H NMR (500 MHz, CDCl3) δ 7.36-7.30 (m,
(125 MHz, CDCl3) δ 137.7, 137.0, 136.2, 132.8, 132.5, 129.6, 128.7, 5ꢀH), 4.87 (br s, 1ꢀH), 4.32 (d, J = 5.1 Hz, 2H), 2.34-2.32 (m, 1H), 1.14-
127.9, 126.2, 47.1, 20.3.
1
1.23 (m, 2H), 0.91 (d, J = 7.7 Hz, 2H); 13C NMR (125 MHz, CDCl3) δ
137.1, 128.7, 127.9, 127.8, 47.2, 30.5, 5.4.
N-Benzyl-4-methoxybenzenesulfonamide (3ca).28 White solid, 87%
yield (241 mg); mp 106-107 oC; 1H NMR (500 MHz, CDCl3) δ 7.79 (d, J Procedure for hydrogen transfer between 4 and 2a catalyzed by
= 8.8 Hz, 2H), 7.28-7.24 (m, 3H), 7.18 (d, J = 7.8 Hz, 2H), 6.96 (d, J = Cp*Ir(biimH2)(H2O)][OTf]2 (Scheme 5). (E)-N-benzylidene-4-
8.9 Hz, 2H), 4.49 (br s, 1H), 4.10 (d, J = 5.1 Hz, 2H), 3.87 (s, 3H); 13C methylbenzenesulfonamide 4 (1 mmol), benzyl alcohol 2a (1.2
NMR (125 MHz, CDCl3) δ 162.9, 136.3, 131.4, 129.3, 128.6, 127.8, mmol), cat. 1 (7.8 mg, 1 mol %), Cs2CO3 (33 mg, 0.1 mmol, 0.1
114.2, 55.6, 47.2.
equiv) and water (1 mL) were added to a microwave vial containing
a stirrer bar. The vial was then placed in a focused, single-mode
N-Benzyl-4-fluorobenzenesulfonamide (3da).14b White solid, 82% microwave synthesizer (Discover CEM, USA) at 130 C for 2 h (300
yield (217 mg); mp 95-97 oC; 1H NMR (500 MHz, CDCl3) δ 7.84 (dd, J W, sealed reaction vessel), and was then cooled to ambient
= 8.7 Hz and 5.1 Hz, 2H), 7.25-7.24 (m, 3H), 7.17-7.12 (m, 4H), 4.80 temperature. The reaction mixture was concentrated under
o
(br s, 1H), 4.13 (s, 2H); 13C NMR (125 MHz, CDCl3) δ 165.0 (d, JC-F
=
254.2 Hz), 136.0, 129.7 (d, JC-F = 9.3 Hz), 128.6, 127.9, 127.8, 116.2 hexanes/ethyl acetate to afford the corresponding product 3aa in
vacuum and purified by flash column chromatography with
(d, JC-F = 22.6 Hz), 47.2.
80% yield (209 mg).
N-Benzyl-4-chlorobenzenesulfonamide (3ea).14b White solid, 85%
yield (239 mg); mp 100-101 oC; 1H NMR (500 MHz,CDCl3) δ 7.78 (d, J Acknowledgements
= 7.8 Hz, 1H), 7.46 (d, J = 7.8 Hz, 2H), 7.32-7.25 (m, 5H), 7.28-7.26
(m, 3H), 7.19-7.17 (m, 2H), 4.82 (br s, 1H), 4.15 (s, 2H); 13C NMR
(125 MHz, CDCl3) δ 139.2, 138.5, 135.9, 129.4, 128.8, 128.6, 128.1,
127.9, 47.3.
Financial support by National Natural Science Foundation of
China (21272115), Natural Science Foundation of Jiangsu
Province (BK20161494) and the State Key Laboratory of Fine
Chemicals (KF1704) is greatly appreciated.
N-Benzyl-4-bromobenzenesulfonamide (3fa).14b White solid, 87%
yield (284 mg); mp 119-120 oC; 1H NMR (500 MHz,CDCl3) δ 7.69 (d, J
= 8.0 Hz, 2ꢀH), 7.60 (d, J = 8.0 Hz, 2H), 7.25 (s, 3H), 7.17 (s, 2H), 5.03
(br s, 1H), 4.13 (s, 2H); 13C NMR (125 MHz, CDCl3) δ 139.0, 135.9,
132.3, 128.7, 128.6, 128.0, 127.8, 127.6, 47.2.
Notes and references
1
M. B. Smith and J. March, in March’s Advanced Organic
Chemistry, Wiley-Interscience, New York, 2001, pp. 499-501.
For selected reviews, see: (a) M. H. S. A. Hamid, P. A. Slatford
and J. M. J. Williams, Adv. Synth. Catal., 2007, 349, 1555-
1575; (b) G. E. Dobereiner and R. H. Grabtree, Chem. Rev.,
2010, 110, 681-703; (c) G. Guillena, D. Ramon and M. Yus,
Chem. Rev., 2010, 110, 1611-1641; (d) S. Bahn, S. Imm, L.
Neubert, M. Zhang, H. Neumann and M. Beller,
N-Benzyl-4-(trifluoromethyl)benzenesulfonamide (3ga).29 White
solid, 90% yield (284 mg); mp 114-115 oC; 1H NMR (500 MHz, CDCl3)
δ 7.95 (d, J = 8.3 Hz, 2H), 7.73 (d, J = 8.6 Hz, 2H), 7.26-7.25 (m, 3H),
7.17-7.17 (m, 2H), 4.19 (s, 2H); 13C NMR (125 MHz, DMSO) δ 145.8,
138.2, 133.0 (q, JC-F = 31.9 Hz), 129.2, 128.6, 128.4, 128.1, 127.3,
124.5 (q, JC-F = 272.2 Hz), 47.1.
2
ChemCatChem, 2011, 3, 1853-1864; (e) Q. Yang, Q. Wang
N-Benzyl-4-(trifluoromethoxy)benzenesulfonamide (3ha).14b White
solid, 88% yield (292 mg); mp 110-111 oC; 1H NMR (500 MHz, CDCl3)
δ 7.85 (d, J = 8.8 Hz, 2H), 7.27-7.23 (m, 5H), 7.16-7.15 (m, 2H), 4.47
(br s, 1H), 4.15 (s, 2H); 13C NMR (125 MHz, CDCl3) δ 151.9, 138.7,
136.0, 129.2, 128.6, 127.9, 127.9, 120.9, 120.2 (q, JC-F = 259.7 Hz),
47.3.
and Z. Yu, Chem. Soc. Rev., 2015, 44, 2305-2329; (f) A. Corma,
J. Navas and M. J. Sabater, Chem. Rev., 2018, 118, 1410-1459.
For selected examples, see: (a) M. H. S. A. Hamid and J. M. J.
Williams, Chem. Commun., 2007, 725-727; (b) C. Gunanathan
and D. Milstein, Angew. Chem. Int. Ed., 2008, 47, 8661-8664;
(c) S. Bahn, A. Tillack, S. Imm, K. Mevius, D. Michalik, D.
3
Hollmann, L. Neubert and M. Beller, ChemSusChem, 2009,
．
2,
551-557; (d) D Pingen, C. Muller and D. Vogt, Angew. Chem.
N-Benzylbenzenesulfonamide (3ia).14h White solid, 83% yield;(205
1
mg); mp 86-87 oC; H NMR (500 MHz, CDCl3) δ 7.86 (d, J = 7.5 Hz,
Int. Ed., 2010, 49, 8130-8133; (e) S. Bahn, S. Imm, K. Mevius,
L. Neubert, A. Tillack, J. M. J. Williams and M. Beller, Chem.
Eur. J., 2010, 16, 3590-3593; (f) S. Imm, S. Bahn, M. Zhang, L.
Neubert, H. Neumann, F. Klasovsky, J. Pfeffer, T. Haas and M.
Beller, Angew. Chem. Int. Ed., 2011, 50, 7599-7603; (g) M.
Zhang, S. Imm, S. Bahn, H. Neumann and M. Beller, Angew.
Chem. Int. Ed., 2011, 50, 11197-11201; (h) A. J. A. Watson, A.
2H), 7.57 (t, J = 7.1 Hz, 1H), 7.49 (t, J = 7.9 Hz, 2H), 7.24 (d, J = 6.8 Hz,
3H), 7.18-7.17 (m, 2H), 4.85 (brs, 1H), 4.12 (s, 2H); 13C NMR (125
MHz, CDCl3) δ 139.8, 136.2, 132.6, 129.1, 128.6, 127.8, 127.0, 47.1.
N-Benzylnaphthalene-2-sulfonamide (3ja).14b White solid, 85%
1
yield (253 mg); mp 105-106 oC; H NMR (500 MHz, CDCl3) δ 8.43 (s,
1ꢀH), 7.95-7.90 (m, 3H), 7.63 (dd, J = 8.7 Hz and 1.8 Hz, 1H), 7.67-
7.60 (m, 2H), 7.25-7.17 (m, 5H), 4.16 (s, 2H); 13C NMR (125 MHz,
CDCl3) δ 136.6, 136.1, 134.8, 132.1, 129.5, 129.2, 128.8, 128.7,
128.6, 127.9, 127.9, 127.6, 122.3, 47.4.
C. Maxwell and J. M. J. Williams, J. Org. Chem., 2011, 76
,
2328-2331; (i) D. Weickmann, W. Frey and B. Plietker, Chem.-
Eur. J., 2013, 19, 2741-2748; (j) K. O. Marichev and J. M.
Takacs, ACS Catal., 2016, 6, 2205-2210; (k) J. J. A. Celaje, X.
6 | J. Name., 2012, 00, 1-3
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