One-Pot Bimetallic Pd/Cu-Catalyzed Synthesis of Sulfonamides from Boronic Acids, DABSO and O-Benzoyl Hydroxylamines

Article abstract of DOI:10.1002/asia.201601732

A practical and straightforward bimetallic Pd/Cu catalytic system has been developed. This system affords various sulfonamides in one pot from easy-to-handle and readily available boronic acids, sulfur dioxide surrogate DABSO and O-benzoyl hydroxylamines in high yields. Without additional ligands, the newly developed catalytic system revealed a broad substrate scope for both partners and tolerated a wide array of functional groups even at low catalyst loadings. Furthermore, based on control experiments, a plausible mechanism has been proposed, in which sodium sulfinate has been isolated and identified as the crucial intermediate for this transformation.

Full text of DOI:10.1002/asia.201601732

CHEMISTRY
AN ASIAN JOURNAL
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Accepted Article
Title: One-pot Bimetallic Pd-Cu Catalyzed Synthesis of Sulfonamides
from Boronic Acids, DABSO and O-Benzoyl Hydroxylamines
Authors: Tao Tu, Haibo Zhu, Yajing Shen, Qinyue Deng, and Changyu
Huang
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To be cited as: Chem. Asian J. 10.1002/asia.201601732
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10.1002/asia.201601732
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One-pot Bimetallic Pd-Cu Catalyzed Synthesis of Sulfonamides
from Boronic Acids, DABSO and O-Benzoyl Hydroxylamines
Haibo Zhu,[a] Yajing Shen,[a] Qinyue Deng,[a] Changyu Huang[a] and Tao Tu*[a,b]
Abstract: A practical and straightforward bimetallic Pd-Cu catalytic
system has been successfully developed for synthesis of
sulfonamides in one-pot manner from easily handle and readily
available boronic acids, sulfur dioxide surrogate DABSO and O-
benzoyl hydroxylamines in high yields. Without additional ligands,
the newly developed catalytic system reveals a broad substrate
scope for both partners and tolerates a wide array of functional
groups even at low catalyst loadings. Furthermore, based on the
control experiments, a plausible mechanism has been proposed, in
which sodium sulfinate has been isolated and identified as the
crucial intermediate for this straightforward bimetallic catalytic
transformation.
amino nucleophiles in these transformations restricted to
hydrazines,[10-12] probably, due to their different necleophility in
comparsion to corresponding amines (Scheme 1a). As a new
kind of electrophilic nitrogen source, O-benzoyl hydroxylamines
have attracted considerable attention because of their easy
preparation and high activity of the N-O bond.[13] However, their
activity in the transition-metal catalyzed electrophilic amination
reactions has been less studied, especially, there is no
precedent utilizing O-benzoyl hydroxylamines as amine sources
in the formation of sulfonamides by the palladium-catalyzed
aminosulfonylation, especially, in one-pot manner.
Introduction
Sulfonamides are versatile building blocks in organic
syntheses.[1] The functionality is broadly featured in
pharmaceuticals,[2] agrochemicals[3] and food additives.[4] The
conventional oxidative methods for their preparation exhibited
severe limitations.[5] For example, aromatic sulfonamides are
generally prepared from the corresponding sulfonyl chlorides
with amines. The harsh reaction conditions employed for the
preparation of sulfonyl chlorides render a number of functional
groups intolerable.[6] Therefore, there is an significant interest in
the development of efficient, practical and straightforward
methodologies to construct the functionality.[7].
Scheme 1. Synthesis of sulfonamides by a) Pd-catalyzed aminosulfonylation
with hydrazines; b) Cu-catalyzed electrophilic amination with O-benzoyl
hydroxylamines; c) this work, bimetal catalyzed aminosulfonylation of boronic
acids with O-benzoyl hydroxylamines in one-pot manner.
Despite the great success of the Pd-catalyzed carbonylation
reactions,[8] the direct utilization of readily available sulfur dioxide
gas for sulfonylation constituted as
probably due to the amphoteric property of SO2 and its possible
multiple coordination modes with the metal center. By using
a
challenging task,[9]
DABSO
(DABCO•(SO2)2:
1,4-diazabicyclo[2.2.2]octane
Recently, we have realized the first copper-catalyzed
bis(sulfur dioxide) adduct,) as SO2 surrogate, Willis and co-
workers accomplished the first example of palladium-catalyzed
aminosulfonylation of aryl halides.[10] Wu and co-workers further
extended this strategy for aminosulfonylation of aryl boronic
acids employing K2S2O5 as the SO2 source.[11] However, the
electrophilic amination of sodium sulfinates by using O-benzoyl
hydroxylamines to produce
a broad range of functional
sulfonamides in good to excellent yields under ambient reaction
conditions without additional base and ligands (Scheme 1b).[14]
However, in comparison with aryl boronic acids and aryl halides,
the availability of sodium sulfinates is rather limited.[15] In light of
possible active sulfinate intermediates involved in the tansition-
metal catalyzed sulfinylation of aryl halides or aryl boronic
acids,[16,17] we sought to explore the possibility to deliver
[a]
[b]
H. Zhu, Y. Shen, Q. Deng, C. Huang, Prof. T. Tu
Department of Chemistry
Fudan University
220 Handan Road, Shanghai, 200433 (China)
E-mail: taotu@fudan.edu.cn
Prof. T. Tu
sulfonamides
in
combination
of
palladium-catalyzed
sulfinylation and copper-catalyzed electrophilic amination
sequences (Scheme 1c). Although, there are a numbered
examples of one-pot catalytic processes to access aryl
sulfonamides,[18] in which sensitive organometallic reagents,
ligands or oxidants usually involved, a more practical catalytic
system avoiding to using sensitive auxiliary reagents for the
State Key Laboratory of Organometallic Chemistry
Shanghai Institute of Organic Chemistry
Chinese Academy of Sciences, Shanghai, 200032 (China)
Supporting Information and the ORCID identification number(s) for
the author(s) of this article can be found under
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10.1002/asia.201601732
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synthesis of a variety of functional sulfonamides under one
general protocol is still higly desirable. Herein, we developed an
operationally simple and efficient bimetal catalytic three-
component system to directly produce various functional
sulfonamides from commerical available aryl and alkenyl boronic
acids, DABSO and O-benzoyl hydroxylamines under mild
reaction conditions in one-pot manner.
prepared using the conventional oxidative methodology,[6] even
with some mild oxidants. Pleasingly, naphthalene-2-boronic acid
even produced a quantitative yield (9a, 99%). In addition, a
number of heteroaromatic boronic acids were well compatible in
this catalytic system, with N, O, S heterocyclic substrates
delivering the corresponding sulfonamides in good to excellent
yields (9b-13). Again, in the case of heterocyclic sulfide, a 97%
isolated yield was obtained, and the structure of compound 13
was unambiguously demonstrated by X-ray diffraction analysis
(In the inset of Table 1). Owing to the side coupling reactions of
thiophen-3-ylboronic acid, none desired sulfonamide product 14
was detected when the reaction was carried out under the
optimized reaction conditions. However, reducing the first
sulfinylation step to 30 minutes, a moderate yield (54%) could be
still achieved. Remarkably, the protocol was readily extended to
Results and Discussion
Optimization of one-pot Bimetallic Pd-Cu Catalyzed
Synthesis of Sulfonamides: Initially, 5 mol% Pd(OAc)2 was
directly added into the reaction mixture along with 5 mol% CuBr,
4-tert-butylphenylboronic
acid
(1a)
and
O-benzoyl
the
challenging
alkenyl
boronic
acids.
The
1-
hydroxylmorpholine (2a) in dichloroethane (DCE), whereas, no
desired product was formed, even at the elevated reaction
temperature with extended reaction time. After carefully
investigation (see SI), we found that only when Pd(OAc)2 was
applied to catalyze the sulfinylation of 1a with DABSO and TBAB
cyclohexenylboronic acid afforded the corresponding product 15
in a 71% yield.
Table 1. Optimization of the reaction conditions.[a]
o
(1.0 eq.) in DCE at 80 C for 5 h first, then Na2CO3, 5 mol%
CuBr2 and 2a were added subsequently, sulfonamide product 3
could be isolated in a 34% yield (Table 1, entry 1). Notably, after
the sulfinylation step, the temperature could be cooled to room
temperature for the later operation and no obvious yield
dropping was found. when other solvents were probed, such as
dioxane and DMF, inferior yields were obtained (Table 1, entries
2-3). And even no product was detected when THF and toluene
was used (Table 1, entries 4-5). Remarkably, the yield could be
dramatically improved to 73% when MeOH was used instead
(Table 1, entry 6). Delightedly, quantitative yield was achieved
with the mixture solvents containing MeOH and dioxane in a 1:1
v/v ratio (Table 1, entry 7).[17b] In the cases of other organic or
inorganic bases including Et3N, Cs2CO3 and K2CO3,
unsatisfactory yields were attained (Table 1, entries 8-10).
Without base addition, no transforamtion was mornitered.
Further decreasing the catalyst loadings of Pd(OAc)2 to 2 mol%
also led to the drop of yield (Table 1, entry 11). It's worth noting
that when the reaction was carried out without CuBr2, no product
was detected under the identical reaction conditions (Table 1,
entry 12).
With a defined catalytic protocol in hand, an intensive
assessment of the scope of boronic acids was then carried out
(Table 2). Aryl boronic acids bearing electronic-donating and
electronic-withdrawing groups were fully investigated (4-8), good
to excellent yields were obtained under the optimized reaction
conditions. The substrates with electron-donating groups proved
to be more effective (5, 6a and 7 vs 6b). In the case of the
substrates bearing strong-withdrawing groups, including -CF3, -
CN, -NO2, only trace amount of products were observed. The
relative position of substituents on the phenyl rings of boronic
acids hardly hampered the bi-metal system catalytic process
efficiency; slightly differences were observed in the yields with o-,
m-, p-isomers (5a-c, 88-95%). In the case of 4-
thiomethylphenylboronic acid bearing sulfide group with strong
coordination ability, an unexpected excellent yield was obtained
to produce sulfide-sulfonamide 8a (93%), a product difficult to
Entry
1
Solvent
DCE
Base
Na2CO3
Yield (%)[b]
34
2
3
Dioxane
DMF
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Na2CO3
Et3N
25
23
4
THF
NR
NR
73
5
Toluene
6
MeOH
7
Dioxane/MeOH
Dioxane/MeOH
Dioxane/MeOH
Dioxane/MeOH
Dioxane/MeOH
Dioxane/MeOH
>99
48
8
9
Cs2CO3
K2CO3
45
10
11[c]
12[d]
82
Na2CO3
Na2CO3
87
NR
[a] Reaction conditions: boronic acid (0.5 mmol, 1.0 equiv.), Pd(OAc)2 (5
mol%), TBAB (1.0 equiv.) and DABSO (1.0 equiv.) were stirred in solvent (2
mL) at 80 oC for 5 h., base (2.0 equiv), CuBr2 (5 mol%) and O-benzoyl
hydroxylamine (2.0 equiv) were added subsequently in the reaction mixture
and stirred at room temperature for additional 12 h. [b] Isolated yield. [c] With 2
mol% Pd(OAc)2. [d] Without CuBr2.
Subsequently, we sought to investigate the protocol feasibility
toward electrophilic O-benzoyl hydroxylamines (2, Table 3).
Apparently, the ring size of cyclic amines strongly affected the
transformation: pyrrolidine and piperidine derivatives delivered
good yields (80% and 90% for 16a and 16b, respectively).
However, only a 60% yield was received with product 16c, when
the azepane analogue was involved, probably due to the steric
hindrance. Intriguingly, other six-member-ring substrates proved
be effective substrates for this type of transformation, N-phenyl-
piperazine, N-Boc-piperazine and 1,2,3,4-tetrahydroisoquinoline
derivatives all afforded corresponding products in good yields
(17a, 17b and 18). Furthermore, the activity of the acyclic O-
benzoyl hydroxylamines was also investigated in the bimetal
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10.1002/asia.201601732
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catalytic system under the standard conditions. To our delight,
good to excellent yields were also observed with products 19-22,
regardless of the alkyl chain length. Particularly, challenging N-
allylmethylamine-substituted product could also be delivered in
moderate yield (22, 66%), allowing for its further transformation.
Other electrophilic acyclic amines bearing (heterocyclic-)aryl
groups were able to produce the corresponding sulfonamides in
good to excellent yields (23-27). These further demonstrated
that electronic and steric properties of the substituents in the
amines were fully compatible. When methyl-(2-thiophen-2-yl-
ethyl)-amine was applied, again a 78% yield was obtained for
product 27.
Furthermore, the crucial intermediate sodium 4-tert-
butylbenzenesulfinate (29) was isolated in 80% yield after the
sulfinylation and Na2CO3 addition and confirmed by NMR
analysis (equation 3).
Table 3. Scope of cyclic and acyclic O-benzoylhydroxylamines in the one-pot
bimetal catalyzed preparation of sulphonamides[a]
Table 2. Scope of aryl, heteroaryl and alkenyl boronic acids in the one-pot
bimetal catalyzed preparation of sulfonamides.[a]
[a] Reaction was carried out under the optimized conditions. [b] Isolated yield.
[c] 30 mins for the sulfinylation step.
In view of CuBr readily generated from CuBr2 by coordination
of copper to sodium sulfonate via a free sulfonyl radical
route,[15a,19] CuBr was used directly instead of CuBr2 under the
standard reactions conditions, sulfonamide 3 was isolated in
86% yield under the standard conditions. Unlike CuBr2, even
with TEMPO addition, a 33% yield of sulfonamide was still
obtained.
[a] Reaction was carried out under the optimized conditions. [b] Isolated yield.
[c] 30 mins for the sulfinylation step.
Optimization of one-pot Bimetallic Pd-Cu Catalyzed
Synthesis of Sulfonamides: In order to elucidate the plausible
reaction mechanism for this bimetallic catalytic system, several
control experiments were carried out (Scheme 2). When the
reaction was treated with TEMPO, a radical scavenger, no
desired product was detected under the optimized reaction
conditions (equation 1). However, with TEMPO addition, when
tert-butyl bromoacetate was applied instead of CuBr2 and O-
benzoyl hydroxylmorpholine after Na2CO3 addition, sulfone 28
was still isolated in 45% yield. In contrast, without TEMPO, a
99% yield was obtained for compound 28 (equation 2). These
tests suggested that the possible intermediate arylsulfinate may
be generated in the first Pd-catalyzed sulfinylation step, and a
radical pathway might be involved in the later reaction
sequences, especially in the Cu-catalyzed amination step.
Scheme 2. Control experiments for mechanism investigation.
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handled under N2. Anhydrous methanol (MeOH) was distilled from
anhydrous calcium chloride, Dioxane, Tetrahydrofuran (THF) and
Toluene were distilled from sodium/benzophenone, 1,2-Dichloroethane
(DCE) were distilled from calcium hydride prior to use. All schlenk tubes
and sealed vessels (50 mL) were purchased from Beijing Synthware
Glass. CDCl3 was purchased from Cambridge Isotope Laboratories.1H
NMR and 13C NMR spectra were recorded on Jeol ECA-400 and Bruker
400 DRX spectrometers. 13C NMR spectra were referenced to the carbon
signal of CDCl3 (77.0 ppm). GC-MS spectra were recorded on Agilent
Technologies 1890A GC system and 5975C inert MSD with Triple-Axis
Detector.
With all information in hand, in combination with our previous
study,[14] a plausible mechanism for this one-pot bi-metal
catalytic reaction is proposed (Scheme 3). Initially, the Pd(II)
species reacts with the aryl boronic acid by trans-metalation and
further undergoes SO2 insertion to afford Pd(II) species A.[20] In
the presence of TBAB, the sulfinylation catalytic cycle is
regenerated with concurrent formation of ammonium sulfinate,
which is subsequently converted to sodium sulfinate after
sodium carbonate addition. CuBr is formed via a free sulfonyl
radical manner from CuBr2 and sodium sulfinate.[15a,19] It then
reacts with sodium sulfinate by the second trans-metalation to
form CuI intermediate B. Oxidative addition with O-benzoyl
hydroxylamine gives the CuIII intermediate C, which readily
delivers the sulfonamide product and BzO-CuI by reductive
elimination due to the crowed steric environment around CuIII
center.[21] CuBr is regenerated from BzO-CuI subsequently to
complete the amination catalytic cycle.
General protocol for bimetallic catalyzed sulfonamination: To a 50
mL Schlenk tube containing boronic acid (0.5 mmol), DABSO (1.0 eq.),
TBAB (1.0 eq.) and Pd(OAc)2 (5 mol%), purged with N2 for 3 times, 2 mL
of Dioxane/MeOH (1:1) mixture was added. The resulted reaction mixture
o
was allowed to stir for 5 h. at 80 C under nitrogen atmosphere. Na2CO3
(2.0 eq.) was then added to the reaction mixture and stirred for additional
5 min. Subsequently, O-benzoyl hydroxylamine (2.0 eq.) and CuBr2 (5
mol%) were added and allowed to stir for additional 12 h. After reaction
completion, the reaction mixture was concentrated under the vacuum
and directly purified by flash chromatography to give the desired product.
4-[[4-(1,1-Dimethylethyl)phenyl]sulfonyl]morpholine (3): white solid, >99%
yield. 1H NMR (400 MHz, CDCl3, 298 K) δ = 7.67 (d, J = 8.4 Hz, 2H),
7.55 (d, J = 8.4 Hz, 2H), 3.75 (t, J = 4.4 Hz, 4H), 3.00 (t, J = 4.0 Hz, 4H),
1.35 (s, 9H); 13C NMR (100 MHz, CDCl3, 298 K, ppm) δ = 156.83, 131.89,
127.75, 126.05, 66.08, 45.94, 35.16, 31.03.
4-(Phenylsulfonyl)morpholine (4): white solid, 91% yield. 1H NMR (400
MHz, CDCl3, 298 K) δ = 7.77-7.75 (m, 2H), 7.65-7.61 (m, 1H), 7.58-7.54
(m, 2H), 3.74 (t, J = 5.0 Hz, 4H), 3.00 (t, J = 5.0 Hz, 4H); 13C NMR (100
MHz, CDCl3, 298 K, ppm) δ 135.00, 133.03, 129.08, 127.77, 66.02,
45.92.
Scheme 3. Plausible mechanism for the one-pot bimetal catalyzed amino
sulfonylation of aryl boronic acid.
4-[(2-Methylphenyl)sulfonyl]morpholine (5a): white solid, 88% yield. 1H
NMR (400 MHz, CDCl3, 298 K) δ = 7.89 (d, J = 8.0 Hz, 1H), 7.50-7.46 (m,
1H), 7.35-7.33 (m, 2H), 3.72 (t, J = 4.4 Hz, 4H), 3.15 (t, J = 4.8 Hz, 4H),
2.65 (s, 3H); 13C NMR: (100 MHz, CDCl3, 298 K, ppm) δ = 138.05,
134.82, 133.02, 132.84, 130.34, 126.09, 66.21, 45.22, 20.75.
Conclusions
4-[(3-Methylphenyl)sulfonyl]morpholine (5b): white solid, 90% yield. 1H
NMR (400 MHz, 298 K): δ = 7.75-7.73 (m, 2H), 7.44-7.43 (m, 2H), 3.74 (t,
J = 4.4 Hz, 4H), 3.00 (t, J = 4.8 Hz, 4H), 2.45 (s, 3H); 13C NMR (100 MHz,
CDCl3, 298 K, ppm) δ = 139.34, 134.82, 133.85, 128.94, 128.07, 124.98,
66.06, 45.96, 21.35.
In conclusion, we have successfully developed an efficient
bimetal catalytic system to delivery structurally diverse
sulfonamides from readily available boronic acids, DABSO and
O-benzoyl hydroxylamines under mild reaction conditions in
one-pot manner. Notably, even without ligands assistance,
Pd(OAc)2 and CuBr2 work cooperatively for a broad spectrum of
both partners with dramatic structural variation. A plausible
4-[(4-Methylphenyl)sulfonyl]morpholine (5c): white solid, 95% yield. 1H
NMR (400 MHz, CDCl3, 298 K) δ = 7.64 (d, J = 8.0 Hz, 2H), 7.35 (d, J =
8.0 Hz, 2H), 3.74 (t, J = 4.8 Hz, 4H), 2.98 (t, J = 4.8 Hz, 4H), 2.45 (s, 3H);
13C NMR (100 MHz, CDCl3, 298 K, ppm) δ = 143.92, 131.99, 129.71,
127.87, 66.07, 45.96, 21.52.
mechanism, involved with
a sodium sulfinate as a key
intermediate, has been proposed. The study represents the
diverse example of (hetero)aryl and alkenyl sulfonamides
synthesis in one-pot bimetallic Pd-Cu catalytic system by using
electrophilic O-benzoyl hydroxylamines directly.
4-[(4-Methoxyphenyl)sulfonyl]morpholine (6a): white solid, 97% yield. 1H
NMR (400 MHz, CDCl3, 298 K) δ = 7.69 (d, J = 8.8 Hz, 2H), 7.01 (d, J =
8.8 Hz, 2H), 3.88 (s, 3H), 3.74 (t, J = 4.4 Hz, 4H), 2.98 (t, J = 4.4 Hz, 4H);
13C NMR (100 MHz, CDCl3, ppm) δ = 163.19, 129.94, 126.54, 114.24,
66.03, 55.61, 45.96.
Experimental Section
4-[(4-4-fluorophenyl)sulfonyl]morpholine (6b): yellow solid, 78% yield. 1H
NMR (400 MHz, CDCl3, 298 K) δ = 7.79-7.76 (m, 2H), 7.24-7.22 (m, 2H),
3.75 (t, J = 4.4 Hz, 4H), 3.00 (t, J = 4.8 Hz, 4H); 13C NMR (100 MHz,
General: All commercial reagents were used directly without further
purification, unless otherwise stated. Dry dimethylsulfoxide (DMSO) was
purchased from J & K chemical, stored over 4 Å molecular sieves and
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10.1002/asia.201601732
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CDCl3, ppm) δ = 166.63, 164.09, 130.55, 130.46, 116.55, 116.32, 66.02,
45.93; 19F NMR (CDCl3, 376 MHz, 298 K): δ = -104.47.
46.07; HR-MS (ESI): m/z 334.0572 (Calcd. [M+H]+), 334.0557 (Found.
[M+H]+).
1
4-[(3,5-dimethylphenyl)sulfonyl]morpholine (7): white solid, 98% yield. H
4-(3-thienylsulfonyl)morpholine (14): white solid, 54% yield. 1H NMR (400
MHz, CDCl3, 298 K) δ = 7.92-7.91 (m, 1H), 7.49-7.47 (m, 1H), 7.29 (d, J
= 4.8 Hz, 1H), 3.76 (t, J = 4.4 Hz, 4H), 3.04 (t, J = 4.8 Hz, 4H); 13C NMR
(100 MHz, CDCl3, 298K, ppm) δ = 135.34, 131.11, 127.93, 125.96, 66.04,
45.87.
NMR (400 MHz, CDCl3, 298 K) δ = 7.35 (s, 2H), 7.24 (s, 1H), 3.75 (t, J =
4.4 Hz, 4H), 2.99 (t, J = 4.4 Hz, 4H), 2.40 (s, 6H); 13C NMR (100 MHz,
CDCl3, 298 K, ppm) δ = 139.13, 134.76, 134.67, 125.34, 66.09, 45.99,
21.24.
4-[[4-(methylthio)phenyl]sulfonyl]morpholine (8a): colourless oil, 93%
yield. 1H NMR (400 MHz, CDCl3, 298 K) δ = 7.64 (d, J = 7.6 Hz, 2H),
7.33 (d, J = 8.0 Hz, 2H), 3.74 (t, J = 4.4 Hz, 4H), 2.99 (t, J = 4.0 Hz, 4H),
2.54 (s, 3H); 13C NMR (100 MHz, CDCl3, ppm) δ = 146.26, 130.58,
128.06, 125.29, 65.99, 45.90, 14.70.
4-(1-cyclohexen-1-ylsulfonyl)morpholine (15): colourless oil, 71% yield.
1H NMR (400 MHz, CDCl3, 298 K) δ = 6.79-6.77 (m, 1H), 3.74 (t, J = 4.4
Hz, 4H), 3.17 (t, J = 4.8 Hz, 4H), 2.31-2.25 (m, 4H), 1.76-1.70 (m, 4H),
1.67-1.61 (m, 4H); 13C NMR (100 MHz, CDCl3, 298 K, ppm) δ = 139.09,
136.18, 66.54, 45.59, 25.35, 24.41, 21.91, 20.92.
1
4-([1,1'-biphenyl]-4-ylsulfonyl)morpholine (8b): white solid, 79% yield. H
1-[(4-tert-butylphenyl)sulfonyl]pyrrolidine (16a): yellow solid,, 80% yield.
1H NMR (400 MHz, CDCl3, 298 K) δ = 7.75 (d, J = 7.6 Hz, 2H), 7.52 (d, J
= 8.0 Hz, 2H), 3.25 (t, J = 6.0 Hz, 4H), 1.76 (t, J = 6.0 Hz, 4H), 1.35 (s,
9H); 13C NMR (100 MHz, CDCl3, 298K, ppm) δ = 156.16, 133.89, 127.37,
125.90, 47.84, 35.08, 31.06, 25.17.
NMR (400 MHz, CDCl3, 298 K) δ = 7.84-7.82 (m, 2H), 7.77-7.75 (m, 2H),
7.63-7.61 (m, 2H), 7.53-7.44 (m, 3H), 3.78 (t, J = 4.4 Hz, 4H), 3.06 (t, J =
4.8 Hz, 4H); 13C NMR (100 MHz, CDCl3, ppm) δ = 146.02, 139.14,
133.59, 129.08, 128.58, 128.37, 127.73, 127.33, 66.10, 45.99.
4-(2-naphthalenylsulfonyl)morpholine (9a): white solid, 99% yield. 1H
NMR (400 MHz, CDCl3, 298 K) δ = 8.34 (S, 1H), 8.01-7.93 (m, 3H), 7.75
(d, J = 11.2 Hz, 1H), 7.70-7.62 (m, 2H), 3.75 (t, J = 4.8 Hz, 4H), 3.07 (t, J
= 4.4 Hz, 4H); 13C NMR (100 MHz, CDCl3, 298 K, ppm) δ = 134.94,
132.24, 132.15, 129.29, 129.22, 129.20, 128.96, 127.93, 127.66, 122.92,
66.09, 46.04.
1-[(4-tert-butylphenyl))sulfonyl]piperidine (16b): yellow solid,, 90% yield.
1H NMR (400 MHz, CDCl3, 298 K) δ = 7.67 (d, J = 8.4 Hz, 2H), 7.52 (d, J
= 8.4 Hz, 2H), 2.99 (t, J = 5.6 Hz, 4H), 1.67-1.62 (m, 4H), 1.45-1.39 (m,
2H), 1.35 (s, 9H); 13C NMR (100 MHz, CDCl3, 298K, ppm) δ = 156.15,
133.21, 127.52, 125.82, 46.86, 35.08, 31.06, 25.16, 23.46.
Hexahydro-1-[(4-4-tert-butylphenyl))sulfonyl]-1H-azepine (16c): colour-
less oil, 60% yield. 1H NMR (400 MHz, CDCl3, 298 K) δ = 7.70 (d, J = 8.4
Hz, 2H), 7.49 (d, J = 8.4 Hz, 2H), 3.27 (t, J = 5.6 Hz, 4H), 1.75-1.69 (m,
4H), 1.61-1.58 (m, 4H), 1.34 (s, 9H); 13C NMR (100 MHz, CDCl3, 298K,
ppm) δ = 155.74, 136.47, 126.73, 125.86, 48.17, 35.02, 31.06, 29.19,
26.84.
4-(6-quinolinylsulfonyl)morpholine (9b): white solid, 92% yield. 1H NMR
(400 MHz, CDCl3, 298 K) δ = 9.09-9.08 (m, 1H), 8.34-8.26 (m, 3H), 7.99
(d, J = 8.8 Hz, 1H), 7.59-7.56 (m, 1H), 3.76 (t, J = 4.4 Hz, 4H), 3.09 (t, J =
4.4 Hz, 4H); 13C NMR (100 MHz, CDCl3, 298K, ppm) δ = 153.18, 149.38,
137.15, 133.25, 131.02, 129.19, 127.28, 126.58, 122.65, 66.02, 45.98;
HR-MS (ESI): m/z 279.0803 (Calcd. [M+H]+), 279.0797 (Found. [M+H]+).
1-[[4-(1,1-dimethylethyl)phenyl]sulfonyl]-4-phenylpiperazine (17a): white
solid, 72% yield. 1H NMR (400 MHz, CDCl3, 298 K) δ = 7.71 (d, J = 8.4
Hz, 2H), 7.55 (d, J = 8.4 Hz, 2H), 7.29-7.22 (m, 2H), 6.96-6.93 (m, 3H),
3.27-3.22 (m, 8H), 1.35 (s, 9H); 13CNMR (100 MHz, CDCl3, 298K, ppm) δ
= 156.77, 150.62, 132.15, 129.23, 127.77, 126.06, 120.84, 116.86, 49.17,
46.07, 35.17, 31.06.
4-[(6-methoxy-3-pyridinyl)sulfonyl]morpholine (10): yellow solid, 71%
yield. 1H NMR (400 MHz, CDCl3, 298 K) δ = 8.58 (d, J = 2.4 Hz, 1H),
7.88 (dd, J = 8.8 Hz, J = 2.4 Hz, 1H), 6.88 (d, J = 0.8 Hz, 1H), 4.04 (s,
3H), 3.78 (t, J = 4.4 Hz, 4H), 3.04 (t, J = 4.8 Hz, 4H); 13C NMR (100 MHz,
CDCl3, 298K, ppm) δ = 166.62, 147.90, 137.72, 124.51, 111.38, 65.91,
54.24, 45.78.
4-((4-(tert-butyl)phenyl)sulfonyl)-tert-butyl-piperazine-1-carboxylate (17b):
white solid, 77% yield. 1H NMR (400 MHz, CDCl3, 298 K) δ = 7.66 (d, J =
8.4 Hz, 2H), 7.54 (d, J = 8.4 Hz, 2H), 3.51 (t, J = 5.2 Hz, 4H), 2.98 (t, J =
4.8 Hz, 4H), 1.40 (s, 9H), 1.35 (s, 9H); 13CNMR (100 MHz, CDCl3, 298K,
ppm) δ = 156.76, 154.16, 132.31, 127.61, 126.08, 80.29, 45.78, 35.13,
31.00, 28.23.
4-(1,3-benzodioxol-5-ylsulfonyl)morpholine (11): colourless oil, 85% yield.
1H NMR (400 MHz, CDCl3, 298 K) δ = 7.33-7.30 (m, 1H), 7.17 (d, J = 1.6
Hz, 1H), 6.93 (d, J = 8.0 Hz, 1H), 6.10 (s, 2H), 3.75 (t, J = 4.8 Hz, 4H),
3.00 (t, J = 4.8 Hz, 4H); 13C NMR (100 MHz, CDCl3, 298 K, ppm) δ =
151.65, 148.25, 128.27, 123.52, 108.34, 107.95, 102.26, 66.04, 45.98.
4-(5-methyl-benzofuranylsulfonyl)morpholine (12): white solid, 97% yield.
1H NMR (400 MHz, CDCl3, 298 K) δ = 8.06 (d, J = 1.6 Hz, 1H), 7.76 (d, J
= 2.0 Hz, 1H), 7.71-7.62 (m, 2H), 6.89 (d, J = 1.2 Hz, 1H), 3.73 (t, J = 4.8
Hz, 4H), 3.00 (t, J = 4.8 Hz, 4H); 13C NMR (100 MHz, CDCl3, 298 K, ppm)
δ = 156.85, 147.23, 129.76, 127.91, 123.91, 122.04, 112.03, 107.04,
66.03, 46.02; HR-MS (ESI): m/z 268.0644 (Calcd. [M+H]+), 268.0633
(Found. [M+H]+).
2-((4-(tert-butyl)phenyl)sulfonyl)-1,2,3,4-tetrahydro-iso-quinoline
(18):
yellow solid, 63% yield. 1H NMR (400 MHz, CDCl3, 298 K) δ= 7.77 (d, J =
8.4 Hz, 2H), 7.54 (d, J = 8.4 Hz, 2H), 7.16-7.14 (m, 2H), 7.09-7.02 (s, 2H),
4.27 (s, 2H), 3.38 (t, J = 6.0 Hz, 4H), 2.95 (t, J = 6.0 Hz, 4H), 1.34 (s, 9H);
13C NMR (100 MHz, CDCl3, 298K, ppm) δ = 156.16, 148.90, 147.65,
134.66, 130.85, 127.15, 125.95, 120.68, 112.01, 111.23, 55.85, 51.92,
35.20, 34.49, 31.02.
4-(2-dibenzothiophenylsulfonyl)morpholine (13): white solid, 97% yield.
1H NMR (400 MHz, CDCl3, 298 K) δ = 8.54 (s, 1H), 8.26-8.24 (m, 1H),
8.02 (d, J = 8.4 Hz, 1H), 7.93-7.90 (m, 1H), 7.80 (d, J = 8.4 Hz, 1H),
7.59-7.53 (m, 2H), 3.77 (t, J = 4.4 Hz, 4H), 3.07 (t, J = 4.8 Hz, 4H); 13C
NMR (100 MHz, CDCl3, 298 K, ppm) δ = 144.43, 139.85, 135.84, 134.43,
131.27, 128.01, 125.16, 124.99, 123.41, 123.01, 122.14, 122.29, 66.06,
N,N-dimethyl-4-(tert-butyl)benzenesulfonamide (19): yellow solid, 90%
yield. 1H NMR (400 MHz, CDCl3, 298 K) δ = 7.70 (d, J = 8.4 Hz, 2H),
7.54 (d, J = 8.4 Hz, 2H), 2.71 (s, 6H), 1.35 (s, 9H); 13C NMR (100 MHz,
CDCl3, 298K, ppm) δ = 156.34, 132.42, 127.62, 125.92, 37.93, 35.10,
31.05.
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10.1002/asia.201601732
Chemistry - An Asian Journal
FULL PAPER
N,N-diethyl-4-(tert-butyl)benzenesulfonamide (20): white solid, 75% yield.
1H NMR (400 MHz, CDCl3, 298 K) δ = 7.72 (d, J = 8.8 Hz, 2H), 7.49 (d, J
= 8.4 Hz, 2H), 3.23 (q, J = 6.8 Hz, 4H), 1.33 (s, 9H), 1.14 (d, J = 7.2 Hz,
6H); 13C NMR (100 MHz, CDCl3, 298K, ppm) δ = 155.87, 137.22, 126.83,
125.90, 42.09, 35.04, 31.07, 14.25.
2-[[4-(1,1-dimethylethyl)phenyl]sulfonyl]-1,1-dimethylethyl acetate (28):
colourless oil, 99% yield. 1H NMR (400 MHz, CDCl3, 298 K) δ = 7.86 (d, J
= 8.4 Hz, 2H), 7.58 (d, J = 8.8 Hz, 2H), 4.02 (s, 2H), 1.35 (s, 18H); 13
C
NMR (100 MHz, CDCl3, 298 K, ppm) δ 161.29, 158.04, 135.90, 128.33,
126.07, 83.38, 62.16, 35.24, 30.97, 27.58.
N-methyl-N-octyl-4-(tert-butyl)benzenesulfonamide (21): colourless oil,
77% yield. 1H NMR (400 MHz, CDCl3, 298 K) δ = 7.70 (d, J = 8.4 Hz, 2H),
7.51 (d, J = 8.4 Hz, 2H), 2.99 (t, J = 7.6 Hz, 2H), 2.72 (s, 3H), 1.34 (s,
9H), 1.28-1.26 (m, 12H), 0.88 (t, J = 6.4 Hz, 3H); 13C NMR (100 MHz,
CDCl3, 298K, ppm) δ = 156.01, 134.57, 127.20, 125.88, 50.06, 35.03,
34.52, 31.73, 31.04, 29.65, 29.15, 27.60, 26.48, 22.59, 14.15; HR-MS
(ESI): m/z 340.2310 (Calcd. [M+H]+), 340.2306 (Found. [M+H]+).
General
protocol
to
synthesize
sodium
50 mL Schlenk tube
4-(1,1-
dimethylethyl)benzenesulfinate (29): To
a
containing 4-tert-Butylphenylboronic acid (0.5 mmol), DABSO (1.0 eq.),
TBAB (1.0 eq.) and Pd(OAc)2 (5 mol%), purged with N2 for 3 times, 2 mL
of Dioxane/MeOH (1:1) mixture was added. The resulted reaction mixture
o
was allowed to stir for 5 h at 80 C under nitrogen atmosphere. Na2CO3
(2.0 eq.) was then added to the reaction mixture and stirred for additional
5 min. The resulting mixture was filtered through a pad of Celite®, the
cake washed with ethyl alcohol (2 x 10 mL) and the filtrate reduced in
volume. This solid was washed with ethyl acetate to give white solid,
80% yield. 1H NMR (400 MHz, CD3OD, 298 K) δ = 7.58 (d, J = 8.0 Hz,
2H), 7.47 (d, J = 8.0 Hz, 2H), 1.32 (s, 9H); 13C NMR (100 MHz, CD3OD,
298 K, ppm) δ = 153.94, 153.51, 126.37, 124.86, 35.46, 31.71. The data
match well with the previous literature.[22]
N-methyl-N-allyl-4-(tert-butyl)benzenesulfonamide (22): yellow solid, 66%
yield. 1H NMR (400 MHz, CDCl3, 298 K) δ = 7.71 (d, J = 8.4 Hz, 2H),
7.53 (d, J = 8.4 Hz, 2H), 5.78-68 (m, 1H), 5.22-5.18 (m, 2H), 3.64 (d, J =
6.4 Hz, 2H), 2.68 (s, 3H), 1.35 (s, 9H); 13C NMR (100 MHz, CDCl3, 298K,
ppm) δ = 156.25, 132.66, 127.27, 125.97, 125.13, 118.99, 52.97, 35.07,
34.17, 31.03; HR-MS (ESI): m/z 268.1371 (Calcd. [M+H]+), 268.1372
(Found. [M+H]+).
N-methyl-N-benzyl-4-(tert-butyl)benzenesulfonamide (23): white solid,
71% yield. 1H NMR (400 MHz, CDCl3, 298 K) δ= 7.77 (d, J = 8.8 Hz, 2H),
7.56 (d, J = 8.4 Hz, 2H), 7.34-7.29 (m, 5H), 4.16 (s, 2H), 2.61 (s, 1H),
1.37 (s, 9H); 13C NMR (100 MHz, CDCl3, 298K, ppm) δ = 156.36, 135.73,
134.36, 128.60, 127.84, 127.34, 126.08, 54.08, 35.14, 34.34, 31.09.
Acknowledgements
Financial support from the National Natural Science Foundation
of China (No. 21572036 and 21172045), Ministry of Science and
Technology of China (2016YFA0202902), the Shanghai
International cooperation Program (14230710600), the Doctoral
Fund of Ministry of Education of China (20130071110032) and
Department of the People’s Republic of Chemistry Fudan
University is gratefully acknowledged.
4-(tert-butyl)-N-methyl-N-phenethylbenzenesulfonamide (24): white solid,
89% yield. 1H NMR (400 MHz, CDCl3, 298 K) δ = 7.68(d, J = 8.4 Hz, 2H),
7.49 (d, J = 8.4 Hz, 2H), 7.31-7.27 (m, 2H), 7.24-7.17 (m, 3H), 3.26 (t, J =
7.8 Hz, 2H), 2.87 (t, J = 8.0 Hz, 2H), 2.76 (s, 3H), 1.33 (s, 9H); 13C NMR
(100 MHz, CDCl3, 298K, ppm) δ = 156.14, 138.30, 134.66, 128.76,
128.51, 127.15, 126.49, 125.95, 51.80, 42.08, 35.16, 34.83, 31.02; HR-
MS (ESI): m/z 332.1684 (Calcd. [M+H]+), 332.1680 (Found. [M+H]+).
Keywords: boronic acids • copper • O-benzoyl hydroxylamines •
palladium • sulfonamides
4-(tert-butyl)-N-methyl-N-(4-fluorophenethyl)-benzene-sulfonamide (25):
yellow solid, 80% yield. 1H NMR (400 MHz, CDCl3, 298 K) δ = 7.67 (d, J
= 8.4 Hz, 2H), 7.50 (d, J = 8.4 Hz, 2H), 7.16-7.12 (m, 2H), 6.97 (t, J = 8.4
Hz, 2H), 3.24 (t, J = 7.8 Hz, 2H), 2.84 (t, J = 8.0 Hz, 2H), 2.75 (s, 3H),
1.33 (s, 9H); 13C NMR (100 MHz, CDCl3, 298K, ppm) δ = 162.82, 160.38,
156.22, 134.62, 133.97, 133.94, 130.24, 130.16, 127.13, 125.98, 115.41,
115.20, 51.75, 35.18, 35.06, 34.01, 31.02; 19F NMR (CDCl3, 376 MHz,
298 K): δ = -116.48; HR-MS (ESI): m/z 350.1590 (Calcd. [M+H]+),
350.1592 (Found. [M+H]+).
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(26): white solid, 85% yield. H NMR (400 MHz, CDCl3, 298 K) δ = 7.68
(d, J = 8.4 Hz, 2H), 7.50 (d, J = 8.4 Hz, 2H), 6.80-6.78 (m,1H), 6.73-6.71
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10.1002/asia.201601732
Chemistry - An Asian Journal
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The first one-pot bimetallic catalytic
system has been successfully
developed to afford various functional
sulfonamides from readily available
boronic acids, DABSO and O-benzoyl
hydroxylamines under very mild
reaction conditions at low catalyst
loadings.
Haibo Zhu, Yajing Shen,
Qinyue Deng, Changyu
Huang and Tao Tu*
Page No. – Page No.
One-pot Bimetallic Pd-Cu
Catalyzed Synthesis of
Sulfonamides from
Boronic Acids, DABSO
and O-Benzoyl
Hydroxylamines
This article is protected by copyright. All rights reserved.