Ruthenium-Catalyzed C–H Amidation and Alkenylation of Cyclic N-Sulfonyl Ketimines

Article abstract of DOI:10.1002/ejoc.201600505

A highly regioselective ruthenium-catalyzed C–H amidation of cyclic N-sulfonyl ketimines with organic sulfonyl azides is described. An alkenylation at the C–H bond of cyclic N-sulfonyl ketimines with various alkenes was also carried out. Only a catalytic

Full text of DOI:10.1002/ejoc.201600505

DOI: 10.1002/ejoc.201600505
Full Paper
C–H Activation
Ruthenium-Catalyzed C–H Amidation and Alkenylation of Cyclic
N-Sulfonyl Ketimines
Ramasamy Manoharan[a] and Masilamani Jeganmohan*[a]
Abstract: A highly regioselective ruthenium-catalyzed C–H Only a catalytic amount of the oxidant Cu(OAc)2 was used in
amidation of cyclic N-sulfonyl ketimines with organic sulfonyl the reaction; the remainder of the required amount of oxidant
azides is described. An alkenylation at the C–H bond of cyclic was formed by regeneration of Cu(OAc)2 under an air atmos-
N-sulfonyl ketimines with various alkenes was also carried out. phere.
Introduction
reports in the literature concerning the functionalization of
sultum derivatives.[9,10] In sultums, an N-sulfonyl imine
(-SO2–N=C-) moiety is present in the cyclic system. This can
be used as a directing group for C–H-bond functionalization
reactions. It is well known that alicyclic N-sulfonyl imines can
be used as directing groups for C–H-bond functionalization re-
actions.[11] However, the use of the cyclic N-sulfonyl imine moi-
ety as a directing group in C–H-bond functionalization has
hardly been explored. This is probably due to the lower chelat-
ing ability of the nitrogen atom, which results from the elec-
tron-withdrawing effect of the conjugated sulfonyl group.
The construction of a C–N bond through the transition-metal-
catalyzed chelation-assisted coupling of an unreactive C–H
bond of an aromatic or heteroaromatic compound with an
amine source is a step- and atom-economical method in or-
ganic synthesis.[1] It is important to note that nitrogen-contain-
ing compounds are present in various natural products, biologi-
cally active molecules, pharmaceuticals, and materials.[2] Tradi-
tionally, the C–N bonds in organic molecules are efficiently con-
structed using copper-catalyzed Ullman–Goldberg coupling
reactions or palladium-catalyzed Buchwald–Hartwig-type cou-
pling reactions.[3] Although these are highly efficient and versa-
tile methods for the construction of C–N bonds in organic mol-
ecules, the reactions require a preactivated species such as C–X or
C–M on the organic moiety, and also bulky phosphine ligands.
This sort of issue can be easily resolved by doing a similar type
of functionalization through C–H-bond activation.[4] For this
type of reaction to be successful, it is very important to choose
an appropriate amine source. Generally, organic azides or N-
halo derivatives of amines are used as amine sources in C–H-
bond functionalization reactions.[1,4] Organic azides have
gained much attention in this type of reaction due to their wide
availability, easy preparation and handling.[1,5]
Sultums (cyclic N-sulfonyl ketimines) are an important class
of sulfur-containing heterocyclic molecules. This subunit is
found in various biologically active molecules and pharmaceuti-
cals.[6] In addition, sultum derivatives are used as key synthetic
intermediates for various organic transformations.[7] Chiral sul-
tums are also widely used as chiral auxiliaries in various asym-
metric reactions.[7,8] Due to the high importance of sultum de-
rivatives, several methods for their synthesis have been
reported in the literature.[8] However, there are only a few
In 2013, the Nishimura and Dong groups independently re-
ported iridium- and rhodium-catalyzed cyclic-N-sulfonyl-imine-
directed C–H activation reactions, followed by cyclization reac-
tions, of sultum derivatives with carbon–carbon π-components
such as 1,3-dienes and alkynes.[9] Later, cyclic-N-sulfonyl-imine-
directed alkenylation and allylation reactions of sultum deriva-
tives in the presence of a rhodium catalyst were demon-
strated.[10a,10b] Very recently, Crammer's group reported an
enantioselective version of the cyclization reaction of sultum
derivatives with alkynes.[10c] To date, only carbon–carbon bonds
have been constructed in the sultum derivatives in these metal-
catalyzed reactions. Our continued interest in the field of direct-
ing-group-assisted C–H-bond activation reactions prompted us
to explore the possibility of cyclic-N-sulfonyl-imine-directed
amination at the C–H bond of sultum derivatives, using organic
azides as a nitrogen source, and in the presence of a less expen-
sive ruthenium catalyst.[12] In this paper, we describe a ruth-
enium-catalyzed cyclic-N-sulfonyl-imine-directed C–H amin-
ation of sultum derivatives with organic azides. The RuII-based
catalytic system was compatible with various substituted or-
ganic azides and sultums. Later, alkenylation was also carried
out at the C–H bond of sultums using various olefins. The
alkenylation reaction worked very well with acrylates, styrene,
and vinyl sulfone. In the reaction, only a catalytic amount of
Cu(OAc)2 was used as a base to deprotonate the C–H bond of
the sultum derivatives. The remaining portion of the required
amount of Cu(OAc)2 was formed by regeneration from CuOAc
and AcOH under an air atmosphere.
[a] Department of Chemistry, Indian Institute of Science Education and
Research,
Pune 411021, India
E-mail: mjeganmohan@iiserpune.ac.in
http://www.iiserpune.ac.in/~mjeganmohan
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/ejoc.201600505.
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Results and Discussion
azides, including phenyl azide, benzyl azide, and benzoyl azide
(Scheme 1). However, in these reactions, none of the expected
product was observed. This result clearly shows that the sulf-
onyl azide is a suitable reaction partner for this amidation reac-
tion.
The scope of the amidation reaction was examined with vari-
ous substituted sulfonyl azides 2b–2g (Table 1). Benzenesulf-
onyl azide (2b) and p-methoxybenzenesulfonyl azide (2c) re-
acted with 1a under the optimized reaction conditions to give
the corresponding amidation products (i.e., 3ab and 3ac) in 76
and 66 % yields, respectively (Table 1, entries 1 and 2). Encour-
N-Sulfonyl ketimine 1a and p-toluenesulfonyl azide (2a) were
taken as model substrates for optimization of the reaction con-
ditions. Although in the reaction, the N–N2 bond of azide 2a
acts as an internal oxidant, a catalytic amount of base is needed
to initiate the catalytic reaction. Thus, the amidation reaction
was examined with various bases (30 mol-%), including
Cu(OAc)2·H2O, NaOAc, KOAc, Ag2CO3, and AgOAc. Silver acetate
was highly effective, providing product 3aa in 86 % GC yield
and 81 % isolated yield. Cu(OAc)2·H2O was partially effective,
providing 3aa in 61 % GC yield. Sodium acetate and potassium
acetate were less effective, giving 3aa in 41 and 36 % GC yields,
respectively. Silver carbonate was totally ineffective for the reac-
tion.
Table 1. The reaction of N-sulfonyl ketimine 1a with substituted azides 2b–
2g.[a]
The amidation reaction was also tested with various solvents,
including 1,2-dichloroethane (DCE), chlorobenzene, CH3CN,
iPrOH, tert-amyl alcohol, DMSO, DMF, THF, 1,2-dimethoxy-
ethane, and toluene, under similar reaction conditions. 1,2-Di-
chloroethane was found to be very effective, providing product
3aa in 86 % GC yield. Chlorobenzene was partially effective,
giving product 3aa in 52 % GC yield. 1,4-Dioxane and isopropa-
nol were less effective, giving product 3aa in 26 and 20 % GC
yields, respectively. The other solvents tested were not effective.
The amidation reaction was also examined with various addi-
tives, including AgBF4, AgOTf, AgSbF6, and KPF6. AgSbF6 was
found to be very effective, giving product 3aa in 86 % GC yield.
AgBF4 was partially effective, giving 3aa in 47 % GC yield.
AgOTf and KPF6 were not suitable for the reaction. A reaction
temperature of 100 °C was also important for obtaining a better
yield of product 3aa. Product 3aa was formed in only 41 %
yield when the reaction temperature was 60 °C. Control reac-
tions were run in which AgSbF6, the [{RuCl2(p-cymene)}2] cata-
lyst, or silver acetate was omitted, and none of the amidation
product (i.e., 3aa) was observed in any of these cases. These
optimization studies clearly revealed [{RuCl2(p-cymene)}2]
(5.0 mol-%), AgSbF6 (20 mol-%), and silver acetate (30 mol-%)
in 1,2-dichloroethane at 100 °C to be the best conditions for
the cyclization reaction. Under the optimized reaction condi-
tions, the amidation reaction was examined with other organic
[a] All reactions were carried out using 1a (100 mg), azide 2b–2g (1.2 equiv.),
[{RuCl2(p-cymene)}2] (5 mol-%), AgSbF6 (20 mol-%), and AgOAc (30 mol-%)
in 1,2-dichloroethane (3.0 mL) at 100 °C for 24 h. [b] Isolated yield.
Scheme 1. Ruthenium-catalyzed amidation of 1a with 2a.
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aged by these results, we explored the amidation reaction fur-
ther with aryl sulfonyl azides bearing electron-withdrawing
groups, such as 4-bromobenzenesulfonyl azide (2d), 4-chloro
benzenesulfonyl azide (2e), and 4-fluorobenzenesulfonyl azide
(2f). Interestingly, these aryl sulfonyl azides participated nicely
in the reaction, giving products 3ad–3af in good yields
(Table 1, entries 3–5). Transition-metal-labile groups such as
bromo and chloro were tolerated in these reactions (Table 1,
entries 3 and 4). Interestingly, 1-naphthylsulfonyl azide (2g) also
reacted nicely with 1a, giving product 3ag in 71 % yield
(Table 1, entry 6).
Table 2. The reaction of substituted N-sulfonyl ketimines 1b–1g with 2a.[a]
The amidation reaction was examined with various substi-
tuted N-sulfonyl ketimines 1b–1g with p-toluenesulfonyl azide
(2a) (Table 2). The reaction of para-methyl- (1b) and para-meth-
oxy- (1c) substituted N-sulfonyl ketimines with 2a under the
optimized reaction conditions gave the expected amidation
products (i.e., 3ba and 3ca) in 73 and 79 % yields, respectively
(Table 2, entries 1 and 2). Interestingly, unsymmetrical meta-
methyl-substituted N-sulfonyl ketimine 1d underwent amid-
ation with 2a selectively at the less hindered C–H bond to give
the expected product (i.e., 3da) in 69 % yield in a highly regio-
selective manner (Table 2, entry 3). Furthermore, ortho-methoxy
substituted N-sulfonyl ketimine 1e gave the expected amid-
ation product (i.e., 3ea) in 61 % yield (Table 2, entry 4). N-Sulf-
onyl ketimine 1f also efficiently participated in the reaction to
give amidation product 3fa in 76 % yield. Fluorine-substituted
N-sulfonyl ketimine 1g also participated in the reaction, giving
amidation product 3ga in 59 % yield (Table 2, entry 6).
These results prompted us to explore the possibility of carry-
ing out an alkenylation at the C–H bond of cyclic N-sulfonyl
ketimines 1 with alkenes in the presence of a less expensive
ruthenium catalyst (Table 3). For this alkenylation reaction, we
used the reaction conditions we previously developed for the
chelation-assisted ortho alkenylation of aromatic carbonyl com-
pounds with alkenes.[12] When N-sulfonyl ketimine 1a was
treated with methyl acrylate (4a) in the presence of [{RuCl2(p-
cymene)}2] (5.0 mol-%), AgSbF6 (20 mol-%), and Cu(OAc)2·H2O
(50 mol-%) under air at 100 °C for 12 h in 1,2-dichloroethane,
an alkenylated cyclic N-sulfonyl ketimine 5aa was formed in an
excellent 86 % yield (Table 3, entry 1). Only a catalytic amount
of the Cu(OAc)2 base was used in the reaction; the remaining
portion of the required amount of the Cu(OAc)2 oxidising agent
was regenerated under an air atmosphere in the presence of
acetic acid and CuOAc.
[a] All reactions were carried out using 1b–1g (100 mg), azide 2a (1.2 equiv.),
[{RuCl2(p-cymene)}2] (5 mol-%), AgSbF6 (20 mol-%), and AgOAc (30 mol-%)
in ClCH2CH2Cl (3.0 mL) at 100 °C for 24 h. [b] Isolated yield.
The alkenylation reaction was also examined with ethyl acryl-
ate (4b), tert-butyl acrylate (4c), and cyclohexyl acrylate (4d)
under similar reaction conditions. As expected, in all cases, the sponding alkenylated products (i.e., 5ba and 5da) in 81 and
alkenylated cyclic N-sulfonyl ketimine derivatives (i.e., 5ab–5ad) 77 % yields, respectively. It is worth noting that in the reaction
were formed in 79, 81, and 69 % yields, respectively (Table 3, of 1d with 4a, alkenylation takes place selectively at the less
hindered side of the aryl ring of 1d.
A plausible mechanism for the amidation reaction is given
in Scheme 3. The active cationic ruthenium species 6 is gener-
entries 2–4). The alkenylation reaction was also compatible with
styrene (4e) and phenyl vinyl sulfone (4f). In these reactions,
the expected alkenylated products (i.e., 5ae and 5af) were
formed in 68 and 82 % yields, respectively (Table 3, entries 5
and 6). After that, the alkenylation reaction was examined with
ated by
a ligand-exchange reaction between [{RuCl2(p-
cymene)}2], AgSbF6, and AgOAc. Coordination of the nitrogen
substituted N-sulfonyl ketimines 1b and 1d (Scheme 2). para- atom of the imine group to active ruthenium species 6, fol-
Methyl- (1b) and meta-methyl- (1d) substituted N-sulfonyl ket- lowed by deprotonation gives a five-membered ruthenacycle 7.
imines reacted with methyl acrylate (4a) to give the corre- After that, coordinative insertion of an aryl azide into intermedi-
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Table 3. The reaction of substituted N-sulfonyl ketimines 1a with alkenes 4a–
4f.[a]
Scheme 3. Proposed mechanism.
Conclusions
In conclusion, we have demonstrated a highly regioselective
C–H amidation of cyclic N-sulfonyl ketimines with substituted
sulfonyl azides in the presence of a ruthenium catalyst. The
catalytic reaction provides the expected amine derivatives in
good to excellent yields. A ruthenium-catalyzed alkenylation at
the C–H bond of cyclic N-sulfonyl ketimines with various alk-
enes was also demonstrated. A possible reaction mechanism
was proposed.
[a] All reactions were carried out using 1a (100 mg), alkene 4a–4f (2.2 equiv.),
[{RuCl2(p-cymene)}2] (5 mol-%), AgSbF6 (20 mol-%), and Cu(OAc)2·H2O
(50 mol-%) in 1,2-dichloroethane (3.0 mL) at 100 °C for 12 h. [b] Isolated
yield.
Experimental Section
General Procedure for the Amidation of N-Sulfonyl Ketimines
with Aryl Azides Using a Ruthenium Complex: A pressure tube
(15 mL) with a septum, containing [{RuCl2(p-cymene)}2] (5.0 mol-
%), N-sulfonyl ketimine 1 (100 mg), AgOAc (30 mol-%), aryl sulfonyl
azide 2 (1.2 equiv.) (if the aryl sulfonyl azide was solid), and AgSbF6
(20 mol-%), was evacuated and purged with nitrogen gas three
times (AgSbF6 and AgOAc were added inside a glove box). 1,2-
Dichloroethane (3 mL) was then added to the tube by syringe. The
tube was then evacuated and purged with nitrogen gas three times
(liquid aryl sulfonyl azides were added at this stage by syringe).
After that, the septum was removed, and the tube was immediately
sealed with a screw cap under a nitrogen atmosphere. The reaction
mixture was stirred at room temperature for 5 min. Then, the reac-
tion mixture stirred at 100 °C for 24 h. After this time, the mixture
was cooled to ambient temperature, diluted with CH2Cl2, and fil-
tered through Celite. The filtrate was concentrated. The crude resi-
due was purified by silica gel column chromatography using hex-
Scheme 2. Ruthenium-catalyzed alkenylation of 1b and 1d with 4a.
ate 7, with concomitant evolution of nitrogen gas, gives nitren-
oid intermediate 8.[1,13] Migratory insertion of the sulfonamido
group into the C–Ru bond of intermediate 8 gives intermediate
9. Later, protonation takes place at the N–Ru bond of intermedi-
ate 9 in the presence of AcOH. This gives amidation product 3,
and regenerates the active cationic Ru complex (i.e., 6) for the
next catalytic cycle. To check the reversibility of the C–H depro- anes and ethyl acetate as eluent to give pure product 3.
tonation, 1a was treated with a ruthenium catalyst, AgSbF6, and
AgOAc in a mixture of DCE and D2O solvents (2:1) at 100 °C for
24 h. As expected, 67 % deuterium incorporation was observed
N-[2-(1,1-Dioxidobenzo[d]isothiazol-3-yl)phenyl]-4-methyl-
benzenesulfonamide (3aa): Compound 1a (100 mg) was used. Pu-
at both ortho carbons of d-1a, which was formed in 74 % yield. rification by column chromatography (30 % ethyl acetate in hex-
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1
anes) gave 3aa (137 mg, 81 %) as a white solid. H NMR (400 MHz,
(100 MHz, CDCl3): δ = 168.3, 166.0, 163.5, 139.8, 136.2, 133.9, 133.8,
CDCl3): δ = 7.94 (d, J = 7.6 Hz, 1 H), 7.87 (d, J = 8.2 Hz, 1 H), 7.80– 133.7, 133.5, 130.1and 130.0 (F coupling), 129.9, 129.5, 128.6, 126.4,
7.74 (m, 1 H), 7.70–7.58 (m, 2 H), 7.54 (dd, J = 7.8, 1.6 Hz, 1 H), 7.45– 123.1, 123.0, 115.9 and 115.7 (F coupling) ppm. HRMS (ESI): calcd.
7.35 (m, 1 H), 7.33–7.27 (m, 2 H), 7.26–7.21 (m, 1 H), 6.71 (d, J = for [(C19H13FN2O4S2)H] [M + H] 417.0379; found 417.0384.
8.0 Hz, 2 H), 1.90 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 168.5,
N-[2-(1,1-Dioxidobenzo[d]isothiazol-3-yl)phenyl]naphthalene-
143.4, 139.8, 136.7, 134.7, 133.9, 133.6, 133.4, 130.2, 129.7, 129.3,
1-sulfonamide (3ag): Compound 1a (100 mg) was used. Purifica-
128.5, 127.3, 126.7, 126.2, 123.0, 122.9, 21.3 ppm. HRMS (ESI): calcd.
tion by column chromatography (30 % ethyl acetate in hexanes)
for [(C20H16N2O4S2)H] [M + H] 413.0630; found 413.0639.
1
gave 3ag (131 mg, 71 %) as an off-white solid. H NMR (400 MHz,
N-[2-(1,1-Dioxidobenzo[d]isothiazol-3-yl)phenyl]benzene-
sulfonamide (3ab): Compound 1a (100 mg) was used. Purification
by column chromatography (30 % ethyl acetate in hexanes) gave
[D6]DMSO): δ = 10.48 (s, 1 H), 8.49–8.36 (m, 1 H), 8.20 (d, J = 7.6 Hz,
1 H), 8.13 (d, J = 8.2 Hz, 1 H), 8.03–7.92 (m, 2 H), 7.87 (t, J = 7.6 Hz,
1 H), 7.76 (t, J = 7.6 Hz, 1 H), 7.61 (d, J = 6.8 Hz, 1 H), 7.58–7.45 (m,
4 H), 7.40 (t, J = 7.0 Hz, 1 H), 7.32 (t, J = 7.4 Hz, 1 H), 6.90 (d, J =
8.0 Hz, 1 H) ppm. 13C NMR (100 MHz, [D6]DMSO): δ = 171.6, 139.3,
135.6, 135.0, 134.6, 134.6, 134.4, 134.0, 133.5, 131.3, 130.8, 129.9,
129.5, 128.5, 127.7, 127.5, 127.4, 126.9, 126.2, 126.0, 124.9, 124.4,
1
3ab (125 mg, 76 %) as a white solid. H NMR (400 MHz, CDCl3): δ =
8.90 (s, 1 H), 8.02–7.95 (m, 1 H), 7.92 (d, J = 8.2 Hz, 1 H), 7.80 (t, J =
7.6 Hz, 1 H), 7.72–7.63 (m, 2 H), 7.59 (dd, J = 8.0, 1.4 Hz, 1 H), 7.54–
7.46 (m, 2 H), 7.43 (td, J = 7.8, 1.2 Hz, 1 H), 7.31–7.26 (m, 1 H), 6.96
(m, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 168.6, 139.6, 137.5, 123.0 ppm. HRMS (ESI): calcd. for [(C23H16N2O4S2)H] [M + H]
136.4, 134.0, 133.9, 133.6, 132.6, 130.4, 129.6, 128.7, 128.1, 127.2, 449.0630; found 449.0637.
127.0, 126.4, 122.9, 122.8 ppm. HRMS (ESI): calcd. for
N-[2-(1,1-Dioxidobenzo[d]isothiazol-3-yl)-5-methylphenyl]-4-
[(C19H14N2O4S2)H] [M + H] 399.0473; found 399.0469.
methylbenzenesulfonamide (3ba): Compound 1b (100 mg) was
N-[2-(1,1-Dioxidobenzo[d]isothiazol-3-yl)phenyl]-4-methoxy-
benzenesulfonamide (3ac): Compound 1a (100 mg) was used. Pu-
rification by column chromatography (35 % ethyl acetate in hex-
anes) gave 3ac (116 mg, 66 %) as an off-white solid. 1H NMR
(400 MHz, CDCl3): δ = 8.75 (s, 1 H), 7.99 (d, J = 7.6 Hz, 1 H), 7.97–
7.90 (m, 1 H), 7.79 (t, J = 7.6 Hz, 1 H), 7.75–7.67 (m, 1 H), 7.69–7.60
(m, 1 H), 7.58 (dd, J = 7.8, 1.6 Hz, 1 H), 7.45 (dd, J = 7.6, 1.2 Hz, 1
H), 7.42–7.37 (m, 2 H), 7.30 (s, 1 H), 6.41 (d, J = 8.0 Hz, 2 H), 3.51 (s,
3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 168.4, 162.6, 139.9, 136.8,
used. Purification by column chromatography (30 % ethyl acetate
in hexanes) gave 3ba (128 mg, 73 %) as a white solid. 1H NMR
(400 MHz, CDCl3): δ = 8.87 (s, 1 H), 7.98 (d, J = 7.6 Hz, 1 H), 7.79 (t,
J = 7.6 Hz, 1 H), 7.74 (s, 1 H), 7.64 (td, J = 7.8, 1.2 Hz, 1 H), 7.48 (d,
J = 8.0 Hz, 1 H), 7.40–7.36 (m, 2 H), 7.34–7.28 (m, 1 H), 7.22 (dd, J =
8.0, 1.0 Hz, 1 H), 6.76 (d, J = 7.8 Hz, 2 H), 2.53 (s, 3 H), 1.94 (s, 3 H)
ppm. 13C NMR (100 MHz, CDCl3): δ = 168.3, 145.4, 143.2, 139.9,
136.8, 134.8, 133.3, 133.0, 129.9, 129.2, 128.7, 127.3, 126.9, 126.5,
122.8, 120.1, 21.9, 21.2 ppm. HRMS (ESI): calcd. for [(C21H18N2O4S2)H]
133.8, 133.4, 133.2, 130.1, 129.7, 129.3, 129.3, 128.5, 126.5, 126.0, [M + H] 427.0786; found 427.0782.
123. 1 , 12 2. 7 , 11 3. 6 , 5 5. 1 pp m . H R MS ( ES I ): c a l c d. for
N-[2-(1,1-Dioxidobenzo[d]isothiazol-3-yl)-5-methoxyphenyl]-4-
methylbenzenesulfonamide (3ca): Compound 1c (100 mg) was
[(C20H16N2O5S2)H] [M + H] 429.0579; found 429.0583.
4-Bromo-N-[2-(1,1-dioxidobenzo[d]isothiazol-3-yl)phenyl]- used. Purification by column chromatography (40 % ethyl acetate
benzenesulfonamide (3ad): Compound 1a (100 mg) was used. Pu- in hexanes) gave 3ca (144 mg, 79 %) as a white solid. 1H NMR
rification by column chromatography (25 % ethyl acetate in hex-
(400 MHz, CDCl3): δ = 9.33 (s, 1 H), 8.00 (d, J = 7.6 Hz, 1 H), 7.79 (t,
anes) gave 3ad (127 mg, 65 %) as a brown solid. 1H NMR (400 MHz, J = 7.6 Hz, 1 H), 7.66 (t, J = 7.8 Hz, 1 H), 7.59 (d, J = 8.8 Hz, 1 H),
CDCl3): δ = 8.80 (s, 1 H), 8.01 (d, J = 7.6 Hz, 1 H), 7.94 (d, J = 8.2 Hz,
1 H), 7.87 (d, J = 7.6 Hz, 1 H), 7.73 (dd, J = 8.6, 7.6 Hz, 2 H), 7.60
(dd, J = 7.8, 1.6 Hz, 1 H), 7.48 (td, J = 7.8, 1.2 Hz, 1 H), 7.38–7.24 (m,
3 H), 7.12–7.01 (m, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 168.3,
7.46 (s, 2 H), 7.42 (dd, J = 12.0, 5.2 Hz, 2 H), 6.90 (dd, J = 8.8, 2.6 Hz,
1 H), 6.85 (d, J = 8.0 Hz, 2 H), 3.98 (s, 3 H), 2.01 (s, 3 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 167.8, 164.1, 143.5, 140.0, 139.9, 134.9,
133.4, 133.3, 132.2, 130.3, 129.3, 127.4, 126.7, 122.9, 114.4, 112.7,
139.6, 136.6, 135.9, 134.1, 133.9, 133.9, 131.9, 130.1, 129.3, 129.0, 111.4, 56.1, 21.4 ppm. HRMS (ESI): calcd. for [(C21H18N2O5S2)H] [M +
128.7, 127.7, 126.6, 126.1, 123.3, 123.0 ppm. HRMS (ESI): calcd. for
[(C19H13BrN2O4S2)H] [M + H] 476.9578; found 476.9573.
H] 443.0735; found 443.0739.
N-[2-(1,1-Dioxidobenzo[d]isothiazol-3-yl)-4-methylphenyl]-4-
4-Chloro-N-[2-(1,1-dioxidobenzo[d]isothiazol-3-yl)phenyl]- methylbenzenesulfonamide (3da): Compound 1d (100 mg) was
benzenesulfonamide (3ae): Compound 1a (100 mg) was used. Pu-
rification by column chromatography (25 % ethyl acetate in hex-
anes) gave 3ae (103 mg, 58 %) as an off-white solid. 1H NMR
(400 MHz, CDCl3): δ = 8.79 (s, 1 H), 8.04–7.99 (m, 1 H), 7.94 (d, J =
used. Purification by column chromatography (30 % ethyl acetate
in hexanes) gave 3da (121 mg, 69 %) as a white solid. 1H NMR
(400 MHz, CDCl3): δ = 8.61 (s, 1 H), 7.98 (d, J = 7.6 Hz, 1 H), 7.80 (m,
2 H), 7.65 (t, J = 7.8 Hz, 1 H), 7.50 (dd, J = 8.4, 1.6 Hz, 1 H), 7.34 (s,
8.2 Hz, 1 H), 7.85 (t, J = 7.5 Hz, 1 H), 7.72 (m, 2 H), 7.60 (dd, J = 7.8, 2 H), 7.32 (s, 1 H), 7.24 (d, J = 7.8 Hz, 1 H), 6.73 (d, J = 8.0 Hz, 2 H),
1.4 Hz, 1 H), 7.48 (td, J = 7.8, 1.2 Hz, 1 H), 7.42–7.37 (m, 2 H), 7.27
(d, J = 7.8 Hz, 1 H), 6.95–6.85 (m, 2 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 168.4, 139.7, 139.2, 136.1, 136.0, 134.1, 134.0, 133.8,
130.2, 129.4, 129.2, 129.0, 128.8, 126.7, 126.3, 123.4, 123.2 ppm.
HRMS (ESI): calcd. for [(C19H13ClN2O4S2)H] [M + H] 433.0084; found
433.0081.
2.45 (s, 3 H), 1.92 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 168.4,
143.1, 139.9, 136.4, 134.7, 134.6, 133.9, 133.4, 133.1, 130.2, 129.7,
129.2, 128.8, 127.3, 126.5, 123.2, 122.8, 21.2, 21.06 ppm. HRMS (ESI):
calcd. for [(C21H18N2O4S2)H] [M + H] 427.0786; found 427.0789.
N-[2-(1,1-Dioxidobenzo[d]isothiazol-3-yl)-3-methoxyphenyl]-4-
methylbenzenesulfonamide (3ea): Compound 1e (100 mg) was
used. Purification by column chromatography (40 % ethyl acetate
in hexanes) gave 3ea (111 mg, 61 %) as a white solid. 1H NMR
(400 MHz, CDCl3): δ = 8.35 (s, 1 H), 7.98 (d, J = 7.6 Hz, 1 H), 7.86 (d,
J = 8.0 Hz, 1 H), 7.80 (t, J = 7.6 Hz, 1 H), 7.62 (t, J = 7.4 Hz, 1 H),
7.30 (d, J = 8.2 Hz, 2 H), 7.27–7.19 (m, 2 H), 7.01 (d, J = 2.8 Hz, 1 H),
6.72 (t, J = 10.0 Hz, 2 H), 3.89 (s, 3 H), 1.89 (s, 3 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 168.1, 157.6, 142.9, 139.9, 134.6, 133.3, 133.0,
N-[2-(1,1-Dioxidobenzo[d]isothiazol-3-yl)phenyl]-4-fluoro-
benzenesulfonamide (3af): Compound 1a (100 mg) was used. Pu-
rification by column chromatography (25 % ethyl acetate in hex-
anes) gave 3af (84 mg, 49 %) as a white solid. 1H NMR (400 MHz,
CDCl3): δ = 8.80 (s, 1 H), 8.01 (d, J = 7.6 Hz, 1 H), 7.94 (d, J = 8.2 Hz,
1 H), 7.88–7.79 (m, 1 H), 7.71 (m, 2 H), 7.62 (s, 1 H), 7.53–7.45 (m, 3
H), 7.29 (d, J = 6.8 Hz, 1 H), 6.62 (t, J = 8.6 Hz, 2 H) ppm. 13C NMR
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131.4, 129.5, 129.2, 128.7, 127.3, 126.3, 124.9, 122.8, 118.2, 115.7, 1 H), 4.16 (q, J = 7.0 Hz, 2 H), 1.24 (t, J = 7.0 Hz, 3 H) ppm. 13C NMR
55.8, 21.2 ppm. HRMS (ESI): calcd. for [(C21H18N2O5S2)H] [M + H] (100 MHz, CDCl3): δ = 171.1, 165.8, 140.5, 140.3, 134.5, 133.8, 133.7,
443.0735; found 443.0737.
132.2, 131.2, 129.9, 129.8, 129.7, 127.9, 126.6, 122.9, 122.2, 60.7,
14.1 ppm. HRMS (ESI): calcd. for [(C18H15NO4S)H] [M + H] 342.0800;
found 342.0809.
4-Methyl-N-[2-(5-methyl-1,1-dioxidobenzo[d]isothiazol-3-yl)-
phenyl]benzenesulfonamide (3fa): Compound 1f (100 mg) was
used. Purification by column chromatography (40 % ethyl acetate Butyl (E)-3-[2-(1,1-Dioxidobenzo[d]isothiazol-3-yl)phenyl]acryl-
in hexanes) gave 3fa (133 mg, 76 %) as a white solid. 1H NMR
(400 MHz, CDCl3): δ = 8.74 (s, 1 H), 7.89 (d, J = 8.0 Hz, 1 H), 7.82 (d,
ate (5ac): Compound 1a (100 mg) was used. Purification by column
chromatography (25 % ethyl acetate in hexanes) gave 5ac (123 mg,
J = 7.8 Hz, 1 H), 7.72–7.62 (m, 1 H), 7.60–7.48 (m, 2 H), 7.41 (t, J = 81 %) as a white solid. 1H NMR (400 MHz, CDCl3): δ = 8.07–7.99 (m,
7.6 Hz, 1 H), 7.33 (d, J = 8.2 Hz, 2 H), 6.96 (s, 1 H), 6.74 (d, J = 8.2 Hz,
1 H), 7.91–7.83 (m, 2 H), 7.80 (t, J = 7.6 Hz, 1 H), 7.75–7.65 (m, 3 H),
2 H), 2.47 (s, 3 H), 1.92 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 7.61 (d, J = 8.0 Hz, 1 H), 7.53–7.46 (m, 1 H), 6.44 (d, J = 15.8 Hz, 1
168.4, 144.4, 143.1, 137.3, 136.6, 134.9, 133.9, 133.6, 130.2, 129.9, H), 4.15 (t, J = 6.6 Hz, 2 H), 1.62 (dt, J = 14.6, 6.6 Hz, 2 H), 1.41–1.29
129.2, 128.4, 127.3, 126.9, 126.0, 123.0, 122.6, 21.7, 21.0 ppm. HRMS
(m, 2 H), 0.92 (t, J = 7.4 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3):
(ESI): calcd. for [(C21H18N2O4S2)H] [M + H] 427.0786; found 427.0791. δ = 171.2, 165.9, 140.4, 140.3, 134.4, 133.8, 133.7, 132.2, 131.2, 129.9,
129.8, 129.7, 127.9, 126.6, 122.9, 122.3, 64.6, 30.6, 19.1, 13.7 ppm.
N-[2-(1,1-Dioxidobenzo[d]isothiazol-3-yl)-5-fluorophenyl]-4-
HRMS (ESI): calcd. for [(C20H19NO4S)H] [M + H] 370.1113; found
methylbenzenesulfonamide (3ga): Compound 1g (100 mg) was
370.1117.
used. Purification by column chromatography (45 % ethyl acetate
1
in hexanes) gave 3ga (97 mg, 59 %) as an off-white solid. H NMR
(400 MHz, CDCl3): δ = 9.15 (s, 1 H), 8.02 (d, J = 7.6 Hz, 1 H), 7.83 (t,
J = 7.2 Hz, 1 H), 7.72–7.61 (m, 2 H), 7.47 (d, J = 8.2 Hz, 2 H), 7.35 (d,
Cyclohexyl (E)-3-[2-(1,1-Dioxidobenzo[d]isothiazol-3-yl)phenyl]-
acrylate (5ad): Compound 1a (100 mg) was used. Purification by
column chromatography (25 % ethyl acetate in hexanes) gave 5ad
J = 7.8 Hz, 1 H), 7.13–7.08 (m, 1 H), 6.87 (d, J = 8.0 Hz, 2 H), 2.03 (s, (112 mg, 69 %) as an off-white solid. 1H NMR (400 MHz, CDCl3): δ =
3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 167.8, 166.7, 163.3, 160.2,
143.8, 139.9, 134.8, 133.8, 133.4, 132.5, 132.4, 129.8, 129.5, 127.3, 7.70 (m, 3 H), 7.64–7.58 (m, 1 H), 7.56–7.48 (m, 1 H), 6.45 (d, J =
8.03 (d, J = 7.6 Hz, 1 H), 7.92–7.84 (m, 2 H), 7.80 (t, J = 7.8 Hz, 1 H),
126.5, 123.2, 118.2, 114.5 and 114.3 (F-coupling), 113.4 and 113.2
(F-coupling), 21.41 ppm. HRMS (ESI): calcd. for [(C20H15FN2O4S2)H]
[M + H] 431.0536; found 431.0539.
15.8 Hz, 1 H), 4.86–4.79 (m, 1 H), 1.80 (s, 2 H), 1.66 (s, 2 H), 1.50–
1.37 (m, 3 H), 1.37–1.29 (m, 3 H) ppm. 13C NMR (100 MHz, CDCl3):
δ = 171.1, 165.3, 140.6, 140.1, 139.0, 134.5, 133.8, 133.6, 132.2, 129.9,
129.8, 129.7, 128.2, 127.8, 126.6, 123.5, 122.9, 122.8, 72.9, 31.4, 25.3,
23.50 ppm. HRMS (ESI): calcd. for [(C22H21NO4S)H] [M + H] 396.1270;
found 396.1271.
General Procedure for the Alkenylation of N-Sulfonyl Ketimines
with Olefins Using a Ruthenium Complex: A pressure tube
(15 mL) with a septum, containing [{RuCl2(p-cymene)}2] (5.0 mol-
%), N-sulfonyl ketimine 1 (100 mg), Cu(OAc)2·H2O (50 mol-%), olefin
4 (2.2 equiv.) (in the case of phenyl vinyl sulfone), and AgSbF6
(20 mol-%), was evacuated and purged with nitrogen gas three
times (AgSbF6 was added inside the glove box). 1,2-Dichloroethane
(3 mL) was then added by syringe. The tube was then evacuated
and purged with nitrogen gas three times (liquid olefins were
added at this stage by syringe). After that, the reaction mixture was
stirred at room temperature for 5 min under a nitrogen atmosphere,
then the septum was removed, and the reaction mixture was stirred
at room temperature for 10 min under an air atmosphere. Then, the
pressure tube was sealed with a screw cap, and the reaction mixture
was stirred at 100 °C for 12 h. After this time, the mixture was
cooled to ambient temperature, diluted with CH2Cl2, and filtered
through Celite. The filtrate was concentrated. The crude residue was
purified by silica gel column chromatography using hexanes and
ethyl acetate as eluent to give pure product 5.
(E)-3-(2-Styrylphenyl)benzo[d]isothiazole 1,1-Dioxide (5ae):
Compound 1a (100 mg) was used. Purification by column chroma-
tography (20 % ethyl acetate in hexanes) gave 5ae (108 mg, 76 %)
as a thick yellow oil. 1H NMR (400 MHz, CDCl3): δ = 8.01 (d, J =
7.6 Hz, 1 H), 7.91 (d, J = 8.0 Hz, 1 H), 7.75 (t, J = 7.6 Hz, 1 H), 7.69–
7.58 (m, 3 H), 7.56–7.45 (m, 2 H), 7.39 (d, J = 7.6 Hz, 2 H), 7.31 (m,
4 H), 7.11 (d, J = 16.2 Hz, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
172.5, 140.3, 137.4, 136.5, 133.8, 133.6, 133.1, 132.12, 131.6, 129.6,
129.1, 128.8, 128.5, 128.4, 128.1, 127.6, 127.5, 127.0, 127.0, 126.9,
125.2, 122.8 ppm. HRMS (ESI): calcd. for [(C21H15NO2S)H] [M + H]
346.0902; found 346.0905.
(E)-3-{2-[2-(Phenylsulfonyl)vinyl]phenyl}benzo[d]isothiazole
1,1-Dioxide (5af): Compound 1a (100 mg) was used. Purification
by column chromatography (30 % ethyl acetate in hexanes) gave
5af (138 mg, 82 %) as an off-white solid. 1H NMR (400 MHz, CDCl3):
δ = 7.99 (d, J = 7.6 Hz, 1 H), 7.94–7.88 (m, 2 H), 7.79 (m, 2 H), 7.74–
7.65 (m, 4 H), 7.65–7.58 (m, 2 H), 7.56–7.49 (m, 3 H), 6.81 (d, J =
15.4 Hz, 1 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 170.4, 140.4,
140.1, 139.7, 133.9, 133.8, 133.6, 133.4, 132.5, 132.0, 130.7, 130.6,
129.9, 129.8, 129.5, 129.1, 127.9, 126.4, 123.1 ppm. HRMS (ESI): calcd.
for [(C21H15NO4S2)H] [M + H] 410.0521; found 410.0520.
Methyl (E)-3-[2-(1,1-Dioxidobenzo[d]isothiazol-3-yl)phenyl]-
acrylate (5aa): Compound 1a (100 mg) was used. Purification by
column chromatography (25 % ethyl acetate in hexanes) gave 5aa
(116 mg, 86 %) as a white solid. 1H NMR (400 MHz, CDCl3): δ = 8.01
(d, J = 7.6 Hz, 1 H), 7.85 (dd, J = 15.2, 8.4 Hz, 2 H), 7.80 (t, J = 7.6 Hz,
1 H), 7.75–7.58 (m, 4 H), 7.50 (t, J = 8.2 Hz, 1 H), 6.44 (d, J = 15.2 Hz,
1 H), 3.74 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 171.2, 166.3,
140.7, 140.3, 134.4, 133.9, 133.8, 132.2, 131.2, 130.3, 129.8, 129.7,
128.0, 126.6, 122.9, 121.8, 51.9 ppm. HRMS (ESI): calcd. for
[(C17H13NO4S)H] [M + H] 328.0644; found 328.0649.
Methyl (E)-3-[2-(1,1-Dioxidobenzo[d]isothiazol-3-yl)-5-methyl-
phenyl]acrylate (5ba): Compound 1b (100 mg) was used. Purifica-
tion by column chromatography (30 % ethyl acetate in hexanes)
gave 5ba (114 mg, 81 %) as a white solid. 1H NMR (400 MHz, CDCl3):
δ = 8.03 (d, J = 7.6 Hz, 1 H), 7.89 (d, J = 15.8 Hz, 1 H), 7.79 (t, J =
7.6 Hz, 1 H), 7.69 (dd, J = 15.6, 8.0 Hz, 2 H), 7.59 (d, J = 8.0 Hz, 1 H),
7.51 (d, J = 7.6 Hz, 1 H), 7.42 (d, J = 8.0 Hz, 1 H), 6.44 (d, J = 15.8 Hz,
1 H), 3.76 (s, 3 H), 2.53 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
171.1, 166.4, 142.9, 141.1, 140.4, 134.5, 133.7, 133.6, 131.3, 130.7,
129.9, 128.7, 127.1, 126.6, 122.9, 121.6, 51.9, 21.6 ppm. HRMS (ESI):
Ethyl (E)-3-[2-(1,1-Dioxidobenzo[d]isothiazol-3-yl)phenyl]acryl-
ate (5ab): Compound 1a (100 mg) was used. Purification by column
chromatography (25 % ethyl acetate in hexanes) gave 5ab (111 mg,
79 %) as a white solid. 1H NMR (400 MHz, CDCl3): δ = 7.98 (d, J =
7.6 Hz, 1 H), 7.83 (m, 2 H), 7.76 (t, J = 7.6 Hz, 1 H), 7.71–7.60 (m, 3
H), 7.59–7.54 (m, 1 H), 7.47 (d, J = 7.6 Hz, 1 H), 6.40 (d, J = 15.8 Hz, calcd. for [(C18H15NO4S)H] [M + H] 342.0800; found 342.0811.
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Methyl (E)-3-[2-(1,1-Dioxidobenzo[d]isothiazol-3-yl)-4-methyl-
phenyl]acrylate (5da): Compound 1d (100 mg) was used. Purifica-
tion by column chromatography (30 % ethyl acetate in hexanes)
gave 5da (108 mg, 77 %) as a white solid. 1H NMR (400 MHz, CDCl3):
δ = 8.04 (d, J = 7.6 Hz, 1 H), 7.81–7.75 (m, 3 H), 7.70 (t, J = 7.6 Hz,
1 H), 7.54–7.41 (m, 3 H), 6.41 (d, J = 15.8 Hz, 1 H), 3.75 (s, 3 H), 2.50
(s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 171.5, 166.5, 140.8,
140.7, 140.3, 133.8, 133.6, 133.00, 131.5, 131.2, 130.1, 129.9, 127.9,
126.6, 122.9, 120.8, 51.8, 21.3 ppm. HRMS (ESI): calcd. for calcd. for
[(C18H15NO4S)H] [M + H] 342.0800; found 342.0807.
Acknowledgments
The authors thank the Department of Science and Technology
(DST)-SERB, India (EMR/2014/000978) for supporting this re-
search. R. M. thanks the Council of Scientific and Industrial Re-
search (CSIR), New Delhi for a fellowship.
Keywords: C–H activation · Amination · Azides · Alkenes ·
Ruthenium
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Received: April 25, 2016
Published Online: ■
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Full Paper
C–H Activation
R. Manoharan, M. Jeganmo-
han* ....................................................... 1–8
Ruthenium-Catalyzed C–H Amid-
ation and Alkenylation of Cyclic N-
Sulfonyl Ketimines
Cyclic N-sulfonyl ketimines undergo reactions with organic sulfonyl azides
highly regioselective ruthenium-cata- or alkenes.
lyzed C–H amidation or alkenylation
DOI: 10.1002/ejoc.201600505
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© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim