Synthesis of N -Sulfonyl- and N -Acylpyrroles via a Ring-Closing Metathesis/Dehydrogenation Tandem Reaction

Article abstract of DOI:10.1055/s-0039-1690002

N -Sulfonyl- and N -acylpyrroles were synthesized via olefin ring-closing metathesis of diallylamines and in situ oxidative aromatization in the presence of the ruthenium Grubbs catalyst and a suitable copper catalyst. In the presence of Cu(OTf) ₂

Full text of DOI:10.1055/s-0039-1690002

SYNTHESIS
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© Georg Thieme Verlag Stuttgart · New York
2019, 51, A–P
paper
A
en
W. C. et al.
Paper
Synthesis
Synthesis of N-Sulfonyl- and N-Acylpyrroles via a Ring-Closing
Metathesis/Dehydrogenation Tandem Reaction
Weiqiang Chena
O
Grubbs II/Cu(OTf)2
Grubbs II/CuBr2
Ts
N
N
R
N
Yin-Lin Zhanga
Hui-Jing Li*a,b
Xiang Nana
Toluene, 110 °C
24 h, O2
Toluene, 110 °C
24 h, O2
Ph
19 additional examples
21 additional examples
one-pot
Ying Liua
Yan-Chao Wu*a,b
broad substrate scope
O2 as oxidant
0
0
0
0-0
0
0
2-0
1
1
1-7
4
8
4
a School of Marine Science and Technology, Harbin Institute of
Technology, 2 Wenhuaxi Road, Weihai 264209, P. R. of China
b Weihai Institute of Marine Biomedical Industrial Technology,
Wendeng District, Weihai 264400, P. R. of China
lihuijing@iccas.ac.cn
ycwu@iccas.ac.cn
Received: 07.06.2019
Accepted after revision: 26.06.2019
Published online: 15.07.2019
as the dehydrogenation catalysts (Scheme 1a). Castagnolo
used monoamine oxidase enzymes (MAO-N and 6-HDNO)
to convert 2,5-dihydro-1H-pyrroles into pyrroles.9d These
synthetic methods could afford useful pyrroles,10–12 but of-
ten suffer from certain drawbacks such as relying on the
use of expensive metal compounds (RuCl3, Pd/C) or nontra-
ditional energy sources (assisted by microwave irradiation
or ultrasound). Moreover, the synthetic approaches men-
tioned above have not been used for the synthesis of N-sul-
fonylpyrroles and N-acylpyrroles,9a,b,d or failed9c to give
these pyrroles, such as N-Ts-pyrrole (Scheme 1a). However,
N-sulfonyl- and N-acylpyrroles are useful heterocyclic com-
pounds that can be used in organic functional materials13
and various organic reactions.14 Inspiringly, Schmidt and
Evans reported a synthesis of pyrroles, including an N-Ts-
pyrrole, by a Ru-catalyzed RCM/oxidative aromatization se-
quence with the use of stoichiometric TBHP or MnO2 as the
oxidant (Scheme 1b).15 Compared with other oxidation
agents, O2 is undoubtedly the most appealing oxidant, be-
cause it is abundant, inexpensive, and non-hazardous. In
this context, we would like to report here the one-pot syn-
thesis of N-sulfonyl- and N-acylpyrroles via olefin ring-clos-
ing metathesis of diallylamines and in situ oxidative aroma-
tization with the use of O2 as the oxidant (Scheme 1c).
N,N-Diallyl-p-methylbenzenesulfonamide (1a) was
used as a probe for optimizing the reaction conditions, and
representative results are summarized in Table 1. Initially,
reaction of the substrate 1a was conducted in the presence
of Grubbs catalyst I/II in toluene at 110 °C for 24 h under a
N2 atmosphere (1 atm). Then, the N2 protective atmosphere
was changed to an O2 atmosphere. No desired pyrrole prod-
uct 2a was observed (entries 1–3), or a trace of 2a was ob-
tained (entry 4). Subsequently, the reaction of substrate 1a
was conducted under an O2 atmosphere (1 atm). The major
product of this reaction was the ring-closing product 3a,
and a small amount of the desired pyrrole product 2a was
DOI: 10.1055/s-0039-1690002; Art ID: ss-2019-f0322-op
Abstract N-Sulfonyl- and N-acylpyrroles were synthesized via olefin
ring-closing metathesis of diallylamines and in situ oxidative aromatiza-
tion in the presence of the ruthenium Grubbs catalyst and a suitable
copper catalyst. In the presence of Cu(OTf)2 and CuBr2, the reaction af-
forded N-sulfonyl- and N-acylpyrroles, respectively, in one pot. Under an
oxygen atmosphere, the reaction went smoothly without the need of
hydroperoxide oxidants. This protocol possesses many advantages,
such as using a nonhazardous oxidant and readily available starting ma-
terials, operating in one pot, and showing a broad substrate scope.
Key words N-substituted pyrroles, ring-closing methathesis, Grubbs
catalyst, Oxydehydrogenation, tandem reactions
Olefin ring-closing metathesis (RCM) is a powerful tool
for the construction of C–C double bonds in the field of or-
ganic chemistry, biology, and pharmaceutical sciences,1 es-
pecially for the synthesis of functionalized pyrroles from
acyclic precursors.2–4 The significance of the ring-closing
metathesis reaction has been witnessed in the facile syn-
thesis of the aromatic ring of streptonigrin.5 Donohoe re-
ported the first RCM–elimination approach to pyrroles,6
which was subsequently used for pyrrole syntheses by oth-
er groups.7 It was discovered by chance that olefin ring-
closing metathesis of diallylamines afforded traces of unex-
pected pyrrole byproducts along with the 2,5-dihydro-1H-
pyrrole products.8 Soon after this discovery, Stevens devel-
oped a straightforward protocol for pyrrole synthesis using
a co-catalytic system of the ruthenium Grubbs catalyst I in
combination with RuCl3 (Scheme 1a).9a Since this seminal
work reported by Stevens, many alternative methods have
been developed for the construction of pyrroles using a
one-pot combination of ring-closing metathesis and in situ
oxidative aromatization. Pujol and Wang synthesized N-
arylpyrroles with the use of Pd/C9b and FeCl3,9c respectively,
© 2019. Thieme. All rights reserved. — Synthesis 2019, 51, A–P
Georg Thieme Verlag KG, Rüdigerstraße 14, 70469 Stuttgart, Germany

B
W. C. et al.
Paper
Synthesis
lected as the optimized reaction conditions for the transfor-
mation of sulfonyldiallylamines to the corresponding pyr-
role products.
a) Stevens's,9a Pujol's,9b Wang's9c and Castagnolo's9d work
Grubbs I/II
Additive
R = Ts
ref. 9c
R
N
R
N
Ts N
R = Ar, Bn, Alkyl Additive: RuCl3, Pd/C, FeCl3, MAO-N
Table 1 Screening the Reaction Conditions for the RCM/Dehydroge-
nation of N-Ts-Substituted Diallylamine (1a)a
b) Schmidt's15a and Evans's15b work
1) Grubbs I/II
Ts
N
Ts N
[Ru] Cat., Additive
2) TBHP/MnO2
Ts
N
+
Ts
3a
N
Ts
N
Toluene, 110 °C
24 h, O2
c) This work
1a
2a
Grubbs II
Ts
N
Cu(OTf)2, O2
Entry
[Ru] Cat.
Additive
Yield of 2a/3ab (%)
19 additional examples
R
N
1c
2c
Grubbs I
Grubbs II
Grubbs I
Grubbs II
Grubbs II
Grubbs II
Grubbs II
Grubbs II
Grubbs II
Grubbs II
Grubbs II
Grubbs II
Grubbs II
Grubbs II
Grubbs II
Grubbs II
Grubbs II
Grubbs II
Grubbs II
Grubbs II
Grubbs I
–
–
–
–
0/91
0/89
O
Grubbs II
CuBr2, O2
N
Ph
3d
0/81
21 additional examples
4d
<5/73
10/82
18/73
27/66
38/53
19/73
21/71
25/63
62/30
36/54
<5/89
<5/65
39/51
12/80
<5/<5
51/36
87/<5
69/20
80/9
Mes
N
N
Mes
Ph
5
FeCl3·6H2O
CuCl2·2H2O
Cu(OAc)2·H2O
CuBr2
PCy3
Ru
Cl
Cl
Cl
Ru
6
Cl
Ph
PCy3
PCy3
7
Grubbs I
Grubbs II
8
Scheme 1 Synthesis of pyrroles based on RCM reactions
9
CuSO4·5H2O
Cu(BF4)2·xH2O
Cu(NO3)2·3H2O
Cu(OTf)2
10
11
12
13
14
15
16
17
18
19
20e
21e
22e
23f
24g
observed with the use of FeCl3-6H2O and CuCl2-2H2O as the
additives (entries 5 and 6). The yield of 2a was increased to
27% when Cu(OAc)2·H2O was used instead of CuCl2·2H2O
(entry 7). Then, several other copper salts [CuBr2,
CuSO4·5H2O, Cu(BF4)2·xH2O, Cu(NO3)2·3H2O] were investi-
gated as the additive in combination with the Grubbs II cat-
alyst under an O2 atmosphere (entries 8–11), but 2a was
still obtained in low yield. We were pleased that pyrrole
product 2a was obtained in 62% yield when Cu(OTf)2 was
used in combination with the Grubbs II catalyst (entry 12).
Subsequently, other triflate salts were investigated as addi-
tives in combination with the Grubbs II catalyst under oth-
erwise identical conditions. Traces of 2a were obtained
when Zn(OTf)2, Mg(OTf)2, AgOTf, or Bi(OTf)3 was used as
the additive (entries 14, 15, 17, and 18). In contrast,
Fe(OTf)3, Al(OTf)3, and Sn(OTf)2 were relatively effective ad-
ditives for the dehydrogenation process (entries 13, 16, and
19). However, Cu(OTf)2 was chosen in our investigations,
because it led to the best yield. The yield of 2a further in-
creased to 87%, and 3a was nearly completely consumed,
when the loading of Cu(OTf)2 was increased from 20 mol%
to 50 mol% (entry 20). No further increase was observed
when the loading of Cu(OTf)2 exceeded 50 mol%. The yield
of 2a decreased to 69% and 80% when the Grubbs I and Hov-
eyda–Grubbs II catalysts were used instead of the Grubbs II
catalyst (entries 21 and 22). When the O2 atmosphere was
changed to air, the yield of 2a also decreased (entry 23).
Furthermore, scaling up the reaction (1a, 0.125 g) provided
the product at good yield (entry 24). Thus, the combination
of the Grubbs II catalyst (5 mol%) with Cu(OTf)2 (50 mol%)
at 110 °C under an atmosphere of oxygen (1 atm) was se-
Fe(OTf)3
Zn(OTf)2
Mg(OTf)2
Al(OTf)3
AgOTf
Bi(OTf)3
Sn(OTf)2
Cu(OTf)2
Cu(OTf)2
Hoveyda–Grubbs II Cu(OTf)2
Grubbs II
Grubbs II
Cu(OTf)2
Cu(OTf)2
51/29
82/8
a Reaction conditions: 1a (0.20 mmol), [Ru] Cat. (0.01 mmol, 5 mol%), addi-
tive (0.04 mmol, 20 mol%), toluene (2.0 mL), 110 °C, 24 h, under O2 (1
atm).
b Isolated yields.
c Reaction conditions: [Ru] Cat. (0.01 mmol, 5 mol%), toluene (2.0 mL), 110
°C, 24 h, under N2 (1 atm).
d Reaction conditions: [Ru] Cat. (0.01 mmol, 5 mol%), toluene (2.0 mL), 110
°C, 24 h, under O2 (1 atm).
e Reaction conditions: [Ru] Cat. (0.01 mmol, 5 mol%), additive (0.10 mmol,
50 mol%), toluene (2.0 mL), 110 °C, 24 h, under O2 (1 atm).
f Reaction conditions: [Ru] Cat. (0.01 mmol, 5 mol%), additive (0.10 mmol,
50 mol%), toluene (2.0 mL), 110 °C, 24 h, under air.
g Reaction was carried out on a 0.125 g scale of 1a (0.50 mmol).
With the optimized reaction conditions in hand, the
scope and limitations of the reaction were subsequently in-
vestigated, and representative results are summarized in
Table 2. With N,N-diallylbenzenesulfonamide (1b) the reac-
tion proceeded smoothly under the optimized reaction
© 2019. Thieme. All rights reserved. — Synthesis 2019, 51, A–P

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W. C. et al.
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Synthesis
conditions to afford pyrrole 2b in 80% yield (entry 2). The
reaction of sulfonyldiallylamines 1a, 1c, 1d, and 1f, each
bearing an electron-donating group on its phenyl group,
proceeded smoothly in the presence of the Grubbs II cata-
lyst (5 mol%) and Cu(OTf)2 (50 mol%) in toluene at 110 °C
under an oxygen atmosphere (1 atm) to generate pyrroles
2a, 2c, 2d, and 2f in good yields (87%, 86%, 83%, and 75%,
respectively) within 24 h (entries 1, 3, 4, and 6). When rela-
tively sterically hindered diallylamine 1e was used as the
substrate, pyrrole 2e was obtained in only moderate yield,
indicating a steric effect on the tandem reaction (entry 5).
With the aromatic rings bearing weak electron-withdraw-
ing groups (entries 7 and 9–12), diallylamines 1g and 1i–l
underwent the RCM/dehydrogenation tandem reaction un-
Table 2 RCM/Dehydrogenation of Sulfonyl Diallylaminesa
Grubbs II (5 mol%)
Cu(OTf)2 (50 mol%)
O
S
O
S
O
S
N
+
N
N
Toluene, 110 °C, 24 h
O
O
O
R
R
R
1
2
3
Entry
1
Product 2
Yield of 2/3b (%)
Entry
Product 2
Yield of 2/3b (%)
O
S
O
S
N
N
87/5
11
12
13
66/29
O
O
Br
2k
2a
O
O
S
N
I
S
N
2
3
80/8
86/6
70/23
60/32
O
O
2b
2l
F
O
O
S
MeO
S
N
N
O
O
2c
2m
O
S
O
O
t-Bu
N
S
N
4
5
83/9
14
15
54/30
51/39
O
O
2d
2n
O
O
S
O2N
S
N
N
N
59/32
O
O
2o
2e
O
S
O
N
S
O
6
75/19
16
43/50
O
O
O2N
2f
2p
O
O
Ph
S
N
S
N
O
O
7
8
72/20
50/40
17
18
50/41
54/39
2g
2q
2r
O
O
F
S
N
S
N
O
O
2h
O
O
S
N
Cl
S
N
N
9
63/30
69/26
19
20
50/38
45/45
S
O
O
2i
2s
O
O
S
S
N
Br
10
S
O
O
Cl
2j
2t
a Reaction conditions: 1 (0.20 mmol), Grubbs II (0.01 mmol, 5 mol%), Cu(OTf)2 (0.10 mmol, 50 mol%), toluene (2.0 mL), 110 °C, 24 h, under O2 (1 atm).
b Isolated yields.
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Synthesis
der the standard conditions well to give pyrroles 2g and 2i–
l in 63–72% yield. Diallylamines 1h and 1n–p, each bearing
an electron-withdrawing group, gave pyrroles 2h and 2n–p
in moderate yields (entries 8 and 14–16). The results indi-
cate that electron-withdrawing groups are unfavorable for
the formation of iminium ion intermediates. Pleasingly, re-
action of diallylamine 1m, bearing an electron-donating
group and an electron-withdrawing group, underwent the
RCM/dehydrogenation tandem reaction smoothly to gener-
ate pyrrole 2m as the major product in 60% yield (entry 13).
Diallylamines 1q and 1r, each bearing a naphthyl group,
also gave the corresponding pyrroles 2q and 2r in 50% and
54% yield, respectively (entries 17 and 18). The thiophene
substrates 1s and 1t were also investigated; they were con-
verted into the corresponding products 2s and 2t in moder-
ate yields under the optimized reaction conditions (entries
19 and 20). These reactions are extremely easy to perform
without the need of using hazardous oxidation agents.
However, the reaction was complex when N,N-diallylcyclo-
propanesulfonamide was used as the substrate and the ex-
pected pyrrole product was not obtained, indicating that
the reaction conditions are not suitable for alkyl-substitut-
ed sulfonyl diallylamines.
under an oxygen atmosphere (1 atm); this gave N-acylpyr-
role 2aa in moderate yield (Table 3, entry 1). Then 1aa was
used as a probe to evaluate the reaction conditions, and the
results are shown in Table 3. Given the importance of cop-
per salts, a series of copper salts was examined for optimiz-
ing the reaction conditions. N-Acylpyrrole 2aa was ob-
tained in low to moderate yields with the use of Cu(OTf)2,
Cu(OAc)2·H2O,
CuSO4·5H2O,
Cu(BF4)2·xH2O,
and
Cu(NO3)2·3H2O as the additive in combination with the
Grubbs II catalyst under an O2 atmosphere (entries 2, 4, and
6–8). The additive CuCl2·2H2O improved the reaction yield
to 83% (entry 3). The most favorable additive was CuBr2,
which gave the desired product 2aa in 91% yield (entry 5).
The yield of 2aa decreased to 73% and 81% when the Grubbs
I and Hoveyda–Grubbs II catalysts were used instead of the
Grubbs II catalyst (entries 9 and 10). Therefore, the combi-
nation of the Grubbs II catalyst (5 mol%) and CuBr2 (20
mol%) at 110 °C under an O2 atmosphere (1 atm) for 24 h
was used as the optimum reaction conditions for the cur-
rent transformation.
Next, the scope of the RCM/dehydrogenation reaction of
acyldiallylamines under the optimized reaction conditions
was investigated, and representative results are summa-
rized in Table 4. Acyldiallylamines 1aa–ee, each bearing an
electron-donating group, underwent the RCM/dehydroge-
nation tandem reaction smoothly in the presence of the
Grubbs II catalyst (5 mol%) and CuBr2 (20 mol%) in toluene
at 110 °C under an oxygen atmosphere (1 atm) to give N-
acylpyrroles 2aa–ee in 90%–93% yields (entries 1–5). Steri-
cally hindered acyldiallylamine 1ff was also a well-tolerat-
ed substrate for the RCM/dehydrogenation tandem reaction
to afford N-acylpyrrole 2ff in 87% yield (entry 6). With elec-
tron-withdrawing groups on the aromatic ring, acyldiallyl-
amines 1gg–oo also gave good results in the RCM/dehydro-
genation tandem reaction under the standard conditions, to
generate N-acylpyrroles 2gg–oo in good yields (entries 7–
15). Furanyl- and thiophenyl-containing diallylamines 1pp–
tt were also found to be suitable substrates for the RCM/de-
hydrogenation tandem reaction, providing the correspond-
ing N-acylpyrroles 2pp–tt in excellent yields (entries 16–
20). Notably, this protocol is also suitable for the N-alkyl-
substituted substrates 1uu and 1vv, which could be con-
verted into pyrroles 2uu and 2vv in 80% and 82% yield, re-
spectively (entries 21 and 22).
Subsequently, the RCM/dehydrogenation reaction of
acyldiallylamines for the synthesis of N-acylpyrroles was
also investigated. The reaction of N,N-diallylbenzamide
(1aa) was examined in the presence of the Grubbs II cata-
lyst (5 mol%) and Cu(OTf)2 (50 mol%) in toluene at 110 °C
Table 3 Conditions for the RCM/Dehydrogenation of N,N-Diallylben-
zamide (1aa)a
O
O
O
[Ru] Cat.
Additive
Ph
N
Ph
N
+
Ph
N
Toluene, 110 °C
24 h, O2
1aa
2aa
3aa
Entry [Ru] Cat.
Additive
Yield of 2aa/3aab (%)
1c
2
3
4
5
6
7
8
9
Grubbs II
Grubbs II
Grubbs II
Grubbs II
Grubbs II
Grubbs II
Grubbs II
Grubbs II
Grubbs I
Cu(OTf)2
Cu(OTf)2
61/30
36/54
83/16
69/22
91/0
CuCl2·2H2O
Cu(OAc)2·H2O
CuBr2
CuSO4·5H2O
29/62
45/51
<5/90
73/20
81/11
The reaction mechanism of this pyrrole synthetic meth-
od was next studied, with representative results illustrated
in Scheme 2. By treating the ring-closing products 3a and
3aa in the presence of the Grubbs II catalyst (5 mol%) in tol-
uene at 110 °C under an atmosphere of oxygen (1 atm) for
24 h, pyrroles 2a and 2aa were obtained in trace and 8%
yield, respectively (Schemes 2a and 2b). With the use of
Cu(OTf)2 (50 mol%) or CuBr2 (20 mol%) instead of the
Grubbs II catalyst (5 mol%) under otherwise identical con-
ditions, the reactions of 3a and 3aa proceeded well to afford
the desired pyrroles 2a and 2aa in 82% and 80% yields, re-
Cu(BF4)2·xH2O
Cu(NO3)2·3H2O
CuBr2
10
Hoveyda–Grubbs II CuBr2
a Reaction conditions: 1aa (0.20 mmol), [Ru] Cat. (0.01 mmol, 5 mol%), ad-
ditive (0.04 mmol, 20 mol%), toluene (2.0 mL), 110 °C, 24 h, under O2 (1
atm).
b Isolated yields.
c Reaction conditions: additive (0.10 mmol, 50 mol%), toluene (2.0 mL),
110 °C, 24 h, under O2 (1 atm).
© 2019. Thieme. All rights reserved. — Synthesis 2019, 51, A–P

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Synthesis
Table 4 RCM/Dehydrogenation of Acyldiallylaminesa
Grubbs II (5 mol%)
CuBr2 (20 mol%)
O
O
O
+
R
N
R
N
R
N
Toluene, 110 °C, 24 h
R = Ar, Alkyl
1
2
3
Entry
1
Product
Yields of 2/3b (%)
Entry
12
Product
Yields of 2/3b (%)
O
OAc O
N
N
91/0
90/0
82/8
2aa
2ll
O
O
O2N
2mm
N
N
2
3
13
14
80/10
80/12
Et
2bb
O
O
MeO
N
N
N
O
92/0
2cc
2nn
2oo
O
N
4
5
6
93/0
90/0
87/0
15
16
17
83/10
82/9
MeO
2dd
O
O
O
O
N
O
N
O
2pp
2ee
2ff
N
N
N
81/12
O
2qq
O
N
7
8
87/5
86/9
18
19
80/10
66/26
S
I
2rr
2gg
O
O
N
N
N
S
Br
2hh
2ss
O
O
Br
N
9
87/9
20
72/16
S
2ii
Cl
2tt
O
O
N
N
10
11
83/10
80/11
21
22
80/12
82/10
Cl
2jj
2uu
O
O
F
N
N
2vv
2kk
a Reaction conditions: 1 (0.20 mmol), Grubbs II (0.01 mmol, 5 mol%), Cu(OTf)2 (0.10 mmol, 50 mol%), toluene (2.0 mL), 110 °C, 24 h, under O2 (1 atm).
b Isolated yields.
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Synthesis
spectively (Schemes 2c and 2d). However, the yields of 2a
and 2aa in the control experiments were all lower than
those obtained when a combination of the Grubbs II cata-
lyst/Cu(OTf)2 or the Grubbs II catalyst/CuBr2 was used.
um ion intermediates, which lead, in turn, to pyrroles by
aromatization. Cu(OTf)2 and CuBr2 played a critical role in
the high conversions of the ring-closing products to pyr-
roles. This is a straightforward one-pot synthetic pathway
for the synthesis of N-sulfonyl- and N-acylpyrroles based on
the RCM reaction. Further applications of this tandem reac-
tion for the diversity-oriented synthesis of N-substituted
pyrroles are currently under investigation, and will be re-
ported in due course.
Grubbs II (5 mol%)
Ts
N
Ts
N
(a)
Toluene, 110 °C
24 h, O2, trace
3a
2a
O
O
Grubbs II (5 mol%)
N
N
(b)
(c)
Toluene, 110 °C
24 h, O2, 8%
Ph
Ph
2aa
3aa
All reactions were carried out under an O2 atmosphere except when
noted otherwise. CH2Cl2 and toluene were distilled prior to use under
a N2 atmosphere. Silica gel (200–300 mesh) was used for flash chro-
matography. The sulfonyl- and acyldiallylamines were prepared ac-
cording to literature procedures.17–22 Sulfonyl chloride, formyl chlo-
ride, diallylamine, and other reagents were purchased from commer-
cial sources and used as received. High-resolution mass spectra were
recorded by using an Electrothermal LTQ-Orbitrap mass spectrome-
ter. Melting points were measured by using a Gongyi X-5 microscopy
digital melting point apparatus and are uncorrected. 1H and 13C NMR
spectra were recorded on a Bruker Avance III 400 MHz NMR spec-
trometer with CDCl3 as solvent. The chemical shifts are reported in
ppm relative to CDCl3 ( = 7.26) for 1H NMR and relative to the central
CDCl3 resonance ( = 77.0) for 13C NMR. NMR data of known com-
pounds are in agreement with literature values.
Cu(OTf)2 (50 mol%)
Ts
N
Ts
N
Toluene, 110 °C
24 h, O2, 82%
3a
2a
O
O
CuBr2 (20 mol%)
N
N
(d)
Toluene, 110 °C
24 h, O2, 80%
Ph
Ph
3aa
2aa
Scheme 2 Control experiments
Based on the above results and related reports in the lit-
erature,9d,15a a plausible pathway for this RCM/dehydroge-
nation tandem reaction is illustrated in Scheme 3. First, the
diallylamines 1 undergo cyclization to form ring-closing
products 3 in the presence of the ruthenium Grubbs cata-
lyst. Meanwhile, Ru–oxo complexes form from the rutheni-
um Grubbs catalyst by oxidation.16 In path A, the ring-clos-
ing products 3 are oxidized to the iminium ion intermedi-
ates 4 by the Ru–oxo complexes.15a The ring-closing
products 3 can also be converted into the final products un-
der the catalysis of Cu(OTf)2 or CuBr2, respectively. Accord-
ingly, intermediates 4 are formed in the presence of
Cu(OTf)2 or CuBr2 in path B. The control experiment data
(Scheme 2) indicate that path A is the minor catalytic path-
way and that path B is the major pathway. Finally, an oxida-
tion–aromatization reaction of the ring-closing products 3
gives the desired pyrrole products 2.
Sulfonyldiallylamines 1a–t; General Procedure17–19
Et3N (116 mg, 1.15 mmol) was added dropwise to a stirred solution of
diallylamine (100 mg, 1.03 mmol) in anhyd CH2Cl2 (3.0 mL) at 0 °C.
After 0.5 h, the appropriate sulfonyl chloride (1.0 mmol) was slowly
added to the mixture. The solution was allowed to warm to room
temperature and stirred overnight. The reaction mixture was poured
into a separation funnel containing H2O (3.0 mL). The aqueous phase
was removed and the organic phase was subsequently washed with 1
M aq HCl (3.0 mL) and brine (3.0 mL), dried over Na2SO4, and filtered.
The volatiles were removed in vacuo and the residue was subjected to
flash column chromatography to give the corresponding sulfonyldial-
lylamine.
N,N-Diallyl-p-methylbenzenesulfonamide (1a)
Compound 1a was prepared according to a literature procedure.17
Yield: 225.9 mg (90%); colorless oil.
LnRuCl2
R
N
R
N
1
3
1H NMR (400 MHz, CDCl3):  = 7.70 (d, J = 8.4 Hz, 2 H), 7.29 (d, J = 8.0
Hz, 2 H), 5.65–5.55 (m, 2 H), 5.16–5.11 (m, 4 H), 3.79 (d, J = 6.0 Hz, 4
H), 2.42 (s, 3 H).
Cu2+
LnCl2Ru=O
H2O
Path A Path B
ref. 15a O2
ref. 9d
minor
major
Cu+
13C NMR (100 MHz, CDCl3):  = 143.2, 137.4, 132.6, 129.6, 127.1,
O2
LnRuCl2
118.9, 49.3, 21.5.
O2 atmosphere
Tautomerization
R
N
R N
N,N-Diallylbenzenesulfonamide (1b)
Compound 1b was prepared according to a literature procedure.17
4
2
H
Scheme 3 A plausible pathway
Yield: 208.6 mg (88%); colorless oil.
1H NMR (400 MHz, CDCl3):  = 7.83–7.81 (m, 2 H), 7.59–7.48 (m, 3 H),
5.65–5.55 (m, 2 H), 5.16–5.11 (m, 4 H), 3.82 (d, J = 6.4 Hz, 4 H).
13C NMR (100 MHz, CDCl3):  = 140.4, 132.5, 129.0, 127.1, 119.0, 49.3.
In summary, a RCM/dehydrogenation tandem reaction
of diallylamines has been developed, which provides a vari-
ety of N-sulfonyl- and N-acylpyrrole derivatives in moder-
ate to good yields under the optimized reaction conditions.
The corresponding pyrrole products are obtained via imini-
N,N-Diallyl-p-methoxybenzenesulfonamide (1c)
Compound 1c was prepared according to a literature procedure.17
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Yield: 243.0 mg (91%); colorless oil.
1H NMR (400 MHz, CDCl3):  = 7.76 (d, J = 8.4 Hz, 2 H), 7.47 (d, J = 8.8
Hz, 2 H), 5.65–5.55 (m, 2 H), 5.17–5.12 (m, 4 H), 3.81 (d, J = 6.4 Hz, 4
H).
13C NMR (100 MHz, CDCl3):  = 139.0, 138.9, 132.2, 129.3, 128.5,
1H NMR (400 MHz, CDCl3):  = 7.74 (d, J = 9.2 Hz, 2 H), 6.96 (d, J = 8.8
Hz, 2 H), 5.66–5.56 (m, 2 H), 5.16–5.11 (m, 4 H), 3.86 (s, 3 H), 3.78 (d,
J = 6.4 Hz, 4 H).
119.3, 49.3.
13C NMR (100 MHz, CDCl3):  = 162.7, 132.7, 132.0, 129.2, 118.9,
114.1, 55.5, 49.3.
N,N-Diallyl-p-bromobenzenesulfonamide (1j)
Compound 1j was prepared according to a literature procedure.17 90%
yield; 284.4mg; colorless oil.
1H NMR (400 MHz, CDCl3):  = 7.69–7.62 (m, 4 H), 5.65–5.55 (m, 2 H),
5.17–5.12 (m, 4 H), 3.81 (d, J = 6.4 Hz, 4 H).
13C NMR (100 MHz, CDCl3):  = 139.5, 132.3, 132.2, 128.6, 127.3,
N,N-Diallyl-p-tert-butylbenzenesulfonamide (1d)
Compound 1d was prepared according to a literature procedure.18
Yield: 254.9 mg (87%); white solid; mp 53–54 °C.
1H NMR (400 MHz, CDCl3):  = 7.74 (d, J = 8.8 Hz, 2 H), 7.50 (d, J = 8.4
Hz, 2 H), 5.68–5.58 (m, 2 H), 5.16–5.13 (m, 4 H), 3.81 (d, J = 6.4 Hz, 4
H), 1.34 (s, 9 H).
119.3, 49.3.
13C NMR (100 MHz, CDCl3):  = 156.2, 137.3, 132.8, 127.0, 126.0,
118.9, 49.4, 35.1, 31.1.
N,N-Diallyl-m-bromobenzenesulfonamide (1k)
Compound 1k was prepared according to a literature procedure.17
Yield: 259.1 mg (82%); colorless oil.
1H NMR (400 MHz, CDCl3):  = 7.96 (t, J = 2.2 Hz, 1 H), 7.75–7.67 (m, 2
H), 7.38 (t, J = 8.0 Hz, 1 H), 5.65–5.55 (m, 2 H), 5.18–5.13 (m, 4 H), 3.82
(d, J = 6.4 Hz, 4 H).
N,N-Diallyl-2,4-dimethylbenzenesulfonamide (1e)
Compound 1e was prepared according to a literature procedure.18
Yield: 235.9 mg (89%); colorless oil.
1H NMR (400 MHz, CDCl3):  = 7.84 (d, J = 8.0 Hz, 1 H), 7.09 (d, J = 8.0
Hz, 2 H), 5.69–5.59 (m, 2 H), 5.18–5.12 (m, 4 H), 3.81 (d, J = 6.4 Hz, 4
H), 2.55 (s, 3 H), 2.36 (s, 3 H).
13C NMR (100 MHz, CDCl3):  = 142.3, 135.5, 132.1, 130.6, 130.0,
125.6, 123.0, 119.3, 49.3.
13C NMR (100 MHz, CDCl3):  = 143.3, 137.4, 135.1, 133.3, 132.7,
130.2, 126.6, 119.2, 48.3, 21.2, 20.2.
N,N-Diallyl-p-iodobenzenesulfonamide (1l)
Compound 1l was prepared according to a literature procedure.17
Yield: 294.0 mg (81%); colorless oil.
1H NMR (400 MHz, CDCl3):  = 7.87 (d, J = 8.4 Hz, 2 H), 7.54 (d, J = 8.4
Hz, 2 H), 5.66–5.56 (m, 2 H), 5.18–5.14 (m, 4 H), 3.82 (d, J = 6.4 Hz, 4
N,N-Diallyl-2,3-dihydrobenzofuran-5-sulfonamide (1f)
Compound 1f was prepared according to a literature procedure.17
Yield: 226.0 mg (81%); colorless oil.
1H NMR (400 MHz, CDCl3):  = 7.62–7.58 (m, 2 H), 6.82 (d, J = 8.4 Hz, 1
H), 5.67–5.57 (m, 2 H), 5.16–5.11 (m, 4 H), 4.66 (t, J = 8.8 Hz, 2 H), 3.77
(d, J = 6.4 Hz, 4 H), 3.25 (t, J = 8.8 Hz, 2 H).
H).
13C NMR (100 MHz, CDCl3):  = 140.1, 138.2, 132.1, 128.5, 119.2, 99.7,
49.2.
13C NMR (100 MHz, CDCl3):  = 163.6, 132.8, 131.8, 128.6, 128.2,
124.4, 118.8, 109.4, 72.2, 49.3, 29.0.
N,N-Diallyl-3-fluoro-4-methylbenzenesulfonamide (1m)
Compound 1m was prepared according to a literature procedure.17
Yield: 239.4 mg (89%); colorless oil.
N,N-Diallyl-p-phenylbenzenesulfonamide (1g)
Compound 1g was prepared according to a literature procedure.17
1H NMR (400 MHz, CDCl3):  = 7.51–7.44 (m, 2 H), 7.32 (t, J = 7.6 Hz, 1
H), 5.66–5.56 (m, 2 H), 5.17–5.12 (m, 4 H), 3.81 (d, J = 6.4 Hz, 4 H),
2.34 (s, 3 H).
13C NMR (100 MHz, CDCl3):  = 162.0, 159.5, 139.6, 139.5, 132.3,
132.1, 132.0, 130.4, 130.2, 122.6, 122.5, 119.2, 114.2, 113.9, 49.3, 14.7,
14.6.
Yield: 272.3 mg (87%); white solid; mp 68–69 °C.
1H NMR (400 MHz, CDCl3):  = 7.89 (d, J = 8.8 Hz, 2 H), 7.72 (d, J = 8.8
Hz, 2 H), 7.63–7.61 (m, 2 H), 7.51–7.40 (m, 3 H), 5.70–5.60 (m, 2 H),
5.19–5.15 (m, 4 H), 3.86 (d, J = 6.4 Hz, 4 H).
13C NMR (100 MHz, CDCl3):  = 145.3, 139.3, 139.0, 132.6, 129.0,
128.4, 127.7, 127.3, 119.1, 49.4.
N,N-Diallyl-p-acetylbenzenesulfonamide (1n)
Compound 1n was prepared according to a literature procedure.19
Yield: 239.9 mg (86%); colorless oil.
1H NMR (400 MHz, CDCl3):  = 8.05 (d, J = 8.8 Hz, 2 H), 7.90 (d, J = 8.8
Hz, 2 H), 5.63–5.53 (m, 2 H), 5.16–5.11 (m, 4 H), 3.83 (d, J = 6.4 Hz, 4
H), 2.64 (s, 3 H).
N,N-Diallyl-p-fluorobenzenesulfonamide (1h)
Compound 1h was prepared according to a literature procedure.17
Yield: 204.0 mg (80%); colorless oil.
1H NMR (400 MHz, CDCl3):  = 7.85–7.82 (m, 2 H), 7.20–7.15 (m, 2 H),
5.65–5.55 (m, 2 H), 5.17–5.12 (m, 4 H), 3.81 (d, J = 6.4 Hz, 4 H).
13C NMR (100 MHz, CDCl3):  = 196.7, 144.4, 139.8, 132.0, 128.9,
127.3, 119.4, 49.3, 26.8.
13C NMR (100 MHz, CDCl3):  = 166.2, 163.7, 136.6, 136.5, 132.3,
129.8, 129.7, 119.2, 116.3, 116.1, 49.2.
N,N-Diallyl-p-nitrobenzenesulfonamide (1o)
Compound 1o was prepared according to a literature procedure.19
N,N-Diallyl-p-chlorobenzenesulfonamide (1i)
Compound 1i was prepared according to a literature procedure.17
Yield: 241.2 mg (89%); colorless oil.
Yield: 231.2 mg (82%); white solid; mp 65–66 °C.
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W. C. et al.
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1H NMR (400 MHz, CDCl3):  = 8.35 (d, J = 9.2 Hz, 2 H), 8.01 (d, J = 8.8
Hz, 2 H), 5.65–5.55 (m, 2 H), 5.20–5.15 (m, 4 H), 3.87 (d, J = 6.4 Hz, 4
H).
1H NMR (400 MHz, CDCl3):  = 5.86–5.76 (m, 2 H), 5.27–5.22 (m, 4 H),
3.86 (d, J = 6.0 Hz, 4 H), 2.35–2.28 (m, 1 H), 1.18–1.15 (m, 2 H), 1.00–
0.94 (m, 2 H).
13C NMR (100 MHz, CDCl3):  = 149.9, 146.5, 131.7, 128.3, 124.4,
13C NMR (100 MHz, CDCl3):  = 132.9, 118.9, 49.1, 30.2, 5.3.
119.8, 49.3.
Acyldiallylamines 1aa–vv; General Procedure20–22
N,N-Diallyl-m-nitrobenzenesulfonamide (1p)
Compound 1p was prepared according to a literature procedure.19
Yield: 228.4 mg (81%); yellow oil.
1H NMR (400 MHz, CDCl3):  = 8.65 (t, J = 2.0 Hz, 1 H), 8.43–8.40 (m, 1
H), 8.16–8.13 (m, 1 H), 7.73 (t, J = 8.0 Hz, 1 H), 5.66–5.56 (m, 2 H),
5.20–5.15 (m, 4 H), 3.87 (d, J = 6.4 Hz, 4 H).
Et3N (126 mg, 1.25 mmol) was added dropwise to a stirred solution of
diallylamine (107 mg, 1.10 mmol) in anhyd CH2Cl2 (3.0 mL) at 0 °C.
Then the appropriate formyl chloride (1.00 mmol) was slowly added
to the mixture. The solution was allowed to warm to room tempera-
ture and stirred until the end of the reaction. The reaction mixture
was poured into a separation funnel containing H2O (3.0 mL). The
aqueous phase was removed and the organic phase was subsequently
washed with 1 M aq HCl (3.0 mL) and brine (3.0 mL), dried over Na2-
SO4, and filtered. The volatiles were removed in vacuo and the residue
was subjected to flash column chromatography to give the corre-
sponding acyldiallylamine.
13C NMR (100 MHz, CDCl3):  = 148.2, 142.8, 132.6, 131.7, 130.4,
126.9, 122.3, 119.7, 49.4.
N,N-Diallyl-1-naphthalenesulfonamide (1q)
Compound 1q was prepared according to a literature procedure.17
Yield: 246.8 mg (86%); colorless oil.
1H NMR (400 MHz, CDCl3):  = 8.63 (d, J = 8.8 Hz, 1 H), 8.27–8.25 (m, 1
H), 8.05 (d, J = 8.0 Hz, 1 H), 7.92 (d, J = 8.0 Hz, 1 H), 7.68–7.50 (m, 3 H),
5.62–5.52 (m, 2 H), 5.13–5.09 (m, 4 H), 3.90 (d, J = 6.4 Hz, 4 H).
N,N-Diallylbenzamide (1aa)
Compound 1aa was prepared according to a literature procedure.20
Yield: 180.9 mg (90%); colorless oil.
1H NMR (400 MHz, CDCl3):  = 7.44–7.34 (m, 5 H), 5.86 (br s, 1 H),
13C NMR (100 MHz, CDCl3):  = 134.9, 134.3, 134.2, 132.5, 130.1,
128.9, 128.4, 128.0, 126.7, 124.9, 124.0, 119.2, 48.4.
5.72 (br s, 1 H), 5.24–5.16 (m, 4 H), 4.13 (br s, 2 H), 3.82 (br s, 2 H).
13C NMR (100 MHz, CDCl3):  = 171.7, 136.2, 133.1, 132.7, 129.5,
128.3, 126.5, 117.6, 50.7, 46.9.
N,N-Diallyl-2-naphthalenesulfonamide (1r)
Compound 1r was prepared according to a literature procedure.17
Yield: 252.6 mg (88%); colorless oil.
N,N-Diallyl-p-ethylbenzamide (1bb)
Compound 1bb was prepared according to a literature procedure.20
1H NMR (400 MHz, CDCl3):  = 8.41 (s, 1 H), 7.97–7.90 (m, 3 H), 7.81–
7.78 (m, 1 H), 7.66–7.59 (m, 2 H), 5.67–5.57 (m, 2 H), 5.17–5.12 (m, 4
H), 3.88 (d, J = 6.4 Hz, 4 H).
13C NMR (100 MHz, CDCl3):  = 137.3, 134.7, 132.6, 132.2, 129.4,
129.2, 128.7, 128.4, 127.9, 127.5, 122.5, 119.1, 49.3.
Yield: 203.8 mg (89%); colorless oil.
1H NMR (400 MHz, CDCl3):  = 7.35 (d, J = 8.4 Hz, 2 H), 7.20 (d, J = 8.0
Hz, 2 H), 5.86 (br s, 1 H), 5.75 (br s, 1 H), 5.24–5.16 (m, 4 H), 4.12 (br s,
2 H), 3.86 (br s, 2 H), 2.65 (q, J = 7.6 Hz, 2 H), 1.23 (t, J = 7.6 Hz, 3 H).
13C NMR (100 MHz, CDCl3):  = 171.9, 145.9, 133.5, 127.7, 126.7,
117.5, 50.8, 46.9, 28.7, 15.3.
N,N-Diallyl-2-thiophenesulfonamide (1s)
Compound 1s was prepared according to a literature procedure.17
N,N-Diallyl-m-methoxybenzamide (1cc)
Compound 1cc was prepared according to a literature procedure.20
Yield: 194.4 mg (80%); colorless oil.
1H NMR (400 MHz, CDCl3):  = 7.58–7.56 (m, 2 H), 7.10–7.08 (m, 1 H),
5.70–5.60 (m, 2 H), 5.19–5.15 (m, 4 H), 3.83 (d, J = 6.4 Hz, 4 H).
13C NMR (100 MHz, CDCl3):  = 140.9, 132.2, 131.7, 131.5, 127.3,
Yield: 205.6 mg (89%); colorless oil.
1H NMR (400 MHz, CDCl3):  = 7.29–7.25 (m, 1 H), 6.99–6.91 (m, 3 H),
5.86 (br s, 1 H), 5.73 (br s, 1 H), 5.24–5.16 (m, 4 H), 4.11 (br s, 2 H),
3.83 (br s, 2 H), 3.79 (s, 3 H).
119.2, 49.7.
13C NMR (100 MHz, CDCl3):  = 171.4, 159.4, 137.4, 133.2, 132.7,
129.4, 118.6, 117.5, 115.6, 111.8, 55.3, 50.6, 46.9.
N,N-Diallyl-5-chlorothiophene-2-sulfonamide (1t)
Compound 1t was prepared according to a literature procedure.17
Yield: 227.1 mg (82%); colorless oil.
1H NMR (400 MHz, CDCl3):  = 7.34 (d, J = 4.0 Hz, 1 H), 6.92 (d, J = 4.0
Hz, 1 H), 5.72–5.62 (m, 2 H), 5.21–5.17 (m, 4 H), 3.82 (d, J = 6.4 Hz, 4
N,N-Diallyl-p-methoxybenzamide (1dd)
Compound 1dd was prepared according to a literature procedure.20
Yield: 203.3 mg (88%); white solid; mp 39–40 °C.
1H NMR (400 MHz, CDCl3):  = 7.41 (d, J = 8.4 Hz, 2 H), 6.87 (d, J = 8.8
H).
13C NMR (100 MHz, CDCl3):  = 139.0, 136.8, 132.0, 131.1, 126.7,
119.5, 49.6.
Hz, 2 H), 5.81 (br s, 2 H), 5.23–5.16 (m, 4 H), 3.98 (br s, 4 H), 3.80 (s, 3
H).
13C NMR (100 MHz, CDCl3):  = 171.5, 160.6, 133.1, 128.6, 128.3,
117.4, 113.5, 55.2, 50.7, 47.4.
N,N-Diallylcyclopropanesulfonamide
This compound was prepared according to a literature procedure.17
N,N-Diallyl-o-methylbenzamide (1ee)
Compound 1ee was prepared according to a literature procedure.21
Yield: 138.7 mg (69%); yellow oil.
Yield: 195.7 mg (91%); colorless oil.
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Synthesis
1H NMR (400 MHz, CDCl3):  = 7.27–7.23 (m, 1 H), 7.20–7.15 (m, 3 H),
5.92–5.83 (m, 1 H), 5.67–5.57 (m, 1 H), 5.26–5.05 (m, 4 H), 3.68 (br s,
4 H), 2.30 (s, 3 H).
1H NMR (400 MHz, CDCl3):  = 7.38–7.33 (m, 1 H), 7.21–7.07 (m, 3 H),
5.86 (br s, 1 H), 5.72 (br s, 1 H), 5.29–5.17 (m, 4 H), 4.12 (br s, 2 H),
3.82 (br s, 2 H).
13C NMR (100 MHz, CDCl3):  = 171.3, 136.3, 134.0, 132.8, 132.7,
130.3, 128.8, 125.7, 125.5, 117.8, 50.1, 46.1, 19.0.
13C NMR (100 MHz, CDCl3):  = 170.2, 163.6, 161.1, 138.1, 132.8,
132.5, 130.2, 130.1, 122.2, 122.1, 117.8, 116.7, 116.5, 114.0, 113.8,
53.4, 50.6, 47.0.
N,N-Diallyl-2,4,6-trimethylbenzamide (1ff)
Compound 1ff was prepared according to a literature procedure.21
Yield: 199.3 mg (82%); colorless oil.
2-(Diallylcarbamoyl)phenyl Acetate (1ll)
Compound 1ll was prepared according to a literature procedure.22
Yield: 207.2 mg (80%); colorless oil.
1H NMR (400 MHz, CDCl3):  = 6.83 (s, 2 H), 5.93–5.83 (m, 1 H), 5.66–
5.56 (m, 1 H), 5.27–5.22 (m, 2 H), 5.14–5.01 (m, 2 H), 4.19 (d, J = 6.4
Hz, 2 H), 3.66 (d, J = 6.0 Hz, 2 H), 2.26 (s, 3 H), 2.20 (s, 6 H).
13C NMR (100 MHz, CDCl3):  = 171.0, 137.9, 133.4, 132.9, 132.8,
128.2, 118.5, 118.4, 50.0, 45.8, 21.0, 19.0.
1H NMR (400 MHz, CDCl3):  = 7.42–7.37 (m, 1 H), 7.32–7.30 (m, 1 H),
7.24–7.20 (m, 1 H), 7.16–7.14 (m, 1 H), 5.87–5.77 (m, 1 H), 5.71–5.61
(m, 1 H), 5.28–5.10 (m, 4 H), 4.11 (br s, 2 H), 3.75 (br s, 2 H), 2.25 (s, 3
H).
13C NMR (100 MHz, CDCl3):  = 169.0, 167.9, 146.9, 133.0, 132.4,
130.1, 129.7, 127.0, 125.8, 122.9, 117.7, 117.6, 50.4, 46.3, 20.8.
N,N-Diallyl-p-iodobenzamide (1gg)
Compound 1gg was prepared according to a literature procedure.22
N,N-Diallyl-m-nitrobenzamide (1mm)
Compound 1mm was prepared according to a literature procedure.22
Yield: 284.5 mg (87%); white solid; mp 50–51 °C.
1H NMR (400 MHz, CDCl3):  = 7.72 (d, J = 8.4 Hz, 2 H), 7.16 (d, J = 8.4
Hz, 2 H), 5.84 (br s, 1 H), 5.70 (br s, 1 H), 5.28–5.15 (m, 4 H), 4.10 (br s,
2 H), 3.80 (br s, 2 H).
13C NMR (100 MHz, CDCl3):  = 170.7, 137.4, 135.5, 132.9, 132.5,
128.3, 117.7, 95.8, 50.6, 47.1.
Yield: 216.5 mg (88%); yellow oil.
1H NMR (400 MHz, CDCl3):  = 8.31 (t, J = 1.8 Hz, 1 H), 8.28–8.25 (m, 1
H), 7.79–7.76 (m, 1 H), 7.59 (t, J = 7.8 Hz, 1 H), 5.87 (br s, 1 H), 5.74 (br
s, 1 H), 5.28–5.20 (m, 4 H), 4.15 (br s, 2 H), 3.82 (br s, 2 H).
13C NMR (100 MHz, CDCl3):  = 169.1, 147.9, 137.7, 132.6, 129.6,
124.4, 121.8, 118.3, 118.0, 50.7, 50.6, 47.4.
N,N-Diallyl-p-bromobenzamide (1hh)
Compound 1hh was prepared according to a literature procedure.22
N,N-Diallyl-1-naphthamide (1nn)
Compound 1nn was prepared according to a literature procedure.22
Yield: 249.2 mg (89%); white solid; mp 55–56 °C.
1H NMR (400 MHz, CDCl3):  = 7.51 (d, J = 8.4 Hz, 2 H), 7.30 (d, J = 8.4
Hz, 2 H), 5.84 (br s, 1 H), 5.71 (br s, 1 H), 5.28–5.16 (m, 4 H), 4.10 (br s,
2 H), 3.80 (br s, 2 H).
13C NMR (100 MHz, CDCl3):  = 170.6, 135.0, 132.9, 132.5, 131.5,
128.3, 123.9, 117.8, 50.6, 47.1.
Yield: 200.8 mg (80%); colorless oil.
1H NMR (400 MHz, CDCl3):  = 7.87–7.84 (m, 3 H), 7.55–7.41 (m, 4 H),
6.06–5.96 (m, 1 H), 5.64–5.55 (m, 1 H), 5.34–5.28 (m, 2 H), 5.14–5.04
(m, 2 H), 4.56 (br s, 1 H), 4.03 (br s, 1 H), 3.66 (d, J = 5.6 Hz, 2 H).
13C NMR (100 MHz, CDCl3):  = 170.7, 134.2, 133.4, 133.0, 132.8,
129.5, 129.0, 128.3, 126.9, 126.3, 124.9, 124.7, 123.4, 118.0, 117.9,
50.6, 46.3.
N,N-Diallyl-m-bromobenzamide (1ii)
Compound 1ii was prepared according to a literature procedure.22
Yield: 232.4 mg (83%); colorless oil.
N,N-Diallyl-2-naphthamide (1oo)
Compound 1oo was prepared according to a literature procedure.22
1H NMR (400 MHz, CDCl3):  = 7.57–7.52 (m, 2 H), 7.35 (d, J = 7.6 Hz, 1
H), 7.27–7.23 (m, 1 H), 5.85 (br s, 1 H), 5.72 (br s, 1 H), 5.29–5.17 (m, 4
H), 4.11 (br s, 2 H), 3.81 (br s, 2 H).
13C NMR (100 MHz, CDCl3):  = 170.0, 138.1, 132.8, 132.7, 132.4,
129.9, 129.7, 125.0, 122.4, 117.9, 53.4, 50.7, 47.1.
Yield: 205.8 mg (82%); colorless oil.
1H NMR (400 MHz, CDCl3):  = 7.94 (d, J = 1.6 Hz, 1 H), 7.87–7.83 (m, 3
H), 7.55–7.50 (m, 3 H), 5.93 (br s, 1 H), 5.77 (br s, 1 H), 5.28–5.21 (m, 4
H), 4.19 (br s, 2 H), 3.89 (br s, 2 H).
13C NMR (100 MHz, CDCl3):  = 171.7, 133.6, 133.5, 132.6, 128.3,
128.2, 127.7, 126.9, 126.6, 126.2, 124.0, 117.6, 50.8, 47.1.
N,N-Diallyl-p-chlorobenzamide (1jj)
Compound 1jj was prepared according to a literature procedure.22
Yield: 202.1 mg (86%); white solid; mp 58–59 °C.
1H NMR (400 MHz, CDCl3):  = 7.39–7.34 (m, 4 H), 5.85 (br s, 1 H),
5.72 (br s, 1 H), 5.29–5.16 (m, 4 H), 4.11 (br s, 2 H), 3.81 (br s, 2 H).
13C NMR (100 MHz, CDCl3):  = 170.6, 135.7, 134.5, 132.9, 132.5,
N,N-Diallylfuran-2-carboxamide (1pp)
Compound 1pp was prepared according to a literature procedure.22
Yield: 152.8 mg (80%); colorless oil.
1H NMR (400 MHz, CDCl3):  = 7.47 (d, J = 0.8 Hz, 1 H), 7.02 (d, J = 3.6
Hz, 1 H), 6.45–6.44 (m, 1 H), 5.91–5.83 (m, 2 H), 5.22–5.17 (m, 4 H),
4.11 (br s, 4 H).
13C NMR (100 MHz, CDCl3):  = 160.0, 147.7, 143.9, 133.3, 132.8,
117.5, 116.1, 111.2, 49.8, 48.4.
128.6, 128.1, 117.7, 50.6, 47.2.
N,N-Diallyl-m-fluorobenzamide (1kk)
Compound 1kk was prepared according to a literature procedure.22
Yield: 194.9 mg (89%); colorless oil.
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N,N-Diallylfuran-3-carboxamide (1qq)
N-Sulfonylpyrroles 2a–t; General procedure I
Compound 1qq was prepared according to a literature procedure.22
A Schlenk tube equipped with a magnetic stir bar was charged with
the Grubbs II cat. (8.5 mg, 0.01 mmol), Cu(OTf)2 (36.2 mg, 0.10 mmol),
the appropriate sulfonyldiallylamine 1 (1.0 equiv, 0.20 mmol), and
toluene (2.0 mL). The tube was under an O2 balloon and the mixture
was stirred at 110 °C in an oil bath for 24 h, after which the mixture
was cooled to room temperature. The solvent was removed under re-
duced pressure, and the residue was purified by flash chromatogra-
phy to give the desired product.
Yield: 154.7 mg (81%); colorless oil.
1H NMR (400 MHz, CDCl3):  = 7.75–7.74 (m, 1 H), 7.38 (t, J = 1.8 Hz, 1
H), 6.63–6.62 (m, 1 H), 5.88–5.78 (m, 2 H), 5.22 (br s, 4 H), 4.04 (s, 4
H).
13C NMR (100 MHz, CDCl3):  = 164.8, 143.4, 142.7, 133.0, 121.0,
117.5, 117.1, 110.3, 50.0, 47.9.
N,N-Diallylthiophene-2-carboxamide (1rr)
Compound 1rr was prepared according to a literature procedure.22
Yield: 169.7 mg (82%); colorless oil.
1-[(4-Methylphenyl)sulfonyl]-1H-pyrrole (2a)
The synthesis was carried out according to general procedure I.
Yield: 38.5 mg (87%); white solid; mp 96–98 °C.
1H NMR (400 MHz, CDCl3):  = 7.44–7.42 (m, 1 H), 7.39–7.38 (m, 1 H),
7.01–6.99 (m, 1 H), 5.92–5.82 (m, 2 H), 5.28–5.21 (m, 4 H), 4.10 (d, J =
5.2 Hz, 4 H).
13C NMR (100 MHz, CDCl3):  = 164.4, 137.7, 132.8, 129.1, 128.4,
126.7, 117.6, 49.6.
IR (film): 1596, 1455, 1364, 1187, 1168, 1057, 734, 673 cm–1
1H NMR (400 MHz, CDCl3):  = 7.74 (d, J = 8.0 Hz, 2 H), 7.28 (d, J = 8.0
Hz, 2 H), 7.15 (s, 2 H), 6.28 (s, 2 H), 2.40 (s, 3 H).
13C NMR (100 MHz, CDCl3):  = 144.9, 136.1, 129.9, 126.8, 120.7,
.
113.5, 21.6.
HRMS (ESI): m/z [M + Na]+ calcd for C11H11NNaO2S: 244.0403; found:
244.0400.
These spectral data correspond to previously reported data.23
N,N-Diallyl-3-methylthiophene-2-carboxamide (1ss)
Compound 1ss was prepared according to a literature procedure.22
Yield: 179.0 mg (81%); colorless oil.
1H NMR (400 MHz, CDCl3):  = 7.22 (d, J = 4.8 Hz, 1 H), 6.82 (d, J = 4.8
Hz, 1 H), 5.83–5.73 (m, 2 H), 5.22–5.14 (m, 4 H), 4.01 (br s, 4 H), 2.26
(s, 3 H).
13C NMR (100 MHz, CDCl3):  = 165.8, 137.5, 132.9, 129.9, 129.6,
125.2, 117.8, 49.1, 14.5.
1-(Phenylsulfonyl)-1H-pyrrole (2b)
The synthesis was carried out according to general procedure I.
Yield: 33.1 mg (80%); white solid; mp 87–89 °C.
IR (film): 1449, 1368, 1190, 1170, 1057, 728, 685 cm–1
1H NMR (400 MHz, CDCl3):  = 7.85 (d, J = 8.0 Hz, 2 H), 7.60 (d, J = 7.2
Hz, 1 H), 7.50 (t, J = 7.6 Hz, 2 H), 7.17 (s, 2 H), 6.30 (s, 2 H).
13C NMR (100 MHz, CDCl3):  = 139.1, 133.8, 129.3, 126.7, 120.8,
.
N,N-Diallyl-5-chlorothiophene-2-carboxamide (1tt)
Compound 1tt was prepared according to a literature procedure.22
Yield: 197.6 mg (82%); colorless oil.
1H NMR (400 MHz, CDCl3):  = 7.18 (d, J = 4.0 Hz, 1 H), 6.82 (d, J = 4.0
Hz, 1 H), 5.90–5.80 (m, 2 H), 5.28–5.20 (m, 4 H), 4.08 (d, J = 5.2 Hz, 4
113.7.
HRMS (ESI): m/z [M + Na]+ calcd for C10H9NNaO2S: 230.0246; found:
230.0243.
These spectral data correspond to previously reported data.23
H).
13C NMR (100 MHz, CDCl3):  = 163.1, 136.5, 134.5, 132.6, 128.2,
126.1, 117.7, 49.7.
1-[(4-Methoxyphenyl)sulfonyl]-1H-pyrrole (2c)
The synthesis was carried out according to general procedure I.
Yield: 40.8 mg (86%); white solid; mp 100–103 °C.
N,N-Diallylcyclohexanecarboxamide (1uu)
Compound 1uu was prepared according to a literature procedure.22
IR (film): 1595, 1499, 1456, 1361, 1183, 1162, 1057, 735, 679 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.80 (d, J = 8.0 Hz, 2 H), 7.14 (d, J = 0.8
Hz, 2 H), 6.94 (d, J = 8.0 Hz, 2 H), 6.27 (d, J = 0.8 Hz, 2 H), 3.84 (s, 3 H).
13C NMR (100 MHz, CDCl3):  = 163.7, 130.6, 129.1, 120.6, 114.5,
Yield: 165.6 mg (80%); colorless oil.
1H NMR (400 MHz, CDCl3):  = 5.82–5.67 (m, 2 H), 5.19–5.05 (m, 4 H),
3.95–3.86 (m, 4 H), 2.42–2.35 (m, 1 H), 1.78–1.64 (m, 5 H), 1.59–1.49
(m, 2 H), 1.29–1.16 (m, 3 H).
13C NMR (100 MHz, CDCl3):  = 176.3, 133.5, 133.4, 116.7, 116.3, 48.9,
47.6, 40.8, 29.6, 25.7.
113.4, 55.7.
HRMS (ESI): m/z [M + Na]+ calcd for C11H11NnaO3S: 260.0352; found:
260.0350.
These spectral data correspond to previously reported data.23
N,N-Diallylacetamide (1vv)
Compound 1vv was prepared according to a literature procedure.22
1-[(4-tert-Butylphenyl)sulfonyl]-1H-pyrrole (2d)
The synthesis was carried out according to general procedure I.
Yield: 43.7 mg (83%); white solid; mp 86–89 °C.
Yield: 125.1 mg (90%); colorless oil.
1H NMR (400 MHz, CDCl3):  = 5.78–5.69 (m, 2 H), 5.18–5.06 (m, 4 H),
3.94 (d, J = 6.0 Hz, 2 H), 3.83–3.82 (m, 2 H), 2.06 (s, 3 H).
13C NMR (100 MHz, CDCl3):  = 170.5, 133.2, 132.6, 117.1, 116.5, 49.8,
47.6, 21.2.
IR (film): 1594, 1455, 1370, 1186, 1171, 1057, 837, 734 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.77 (d, J = 8.0 Hz, 2 H), 7.50 (d, J = 7.6
Hz, 2 H), 7.17 (d, J = 1.6 Hz, 2 H), 6.30 (d, J = 2.0 Hz, 2 H), 1.31 (s, 9 H).
13C NMR (100 MHz, CDCl3):  = 157.8, 136.1, 126.6, 126.4, 120.7,
113.4, 35.2, 30.9.
© 2019. Thieme. All rights reserved. — Synthesis 2019, 51, A–P

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Synthesis
HRMS (ESI): m/z [M + Na]+ calcd for C14H17NNaO2S: 286.0872; found:
IR (film): 1585, 1477, 1456, 1365, 1187, 1173, 1057, 829, 757 cm–1
.
286.0880.
1H NMR (400 MHz, CDCl3):  = 7.79 (d, J = 7.6 Hz, 2 H), 7.47 (d, J = 7.6
Hz, 2 H), 7.14 (d, J = 1.2 Hz, 2 H), 6.31 (d, J = 1.2 Hz, 2 H).
1-[(2,4-Dimethylphenyl)sulfonyl]-1H-pyrrole (2e)
The synthesis was carried out according to general procedure I.
Yield: 27.7 mg (59%); white solid; mp 58–60 °C.
13C NMR (100 MHz, CDCl3):  = 140.5, 137.5, 129.7, 128.2, 120.8,
114.1.
HRMS (ESI): m/z [M + Na]+ calcd for C10H8ClNNaO2S: 263.9856; found:
263.9860.
IR (film): 1602, 1455, 1355, 1173, 1057, 823, 745, 670 cm–1
.
These spectral data correspond to previously reported data.23
1H NMR (400 MHz, CDCl3):  = 7.60 (d, J = 8.4 Hz, 1 H), 7.14–7.08 (m, 4
H), 6.30 (d, J = 1.6 Hz, 2 H), 2.52 (s, 3 H), 2.35 (s, 3 H).
13C NMR (100 MHz, CDCl3):  = 144.9, 137.8, 134.8, 133.6, 128.7,
1-[(4-Bromophenyl)sulfonyl]-1H-pyrrole (2j)
127.2, 121.0, 112.6, 21.3, 20.0.
The synthesis was carried out according to general procedure I.
HRMS (ESI): m/z [M + Na]+ calcd for C12H13NNaO2S: 258.0559; found:
Yield: 39.5 mg (69%); white solid; mp 113–116 °C.
258.0568.
IR (film): 1574, 1456, 1364, 1186, 1173, 1058, 821, 743, 700 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.71 (d, J = 8.4 Hz, 2 H), 7.63 (d, J = 8.4
Hz, 2 H), 7.14 (s, 2 H), 6.32 (s, 2 H).
13C NMR (100 MHz, CDCl3):  = 138.0, 132.7, 129.1, 128.2, 120.8,
114.1.
1-[(2,3-Dihydrobenzofuran-5-yl)sulfonyl]-1H-pyrrole (2f)
The synthesis was carried out according to general procedure I.
Yield: 37.3 mg (75%); white solid; mp 136–139 °C.
HRMS (ESI): m/z [M + Na]+ calcd for C10H8BrNNaO2S: 307.9351;
found: 307.9359.
IR (film): 1604, 1484, 1456, 1357, 1180, 1151, 1053, 891, 822, 745,
702 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.68 (d, J = 8.0 Hz, 2 H), 7.14 (s, 2 H),
6.80 (d, J = 8.4 Hz, 1 H), 6.28 (s, 2 H), 4.66 (t, J = 8.8 Hz, 2 H), 3.23 (t, J =
8.8 Hz, 2 H).
13C NMR (100 MHz, CDCl3):  = 164.8, 130.4, 128.8, 128.7, 124.1,
120.5, 113.2, 109.8, 72.5, 28.9.
These spectral data correspond to previously reported data.23
1-[(3-Bromophenyl)sulfonyl]-1H-pyrrole (2k)
The synthesis was carried out according to general procedure I.
Yield: 37.8 mg (66%); white solid; mp 90–93 °C.
HRMS (ESI): m/z [M + Na]+ calcd for C12H11NNaO3S: 272.0352; found:
272.0360.
IR (film): 1572, 1456, 1375, 1191, 1172, 1057, 735, 676 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.99 (s, 1 H), 7.77 (d, J = 7.6 Hz, 1 H),
7.71 (d, J = 7.6 Hz, 1 H), 7.37 (t, J = 8.0 Hz, 1 H), 7.16 (s, 2 H), 6.33 (s, 2
H).
13C NMR (100 MHz, CDCl3):  = 140.7, 136.9, 130.8, 129.6, 125.3,
123.2, 120.8, 114.2.
HRMS (ESI): m/z [M + Na]+ calcd for C10H8BrNNaO2S: 307.9351;
found: 307.9360.
1-([1,1′-Biphenyl]-4-ylsulfonyl)-1H-pyrrole (2g)
The synthesis was carried out according to general procedure I.
Yield: 40.8 mg (72%); white solid; mp 109–112 °C.
IR (film): 1593, 145, 1367, 1188, 1168, 1057, 840, 736, 678 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.92 (d, J = 7.6 Hz, 2 H), 7.69 (d, J = 7.6
Hz, 2 H), 7.56 (d, J = 7.2 Hz, 2 H), 7.49–7.42 (m, 3 H), 7.21 (d, J = 1.6 Hz,
2 H), 6.33 (d, J = 1.6 Hz, 2 H).
13C NMR (100 MHz, CDCl3):  = 146.8, 138.8, 137.5, 129.1, 128.7,
127.9, 127.3, 120.8, 113.7.
1-[(4-Iodophenyl)sulfonyl]-1H-pyrrole (2l)
The synthesis was carried out according to general procedure I.
Yield: 46.6 mg (70%); white solid; mp 125–127 °C.
HRMS (ESI): m/z [M + Na]+ calcd for C16H13NNaO2S: 306.0559; found:
306.0567.
IR (film): 1568, 1456, 1386, 1363, 1188, 1170, 1054, 818, 735 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.85 (d, J = 8.0 Hz, 2 H), 7.55 (d, J = 8.0
Hz, 2 H), 7.13 (s, 2 H), 6.31 (s, 2 H).
13C NMR (100 MHz, CDCl3):  = 138.7, 128.0, 120.8, 114.1, 101.7.
HRMS (ESI): m/z [M + Na]+ calcd for C10H8INNaO2S: 355.9213; found:
355.9209.
1-[(4-Fluorophenyl)sulfonyl]-1H-pyrrole (2h)
The synthesis was carried out according to general procedure I.
Yield: 22.5 mg (50%); yellowish solid; mp 96–99 °C.
IR (film): 1590, 1493, 1373, 1189, 1173, 1057, 835, 741, 678 cm–1
1H NMR (400 MHz, CDCl3):  = 7.89–7.86 (m, 2 H), 7.19–7.15 (m, 4 H),
6.31 (d, J = 1.6 Hz, 2 H).
13C NMR (100 MHz, CDCl3):  = 166.9, 164.4, 135.1, 135.0, 129.7,
129.6, 120.7, 116.8, 116.6, 113.9.
HRMS (ESI): m/z [M + Na]+ calcd for C10H8FNNaO2S: 248.0152; found:
248.0154.
.
These spectral data correspond to previously reported data.25
1-[(3-Fluoro-4-methylphenyl)sulfonyl]-1H-pyrrole (2m)
The synthesis was carried out according to general procedure I.
Yield: 28.7 mg (60%); yellowish solid; mp 102–105 °C.
IR (film): 1490, 1456, 1364, 1186, 1165, 1058, 822, 751, 680 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.54 (d, J = 8.0 Hz, 1 H), 7.48 (d, J = 8.8
Hz, 1 H), 7.32 (t, J = 7.6 Hz, 1 H), 7.14 (d, J = 1.6 Hz, 2 H), 6.30 (d, J = 1.6
Hz, 2 H), 2.32 (s, 3 H).
13C NMR (100 MHz, CDCl3):  = 161.9, 159.4, 138.0, 137.9, 132.5,
132.4, 132.3, 132.1, 122.4, 122.3, 120.8, 113.9, 113.6, 14.9, 14.8.
These spectral data correspond to previously reported data.24
1-[(4-Chlorophenyl)sulfonyl]-1H-pyrrole (2i)
The synthesis was carried out according to general procedure I.
Yield: 30.4 mg (63%); white solid; mp 106–108 °C.
© 2019. Thieme. All rights reserved. — Synthesis 2019, 51, A–P

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Synthesis
HRMS (ESI): m/z [M + Na]+ calcd for C11H10FNNaO2S: 262.0308; found:
1-(2-Naphthylsulfonyl)-1H-pyrrole (2r)
262.0316.
The synthesis was carried out according to general procedure I.
Yield: 27.8 mg (54%); white solid; mp 125–127 °C.
IR (film): 1589, 1455, 1361, 1185, 1167, 1060, 859, 813, 738, 667 cm–1
1H NMR (400 MHz, CDCl3):  = 8.48 (s, 1 H), 7.98–7.87 (m, 3 H), 7.78
(d, J = 8.8 Hz, 1 H), 7.68–7.60 (m, 2 H), 7.23 (d, J = 1.6 Hz, 2 H), 6.29 (d,
J = 1.6 Hz, 2 H).
13C NMR (100 MHz, CDCl3):  = 135.9, 135.2, 131.9, 129.8, 129.5,
129.4, 128.5, 127.9, 127.8, 121.5, 120.8, 113.7.
HRMS (ESI): m/z [M + Na]+ calcd for C14H11NNaO2S: 280.0403; found:
280.0409.
1-[(4-Acetylphenyl)sulfonyl]-1H-pyrrole (2n)
.
The synthesis was carried out according to general procedure I.
Yield: 26.9 mg (54%); yellowish solid; mp 133–136 °C.
IR (film): 2922, 1688, 1456, 1372, 1260, 1192, 1171, 1061, 837, 748
cm–1
.
1H NMR (400 MHz, CDCl3):  = 8.04 (d, J = 8.0 Hz, 2 H), 7.93 (d, J = 8.0
Hz, 2 H), 7.16 (d, J = 0.8 Hz, 2 H), 6.32 (d, J = 1.2 Hz, 2 H), 2.62 (s, 3 H).
13C NMR (100 MHz, CDCl3):  = 196.3, 142.7, 140.8, 129.1, 127.1,
120.9, 114.3, 26.8.
HRMS (ESI): m/z [M + Na]+ calcd for C12H11NNaO3S: 272.0352; found:
These spectral data correspond to previously reported data.23
272.0360.
1-(2-Thiophenesulfonyl)-1H-pyrrole (2s)
The synthesis was carried out according to general procedure I.
1-[(4-Nitrophenyl)sulfonyl]-1H-pyrrole (2o)
Yield: 21.3 mg (50%); yellowish solid; mp 81–83 °C.
The synthesis was carried out according to general procedure I.
IR (film): 1455, 1373, 1189, 1166, 1057, 857, 733, 672 cm–1
.
Yield: 25.7 mg (51%); yellowish solid; mp 129–132 °C.
IR (film): 1533, 1456, 1378, 1349, 1192, 1171, 1057, 855, 739 cm–1
1H NMR (400 MHz, CDCl3):  = 8.33 (d, J = 8.0 Hz, 2 H), 8.02 (d, J = 8.0
Hz, 2 H), 7.16 (d, J = 1.2 Hz, 2 H), 6.36 (d, J = 1.2 Hz, 2 H).
13C NMR (100 MHz, CDCl3):  = 150.6, 144.4, 128.1, 124.6, 120.9,
1H NMR (400 MHz, CDCl3):  = 7.67–7.63 (m, 2 H), 7.18 (d, J = 0.8 Hz, 2
H), 7.06 (s, 1 H), 6.32 (s, 2 H).
13C NMR (100 MHz, CDCl3):  = 133.8, 133.4, 127.5, 120.8, 113.9.
HRMS (ESI): m/z [M + Na]+ calcd for C8H7NNaO2S2: 235.9810; found:
.
235.9816.
114.9.
These spectral data correspond to previously reported data.26
HRMS (ESI): m/z [M + Na]+ calcd for C10H8N2NaO4S: 275.0097; found:
275.0105.
1-[(5-Chlorothiophen-2-yl)sulfonyl]-1H-pyrrole (2t)
The synthesis was carried out according to general procedure I.
Yield: 22.2 mg (45%); yellowish solid; mp 89–92 °C.
IR (film): 1456, 1409, 1380, 1191, 1167, 1057, 994, 736, 681 cm–1
1H NMR (400 MHz, CDCl3):  = 7.46 (s, 1 H), 7.14 (s, 2 H), 6.90 (s, 1 H),
These spectral data correspond to previously reported data.23
1-[(3-Nitrophenyl)sulfonyl]-1H-pyrrole (2p)
.
The synthesis was carried out according to general procedure I.
Yield: 21.7 mg (43%); yellow solid; mp 81–84 °C.
IR (film): 1535, 1379, 1352, 1193, 1174, 1056, 878, 733, 664 cm–1
1H NMR (400 MHz, CDCl3):  = 8.68 (s, 1 H), 8.44 (d, J = 8.0 Hz, 1 H),
8.16 (d, J = 8.0 Hz, 1 H), 7.74 (t, J = 8.0 Hz, 1 H), 7.19 (s, 2 H), 6.36 (s, 2
6.34 (s, 2 H).
.
13C NMR (100 MHz, CDCl3):  = 132.8, 132.0, 126.9, 120.7, 119.5,
114.3.
HRMS (ESI): m/z [M + Na]+ calcd for C8H6ClNNaO2S2: 269.9421; found:
269.9430.
H).
13C NMR (100 MHz, CDCl3):  = 148.3, 141.0, 132.1, 130.9, 128.2,
122.1, 120.9, 114.8.
HRMS (ESI): m/z [M + Na]+ calcd for C10H8N2NaO4S: 275.0097; found:
N-Acylpyrroles 2aa–vv; General Procedure II
A Schlenk tube equipped with a magnetic stir bar was charged with
the Grubbs II cat. (8.5 mg, 0.01 mmol), CuBr2 (8.9 mg, 0.04 mmol), the
appropriate acyldiallylamine 1 (1.0 equiv, 0.20 mmol), and toluene
(2.0 mL). The tube was under an O2 balloon and the mixture was
stirred at 110 °C in an oil bath for 24 h, after which the mixture was
cooled to room temperature. The solvent was removed under reduced
pressure, and the residue was purified by flash chromatography to
give the desired product.
275.0106.
1-(1-Naphthylsulfonyl)-1H-pyrrole (2q)
The synthesis was carried out according to general procedure I.
Yield: 25.7 mg (50%); white solid; mp 130–133 °C.
IR (film): 1508, 1454, 1363, 1182, 1163, 1056, 831, 797, 765, 731, 681
cm–1
.
1H NMR (400 MHz, CDCl3):  = 8.74 (d, J = 8.4 Hz, 1 H), 8.11 (d, J = 8.0
Hz, 1 H), 7.99–7.93 (m, 2 H), 7.71 (t, J = 7.6 Hz, 1 H), 7.62 (t, J = 7.4 Hz,
1 H), 7.54 (t, J = 7.8 Hz, 1 H), 7.27 (d, J = 1.2 Hz, 2 H), 6.32 (d, J = 0.8 Hz,
2 H).
Phenyl(1H-pyrrol-1-yl)methanone (2aa)
The synthesis was carried out according to general procedure II.
Yield: 31.1 mg (91%); yellow oil.
IR (film): 2925, 1692, 1466, 1324, 1089, 1072, 879, 719, 696 cm–1
.
13C NMR (100 MHz, CDCl3):  = 135.5, 134.7, 134.1, 129.1, 128.8,
1H NMR (400 MHz, CDCl3):  = 7.75 (d, J = 7.6 Hz, 2 H), 7.60 (t, J = 7.4
Hz, 1 H), 7.51 (t, J = 7.4 Hz, 2 H), 7.29 (d, J = 1.6 Hz, 2 H), 6.35 (d, J = 1.6
Hz, 2 H).
128.6, 128.0, 127.3, 124.2, 123.9, 121.2, 113.0.
HRMS (ESI): m/z [M + Na]+ calcd for C14H11NNaO2S: 280.0403; found:
280.0406.
13C NMR (100 MHz, CDCl3):  = 167.7, 133.2, 132.2, 129.4, 128.4,
These spectral data correspond to previously reported data.23
121.2, 113.1.
© 2019. Thieme. All rights reserved. — Synthesis 2019, 51, A–P

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Synthesis
HRMS (ESI): m/z [M + Na]+ calcd for C11H9NNaO: 194.0576; found:
Yield: 37.1 mg (87%); yellowish oil.
194.0571.
IR (film): 2922, 1702, 1465, 1325, 1070, 866, 850, 738 cm–1
1H NMR (400 MHz, CDCl3):  = 7.66 (s, 1 H), 6.91 (s, 2 H), 6.51 (s, 1 H),
.
These spectral data correspond to previously reported data.27
6.38 (s, 1 H), 6.21 (s, 1 H), 2.33 (s, 3 H), 2.17 (s, 6 H).
13C NMR (100 MHz, CDCl3):  = 169.0, 139.6, 134.7, 131.8, 128.2,
121.1, 118.3, 113.7, 113.4, 21.2, 19.0.
HRMS (ESI): m/z [M + Na]+ calcd for C14H15NNaO: 236.1046; found:
(4-Ethylphenyl)(1H-pyrrol-1-yl)methanone (2bb)
The synthesis was carried out according to general procedure II.
Yield: 35.8 mg (90%); yellowish oil.
IR (film): 2931, 1691, 1465, 1325, 1087, 1073, 881, 736 cm–1
.
236.1041.
1H NMR (400 MHz, CDCl3):  = 7.69 (d, J = 7.6 Hz, 2 H), 7.34–7.30 (m, 4
H), 6.34 (s, 2 H), 2.75 (q, J = 7.4 Hz, 2 H), 1.29 (t, J = 7.4 Hz, 3 H).
13C NMR (100 MHz, CDCl3):  = 167.7, 149.2, 130.5, 129.8, 127.9,
(4-Iodophenyl)(1H-pyrrol-1-yl)methanone (2gg)
The synthesis was carried out according to general procedure II.
Yield: 51.7 mg (87%); white solid; mp 69–70 °C.
121.3, 112.9, 28.9, 15.2.
HRMS (ESI): m/z [M + Na]+ calcd for C13H13NNaO: 222.0889; found:
IR (film): 2925, 1694, 1466, 1329, 1089, 1074, 878, 739 cm–1
.
222.0896.
1H NMR (400 MHz, CDCl3):  = 7.87 (d, J = 8.4 Hz, 2 H), 7.47 (d, J = 8.4
Hz, 2 H), 7.25 (t, J = 1.8 Hz, 2 H), 6.36 (t, J = 2.2 Hz, 2 H).
(3-Methoxyphenyl)(1H-pyrrol-1-yl)methanone (2cc)
The synthesis was carried out according to general procedure II.
Yield: 37.0 mg (92%); yellowish oil.
13C NMR (100 MHz, CDCl3):  = 166.9, 137.7, 132.5, 130.9, 121.1,
113.4, 99.6.
HRMS (ESI): m/z [M + Na]+ calcd for C11H8INNaO: 319.9543; found:
319.9540.
IR (film): 2924, 1694, 1466, 1326, 1074, 1047, 793, 737 cm–1
.
These spectral data correspond to previously reported data.28
1H NMR (400 MHz, CDCl3):  = 7.41 (t, J = 8.0 Hz, 1 H), 7.31–7.27 (m, 4
H), 7.15–7.12 (m, 1 H), 6.35 (t, J = 2.2 Hz, 2 H), 3.86 (s, 3 H).
13C NMR (100 MHz, CDCl3):  = 167.5, 159.5, 134.4, 129.5, 121.7,
121.3, 118.4, 114.3, 113.1, 55.5.
HRMS (ESI): m/z [M + Na]+ calcd for C12H11NNaO2: 224.0682; found:
(4-Bromophenyl)(1H-pyrrol-1-yl)methanone (2hh)
The synthesis was carried out according to general procedure II.
Yield: 42.8 mg (86%); white solid; mp 68–69 °C.
224.0686.
IR (film): 2925, 1694, 1466, 1329, 1089, 1070, 878, 738 cm–1
1H NMR (400 MHz, CDCl3):  = 7.70–7.64 (m, 4 H), 7.27 (t, J = 2.2 Hz, 2
H), 6.38 (t, J = 2.4 Hz, 2 H).
.
These spectral data correspond to previously reported data.27
(4-Methoxyphenyl)(1H-pyrrol-1-yl)methanone (2dd)
The synthesis was carried out according to general procedure II.
Yield: 37.4 mg (93%); yellowish oil.
13C NMR (100 MHz, CDCl3):  = 166.7, 132.0, 131.8, 131.0, 127.2,
121.1, 113.4.
HRMS (ESI): m/z [M + Na]+ calcd for C11H8BrNNaO: 271.9681; found:
271.9687.
IR (film): 2931, 1685, 1464, 1326, 1088, 1073, 881, 737 cm–1
.
These spectral data correspond to previously reported data.29
1H NMR (400 MHz, CDCl3):  = 7.76 (d, J = 8.4 Hz, 2 H), 7.29 (t, J = 2.0
Hz, 2 H), 6.99 (d, J = 8.8 Hz, 2 H), 6.34 (t, J = 2.0 Hz, 2 H), 3.89 (s, 3 H).
13C NMR (100 MHz, CDCl3):  = 167.1, 163.0, 132.0, 125.2, 121.3,
113.8, 112.7, 55.5.
HRMS (ESI): m/z [M + Na]+ calcd for C12H11NNaO2: 224.0682; found:
(3-Bromophenyl)(1H-pyrrol-1-yl)methanone (2ii)
The synthesis was carried out according to general procedure II.
Yield: 43.3 mg (87%); yellowish oil.
224.0687.
IR (film): 2924, 1694, 1466, 1327, 1088, 1075, 889, 729 cm–1
1H NMR (400 MHz, CDCl3):  = 7.91 (s, 1 H), 7.77–7.68 (m, 2 H), 7.42
(t, J = 7.8 Hz, 1 H), 7.28 (s, 2 H), 6.39 (s, 2 H).
.
These spectral data correspond to previously reported data.27
(1H-Pyrrol-1-yl)(o-tolyl)methanone (2ee)
The synthesis was carried out according to general procedure II.
Yield: 33.3 mg (90%); yellowish oil.
13C NMR (100 MHz, CDCl3):  = 166.1, 135.2, 135.1, 132.3, 130.0,
127.9, 122.6, 121.1, 113.6.
HRMS (ESI): m/z [M + Na]+ calcd for C11H8BrNNaO: 271.9681; found:
271.9689.
IR (film): 2925, 1702, 1466, 1326, 1083, 1072, 882, 737, 664 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.44–7.39 (m, 2 H), 7.30 (t, J = 6.6 Hz, 2
H), 7.15 (s, 2 H), 6.31 (d, J = 1.2 Hz, 2 H), 2.34 (s, 3 H).
13C NMR (100 MHz, CDCl3):  = 168.2, 136.4, 133.7, 130.8, 130.7,
(4-Chlorophenyl)(1H-pyrrol-1-yl)methanone (2jj)
The synthesis was carried out according to general procedure II.
Yield: 34.0 mg (83%); yellowish oil.
127.8, 125.5, 120.6, 113.4, 19.3.
HRMS (ESI): m/z [M + Na]+ calcd for C12H11NNaO: 208.0733; found:
IR (film): 2925, 1698, 1465, 1328, 1091, 1075, 880, 741 cm–1
.
208.0730.
1H NMR (400 MHz, CDCl3):  = 7.70 (d, J = 8.4 Hz, 2 H), 7.49 (d, J = 8.8
Hz, 2 H), 7.25 (t, J = 2.4 Hz, 2 H), 6.36 (t, J = 2.4 Hz, 2 H).
These spectral data correspond to previously reported data.27
13C NMR (100 MHz, CDCl3):  = 166.6, 138.7, 131.5, 130.9, 128.8,
121.1, 113.4.
Mesityl(1H-pyrrol-1-yl)methanone (2ff)
The synthesis was carried out according to general procedure II.
© 2019. Thieme. All rights reserved. — Synthesis 2019, 51, A–P

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HRMS (ESI): m/z [M + Na]+ calcd for C11H8ClNNaO: 228.0187; found:
Yield: 36.7 mg (83%); white solid; mp 85–87 °C.
228.0181.
IR (film): 2923, 1695, 1465, 1325, 1087, 1074, 830, 746 cm–1
.
1H NMR (400 MHz, CDCl3):  = 8.27 (s, 1 H), 7.98–7.92 (m, 3 H), 7.82
(d, J = 8.4 Hz, 1 H), 7.66–7.58 (m, 2 H), 7.36 (s, 2 H), 6.39 (s, 2 H).
13C NMR (100 MHz, CDCl3):  = 167.8, 134.9, 132.2, 130.7, 130.4,
129.1, 128.5, 128.4, 127.9, 127.1, 125.5, 121.4, 113.1.
HRMS (ESI): m/z [M + Na]+ calcd for C15H11NNaO: 244.0733; found:
(3-Fluorophenyl)(1H-pyrrol-1-yl)methanone (2kk)
The synthesis was carried out according to general procedure II.
Yield: 30.2 mg (80%); yellowish oil.
IR (film): 2925, 1695, 1467, 1327, 1091, 1073, 815, 736 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.54–7.44 (m, 3 H), 7.33–7.28 (m, 1 H),
7.27 (t, J = 2.2 Hz, 2 H), 6.36 (t, J = 2.2 Hz, 2 H).
244.0739.
13C NMR (100 MHz, CDCl3):  = 166.2, 163.5, 161.0, 135.2, 135.1,
130.3, 130.2, 125.2, 125.1, 121.1, 119.4, 119.2, 116.7, 116.4, 113.5.
HRMS (ESI): m/z [M + Na]+ calcd for C11H8FNNaO: 212.0482; found:
Furan-2-yl(1H-pyrrol-1-yl)methanone (2pp)
The synthesis was carried out according to general procedure II.
Yield: 26.4 mg (82%); yellowish oil.
212.0490.
IR (film): 2926, 1682, 1461, 1330, 1100, 1074, 837, 734 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.69–7.66 (m, 3 H), 7.43–7.42 (m, 1 H),
6.63–6.62 (m, 1 H), 6.36 (t, J = 2.4 Hz, 2 H).
13C NMR (100 MHz, CDCl3):  = 155.5, 146.7, 146.5, 121.2, 120.7,
2-(1H-Pyrrole-1-carbonyl)phenyl Acetate (2ll)
The synthesis was carried out according to general procedure II.
Yield: 37.6 mg (82%); yellowish oil.
113.2, 112.4.
HRMS (ESI): m/z [M + Na]+ calcd for C9H7NNaO2: 184.0369; found:
184.0378.
IR (film): 2925, 1767, 1700, 1467, 1332, 1178, 1084, 1073, 886, 738
cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.60–7.54 (m, 2 H), 7.37–7.33 (m, 1 H),
7.27–7.25 (m, 1 H), 7.17 (t, J = 2.4 Hz, 2 H), 6.32 (t, J = 2.4 Hz, 2 H), 2.12
(s, 3 H).
13C NMR (100 MHz, CDCl3):  = 168.8, 164.8, 148.3, 132.4, 129.6,
126.9, 125.7, 123.4, 120.7, 113.4, 20.6.
Furan-3-yl(1H-pyrrol-1-yl)methanone (2qq)
The synthesis was carried out according to general procedure II.
Yield: 26.1 mg (81%); yellowish oil.
IR (film): 2924, 1691, 1465, 1335, 1074, 875, 837, 735 cm–1
.
HRMS (ESI): m/z [M + Na]+ calcd for C13H11NNaO3: 252.0631; found:
252.0639.
1H NMR (400 MHz, CDCl3):  = 8.02 (s, 1 H), 7.53 (s, 1 H), 7.40 (s, 2 H),
6.86 (s, 1 H), 6.37 (s, 2 H).
13C NMR (100 MHz, CDCl3):  = 161.1, 147.2, 143.9, 120.6, 120.4,
113.3, 110.8.
HRMS (ESI): m/z [M + Na]+ calcd for C9H7NNaO2: 184.0369; found:
184.0373.
(3-Nitrophenyl)(1H-pyrrol-1-yl)methanone (2mm)
The synthesis was carried out according to general procedure II.
Yield: 34.6 mg (80%); yellow oil.
IR (film): 2923, 1697, 1467, 1329, 1099, 1075, 852, 741, 713 cm–1
1H NMR (400 MHz, CDCl3):  = 8.63 (s, 1 H), 8.49 (d, J = 8.0 Hz, 1 H),
.
These spectral data correspond to previously reported data.28
8.11 (d, J = 7.6 Hz, 1 H), 7.77 (t, J = 7.8 Hz, 1 H), 7.27 (s, 2 H), 6.44 (s, 2
H).
13C NMR (100 MHz, CDCl3):  = 165.2, 148.0, 134.9, 134.8, 129.9,
126.7, 124.3, 121.0, 114.2.
HRMS (ESI): m/z [M + Na]+ calcd for C11H8N2NaO3: 239.0427; found:
239.0421.
These spectral data correspond to previously reported data.30
(1H-Pyrrol-1-yl)(thiophen-2-yl)methanone (2rr)
The synthesis was carried out according to general procedure II.
Yield: 28.3 mg (80%); yellowish oil.
IR (film): 2924, 1665, 1464, 1318, 1070, 816, 719 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.77–7.76 (m, 1 H), 7.72–7.71 (m, 1 H),
7.47 (t, J = 2.4 Hz, 2 H), 7.20–7.18 (m, 1 H), 6.38 (t, J = 2.2 Hz, 2 H).
13C NMR (100 MHz, CDCl3):  = 160.6, 135.8, 134.0, 133.3, 127.7,
121.0, 113.2.
Naphthalen-1-yl(1H-pyrrol-1-yl)methanone (2nn)
The synthesis was carried out according to general procedure II.
Yield: 35.4 mg (80%); yellowish oil.
HRMS (ESI): m/z [M + Na]+ calcd for C9H7NNaOS: 200.0141; found:
200.0138.
IR (film): 2922, 1694, 1465, 1321, 1105, 1068, 887, 737 cm–1
1H NMR (400 MHz, CDCl3):  = 8.03 (d, J = 8.0 Hz, 1 H), 7.96–7.92 (m, 2
H), 7.67–7.65 (m, 1 H), 7.59–7.52 (m, 3 H), 7.22 (s, 2 H), 6.33 (s, 2 H).
13C NMR (100 MHz, CDCl3):  = 167.6, 133.4, 131.4, 131.2, 130.4,
128.4, 127.6, 126.9, 126.7, 125.0, 124.4, 121.0, 113.4.
HRMS (ESI): m/z [M + Na]+ calcd for C15H11NNaO: 244.0733; found:
244.0737.
.
(3-Methylthiophen-2-yl)(1H-pyrrol-1-yl)methanone (2ss)
The synthesis was carried out according to general procedure II.
Yield: 25.2 mg (66%); white solid; mp 70–71 °C.
IR (film): 2924, 1675, 1466, 1320, 1073, 866, 741 cm–1
.
1H NMR (400 MHz, CDCl3):  = 7.50 (d, J = 5.2 Hz, 1 H), 7.40 (t, J = 2.2
Hz, 2 H), 6.99 (d, J = 4.8 Hz, 1 H), 6.34 (t, J = 2.4 Hz, 2 H), 2.45 (s, 3 H).
13C NMR (100 MHz, CDCl3):  = 161.7, 145.8, 131.3, 129.9, 127.6,
These spectral data correspond to previously reported data.31
121.1, 113.0, 15.8.
HRMS (ESI): m/z [M + Na]+ calcd for C10H9NNaOS: 214.0297; found:
214.0305.
Naphthalen-2-yl(1H-pyrrol-1-yl)methanone (2oo)
The synthesis was carried out according to general procedure II.
© 2019. Thieme. All rights reserved. — Synthesis 2019, 51, A–P

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Synthesis
(5-Chlorothiophen-2-yl)(1H-pyrrol-1-yl)methanone (2tt)
The synthesis was carried out according to general procedure II.
Yield: 30.4 mg (72%); white solid; mp 39–40 °C.
IR (film): 2925, 1670, 1464, 1417, 1331, 1073, 1010, 824, 727 cm–1
1H NMR (400 MHz, CDCl3):  = 7.56 (d, J = 3.6 Hz, 1 H), 7.41 (d, J = 1.2
Hz, 2 H), 7.02 (d, J = 3.6 Hz, 1 H), 6.38 (d, J = 1.2 Hz, 2 H).
13C NMR (100 MHz, CDCl3):  = 159.4, 139.0, 134.3, 133.7, 127.2,
120.8, 113.5.
HRMS (ESI): m/z [M + Na]+ calcd for C9H6ClNNaOS: 233.9751; found:
233.9756.
(3) For the synthesis of pyrroles without the use of RCM strategy,
see: (a) Cooney, J. V.; McEwen, W. E. J. Org. Chem. 1981, 46,
2570. (b) Minetto, G.; Raveglia, L. F.; Taddei, M. Org. Lett. 2004,
6, 389. (c) Clauson-Kaas, N.; Tyle, Z. Acta Chem. Scand. 1952, 6,
667. (d) Rochais, C.; Lisowski, V.; Dallemagne, P.; Rault, S. Tetra-
hedron Lett. 2004, 45, 6353. (e) Katritzky, A. R.; Jiang, J. L.; Steel,
P. J. J. Org. Chem. 1994, 59, 4551. (f) Arcadi, A.; Rossi, E. Tetrahe-
dron 1998, 54, 15253. (g) Periasamy, M.; Srinivas, G.; Bharathi,
P. J. Org. Chem. 1999, 64, 4204. (h) Dieter, R. K.; Yu, H. Y. Org.
Lett. 2000, 2, 2283. (i) Ma, H. C.; Jiang, X. Z. J. Org. Chem. 2007,
72, 8943. (j) Deng, H. J.; Fang, Y. J.; Chen, G. W.; Liu, M. C.; Wu,
H. Y.; Chen, J. X. Appl. Organomet. Chem. 2012, 26, 164.
(k) Bandyopadhyay, D.; Mukherjee, S.; Banik, B. K. Molecules
2010, 15, 2520.
.
Cyclohexyl(1H-pyrrol-1-yl)methanone (2uu)
(4) Fürstner, A. Angew. Chem. Int. Ed. 2000, 39, 3012.
The synthesis was carried out according to general procedure II.
(5) Donohoe, T. J.; Jones, C. R.; Barbosa, L. C. A. J. Am. Chem. Soc.
2011, 133, 16418.
Yield: 28.3 mg (80%); white solid; mp 54–55 °C.
IR (film): 2929, 1714, 1466, 1336, 1272, 1112, 1072, 924, 741 cm–1
1H NMR (400 MHz, CDCl3):  = 7.33 (t, J = 2.0 Hz, 2 H), 6.29 (t, J = 2.4
Hz, 2 H), 2.96–2.89 (m, 1 H), 1.97–1.85 (m, 4 H), 1.76–1.58 (m, 3 H),
1.43–1.24 (m, 3 H).
13C NMR (100 MHz, CDCl3):  = 173.8, 118.9, 112.9, 42.8, 29.6, 25.6,
25.5.
HRMS (ESI): m/z [M + Na]+ calcd for C11H15NNaO: 200.1046; found:
200.1041.
.
(6) (a) Donohoe, T. J.; Orr, A. J.; Gosby, K.; Bingham, M. Eur. J. Org.
Chem. 2005, 1969. (b) Donohoe, T. J.; Orr, A. J.; Bingham, M.
Angew. Chem. Int. Ed. 2006, 45, 2664. (c) De Matteis, V.; Dufay,
O.; Waalboer, D. C. J.; van Delft, F. L.; Tiebes, J.; Rutjes, F. P. J. T.
Eur. J. Org. Chem. 2007, 2667. (d) Donohoe, T. J.; Fishlock, L. P.;
Procopiou, P. A. Chem. Eur. J. 2008, 14, 5716. (e) Donohoe, T. J.;
Kershaw, N. M.; Orr, A. J.; Wheelhouse, K. M. P.; Fishlock, L. P.;
Lacy, A. R.; Bingham, M.; Procopiou, P. A. Tetrahedron 2008, 64,
809.
These spectral data correspond to previously reported data.29
(7) (a) Declerck, V.; Ribière, P.; Martinez, J.; Lamaty, F. J. Org. Chem.
2004, 69, 8372. (b) Chachignon, H.; Scalacci, N.; Petricci, E.;
Castagnolo, D. J. Org. Chem. 2015, 80, 5287.
1-(1H-Pyrrol-1-yl)ethan-1-one (2vv)
(8) (a) Evans, P.; Grigg, R.; Monteith, M. Tetrahedron Lett. 1999, 40,
5247. (b) Yang, C.; Murray, W. V.; Wilson, L. J. Tetrahedron Lett.
2003, 44, 1783.
(9) (a) Dieltiens, N.; Stevens, C. V.; Vos, D. D.; Allaert, B.; Drozdzak,
R.; Verpoort, F. Tetrahedron Lett. 2004, 45, 8995. (b) Sánchez, I.;
Pujol, M. D. Synthesis 2006, 1823. (c) Chen, W.; Wang, J. Organo-
metallics 2013, 32, 1958. (d) Scalacci, N.; Black, G. W.; Mattedi,
G.; Brown, N. L.; Turner, N. J.; Castagnolo, D. ACS Catal. 2017, 7,
1295.
(10) For pyrroles as pharmaceuticals, see: (a) Artico, M.; Silvestri, R.;
Massa, S.; Loi, A. G.; Corrias, S.; Piras, G.; Colla, P. L. J. Med. Chem.
1996, 39, 522. (b) Silvestri, R.; Regina, G. L.; Martino, G. D.;
Artico, M.; Befani, O.; Palumbo, M.; Agostinelli, E.; Turini, P.
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Isherwood, M. L.; Wiley, J. L.; Martin, B. R. Bioorg. Med. Chem.
Lett. 2006, 16, 5432. (d) Liu, K.; Lu, H.; Hou, L.; Qi, Z.; Teixeira, C.;
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2008, 51, 7843. (e) Watanabe, T.; Umezawa, Y.; Takahashi, Y.;
Akamatsu, Y. Bioorg. Med. Chem. Lett. 2010, 20, 5807. (f) Ghorab,
M. M.; Ragab, F. A.; Heiba, H. I.; Youssef, H. A.; El-Gazzar, M. G.
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(11) For pyrrole-type biologically active natural products, see:
(a) Boger, D. L.; Boyce, C. W.; Labrili, M. A.; Sehon, C. A.; Jin, Q.
J. Am. Chem. Soc. 1999, 121, 54. (b) Jacobi, P. A.; Coutts, L. D.;
Guo, J. S.; Hauck, S. I.; Leung, S. H. J. Org. Chem. 2000, 65, 205.
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Chem. 2015, 100, 176.
The synthesis was carried out according to general procedure II.
Yield: 17.9 mg (82%); yellowish oil.
1H NMR (400 MHz, CDCl3):  = 7.29 (s, 2 H), 6.30 (t, J = 2.2 Hz, 2 H),
2.53 (s, 3 H).
13C NMR (100 MHz, CDCl3):  = 167.7, 119.3, 113.2, 22.3.
HRMS (ESI): m/z [M + Na]+ calcd for C6H7NNaO: 132.0420; found:
132.0426.
These spectral data correspond to previously reported data.32
Funding Information
This work was supported by the Natural Science Foundation of Shan-
dong Province (ZR2019MB009), the Fundamental Research Funds for
the Central Universities (HIT.NSRIF.201701), the Natural Science
Foundation of China (21672046, 21372054), and funding from the
Huancui District of Weihai City.
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Supporting Information
Supporting information for this article is available online at
https://doi.org/10.1055/s-0039-1690002.
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