Rhodium(II)-Catalyzed Reaction of 1-Tosyl-1,2,3-triazoles with Morita–Baylis–Hillman Adducts: Synthesis of 3,4-Fused Pyrroles

Article abstract of DOI:10.1002/asia.201800057

A cascade reaction of rhodium azavinylcarbenes with Morita–Baylis–Hillman (MBH) adducts enables a novel synthetic approach to 3,4-fused pyrroles. The cascade reaction begins with the insertion of O?H bond into rhodium azavinylcarbenes, subsquent sigmatropic rearrangement provides substituted α,β-unsaturated cyclic ketone intermediates. Then the intramolecular aza Michael addition/oxidative aromatization sequence give rise to a wide range of 3,4-fused pyrroles in good yields, and with excellent functional group compatibility.

Full text of DOI:10.1002/asia.201800057

CHEMISTRY
AN ASIAN JOURNAL
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Accepted Article
Title: Rhodium(II)-Catalyzed Reaction of 1-Tosyl-1,2,3-triazoles with
Morita-Baylis-Hillman adducts: Synthesis of 3,4-Fused Pyrroles
Authors: Wei-Ping Deng, Renmeng Jia, Jiang Meng, Jiaying Leng, and
Xingxin Yu
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10.1002/asia.201800057
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Rhodium(II)-Catalyzed Reaction of 1-Tosyl-1,2,3-triazoles with
Morita–Baylis–Hillman adducts: Synthesis of 3,4-Fused Pyrroles
Renmeng Jia, Jiang Meng, Jiaying Leng, Xingxin Yu* and Wei-Ping Deng*
Abstract: A cascade reaction of rhodium azavinylcarbenes with
MBH adducts enables a novel synthetic approach to 3,4-fused
pyrroles. The cascade reaction begins with the insertion of O-H bond
way to synthesize 3,4-fused cycloalkanopyrroles is the 1,3-
dipolar cycloaddition of Michael acceptors and isonitrile anions.6k
Recently, Sarpong and coworkers6h reported an elegant method
for the synthesis of 3,4-fused pyrroles using in situ generated
Rh-bound trimethylenemethane variants (Scheme 1a). At nearly
the same time, the group of Gevorgyan6i developed an
intramolecular Rh-catalyzed transannulation reaction of alkynyl-
tethered triazoles to construct the 3,4-fused pyrroles (Scheme
1b). However, these reported methods have drawbacks such as
limitations of substitution of products and ring members of
pyrroles-fused cyclanes. Thus, the development of a streamlined
method for the synthesis of 3,4-fused pyrroles containing a
variety of substituents starting from easily available substrates is
highly desired.
into
rearrangement provides substituted ɑ,β-unsaturated cyclic ketone
intermediates. Then the intramolecular aza Michael
rhodium
azavinylcarbenes,
subsquent
sigmatropic
addition/oxidative aromatization sequence give rise to a wide range
of 3,4-fused pyrroles in good yields, and with excellent functional
group compatibility.
As one of the most valuable heterocycle skeletons, 3,4-fused
pyrroles are widely found in natural products and bioactive
compounds.1 For instance, Bhimamycin
D
shows good
antibacterial activities.2 The cycloprodigiosin isolated from the
marine bacteria, Beneckea gazogenes and Alteromonas rubra,
has been used as an effective anti-cancer compound and
immunosuppressant.3 In addition,
a series of compounds
containing a fused pyrrole framework have been evaluated as
BET inhibitors4 and COX-2 inhibitors.5 (Figure 1)
Scheme 1 Rh (II) catalyzed reaction for the construction of 3,4-fused pyrroles.
Triazole chemistry has been extensively studied over the
last decade, in which the N-sulfuryl-1,2,3-triazoles have been
used as versatile synthetic precursors for the synthesis of
nitrogen-containing heterocycles.7-11 We have a great interest in
azaheterocycle
synthesis
and
N-sulfonyl-1,2,3-triazoles
Figure 1 Selected natural products and pharmaceutical compounds．
chemistry. We have reported a practical and efficient method for
divergent synthesis of 3,6-disubstituted- and 3,5,6-trisubstituted-
1,2,4-triazines via unexpected rhodium-catalyzed O−H
insertion/rearrangement/ conditions-controlled intramolecular
cyclization and oxidation reaction under mild conditions.12 Soon
afterwards, a novel protocol for the synthesis of unsymmetrical
indigo-like (E)-α-amino enaminones by rhodium catalyzed O−H
insertion and subsequent rearrangement of isatins with 1-tosyl-
1,2,3-triazoles has also been reported by us.13 Up to now, the
direct O-H insertions of α-imino rhodium carbenoids with proper
substrates14, taking benzylic alcohol14e for example, have been
well studied. Moreover, some methods have been developed for
the construction of nitrogen-containing heterocycles (such as
pyrrole skeleton) based on O-H insertion and subsequent
rearrangement.14a With our continuing studies on the Rh(II)-
catalyzed transformation of triazoles, we supposed this rhodium-
catalyzed O−H insertion/rearrangement strategy can be further
applied to afford more attractive nitrogen-containing
heterocycles such as 3,4-fused pyrroles by using Morita-Baylis-
In view of the impressive biological activities of 3,4-fused
pyrroles, several strategies for the synthesis of this skeleton
have been developed.6 However, to the best of our knowledge,
the efficient method for the construction of 3,4-fused
cycloalkanopyrroles is rarely achieved up to now. Generally, the
R. Jia, J. Meng, J. Leng, Prof. Dr. X. Yu, Prof. Dr. W.-P. Deng
School of Pharmacy and Shanghai Key Laboratory of New Drug
Design
East China University of Science and Technology,
130 Meilong Road,Shanghai 200237 (China)
xxyu@ecust.edu.cn, weiping_deng@ecust.edu.cn.
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Hillman adducts as starting materials. Thus, we envisioned that
triazoles could first react with Morita-Baylis-Hillman adducts of
ɑ,β-unsaturated cyclic ketones.[15] through O-H insertion and
rearrangement to provide an intermediate, which can be further
converted into 3,4-fused pyrroles (Scheme 1c). Herein, we
disclose a novel method for the synthesis of 3,4-fused pyrroles
via a tandem rhodium catalyzed O−H insertion, [3,3]-sigmatropic
rearrangement, intramolecular aza-Michael addition and
oxidation.
As envisaged, key step for the formation of 3,4-fused
pyrrole 4aa is the intramolecular aza-Michael addition of 3aa.
Certainly, base would promote the intramolecular cyclization of
3aa to afford 4aa. So, 2 equiv CH3ONa was added into the
solution of 3aa (two diastereomers) to promote the cyclization.
As expected, 3,4-fused pyrrole 4aa was obtained in 53% yield
within 12 hours (Table 2, entry 1). The structure of 4aa was
unambiguously determined by spectroscopic analysis and X-ray
crystallography (Figure 2). After the screening of different bases,
we found that t-BuOK, NaH, TEA, Cs2CO3, DABCO did not give
a better result (Table 2, entry 2-6). Gratifyingly, we found that
DBU promoted the cyclization smoothly to afford 4aa in 63%
yield (Table 2, entry 7). Solvent effect was then tested with DBU
as the base (Table 2, entry 8-11). The results show that the
nonpolar solvent toluene is the best choice. Moreover, the yield
did not increase either at a higher reaction temperature or a
lower reaction temperature (Table 2, entry 12-14). We
envisioned that the additional oxidants would promote the
reaction. Therefore, oxidants like DDQ or PIDA were added, but
the desired product could not be obtained (Table 2, entry 15-16).
After optimization, the combination of 3aa and DBU (2 equiv) in
toluene at 75 °C was determined as the optimum reaction
conditions.
Table 1 Optimization of reaction conditions for the Rh-catalyzed reaction of
MBH adduct 1a and triazole 2a[a]
additive
temp (oC)
75
yieldb (%)
65
entry
1c
catlyst
solvent
CHCl3
Rh2(OAc)4
Rh2(Oct)4
Rh2(Piv)4
Rh2(S-nttl)4
Rh2(Oct)4
Rh2(Oct)4
Rh2(Oct)4
Rh2(Oct)4
Rh2(Oct)4
Rh2(Oct)4
Rh2(Oct)4
Rh2(Oct)4
Rh2(Oct)4
Rh2(Oct)4
-
2c
3c
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
CH2Cl2
toluene
CHCl3
CHCl3
CHCl3
CHCl3
CHCl3
-
75
82
-
75
78
4c
5d
-
75
67
-
75
86
Table 2 Optimization of reaction conditions for the intramolecular Michael
cyclization of 3aa[a]
6
-
75
90g
7
-
85
88
8
-
75
77
9
-
75
73
10f
11f
12f
13f
14f
Cu(OTf)2
ZnCl2
TsOH
CF3COOH
Ni(acac)2
75
tracee
tracee
66
75
75
base
oxidation
Air
temp (oC)
rt
yieldb (%)
53
75
70
entry
1
solvent
CH3OH
t-BuOH
THF
75
73
CH3ONa
t-BuOK
NaH
[a] Reaction conditions: under N2, 1a (0.2 mmol), 2a (0.24 mmol), Rh cat. (2
mol %), and solvent (1.0 mL) were heated until 1a was consumed; [b] Isolated
overall yield in two isomers of 3aa; [c] 1a (0.2 mmol) and 2a (0.22 mmol) were
used; [d] 1a (0.22 mmol) and 2a (0.2 mmol) were used; [e] degradation of 1a;
[f] 20 mol% of additive was added after 1 h; [g] The diastereo ratio of two
isomers is 1:1.16 and two diastereomers of 3aa could be isolated, in 40% and
in 46% yield, respectively.
2
Air
rt
trace
trace
trace
40
3
Air
75
4
TEA
CHCl3
CHCl3
CHCl3
CHCl3
THF
Air
75
5
Cs2CO3
DABCO
DBU
Air
75
6
Air
75
NR
7
Air
75
63
We commenced the study by choosing MBH adduct 1a and
ready available triazole 2a as model substrates. Gratifyingly,
when 2 mol% Rh2(OAc)4 was used as catalyst in CHCl3 at 75 oC
for 15 h, two isomers of 3aa were isolated in 65% overall yield
(Table 1, entry 1). These two isomers were assigned as syn-
and anti- diastereomers caused by two chiral centers according
to mechanistic speculation (See SI for more details).
Encouraged by this result, other catalysts, such as Rh2(Oct)4,
Rh2(Piv)4, and Rh2(S-nttl)4, were screened and found more
effective, providing higher yields of 3aa (Table 1, entry 2-4).
Increasing the amount of 2a to 1.2 equivalent (Table 1, entry 5-
6), the overall yield of 3aa was improved to 90%. However,
raising the temperature to 85 oC resulted in a lower yield (Table
1, entry 7). Moreover, the use of 1,2-dichloroethane (DCE) or
toluene as the solvent did not increase the yield of 3aa (Table 1,
entry 8-9). The addition of Lewis acid have no positive effects
(Table 1, entry 10-14). Finally, the reaction of MBH adduct 1a
with 1.2 equiv of triazole 2a catalyzed by Rh2(Oct)4 in CHCl3 at
75 °C were set as the optimum reaction conditions.
8
DBU
Air
75
66
9
DBU
DMF
Air
75
65
10
11
12
13
14
15
16
DBU
toluene
CH3CN
toluene
toluene
toluene
toluene
toluene
Air
75
78
DBU
Air
75
56
DBU
Air
rt
NR
DBU
Air
85
78
DBU
Air
115
75
78
DBU
DDQ
PIDA
trace
trace
DBU
75
[a] Reaction conditions: 3a (0.2 mmol), base (0.4 mmol) and solvent (1.0 mL)
were heated until 3a was consumed; [b] Isolated yield; PIDA =
phenyliodine(III) diacetate
In order to improve the convenience and practicability of this
transformation, DBU and toluene were added directly after the
rhodium catalyzed reaction in the one-pot process. The desired
product 4aa could also been obtained in comparable yield
(Scheme 2).
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Scheme 2 One-pot process for the synthesis 4aa
With the optimized reaction conditions in hand, the
generality and substrate scope of this process was investigated,
and the result was presented in Table 3 and Table 4. Firstly, a
series of 4-substituted triazoles were tested (Table 3). The
results showed that various substituted triazoles 2b-2p reacted
smoothly with MBH adduct 1a to afford 4ab-4ap in moderate to
good yields.This proved that the reactions were not affected by
the substituent position or the electronic properties of C4 aryl-
substituted triazoles 4ab-4ai. Moreover, the substrates can also
be extended to heteroaromatic substituted triazoles, such as
thienyl substituted 2j and indolyl substituted triazoles 2k, to yield
product 4aj in 62% and 4ak in 46% yield, respectively. However,
when using C4 alkyl-substituted triazoles such as cyclopropyl 2l
and tert-butyl substituted 2m as substrates, only a trace amount
of the desired products were observed. It is noteworthy that the
MBH adducts of cyclohept-2-en-1-one can also be used to
synthesize a variety of seven-membered ring fused pyrroles
4an-4ap in good yields.
Figure 2 X-ray structure for 4aa
Table 3 Substrate scope of triazolesa
Next, various MBH adducts were investigated under the
optimized conditions to test the scope of this reaction, and the
results were summarized in Table 4. The MBH adducts 1b-1n
bearing ortho- para- or meta-substituents including OMe, F, Br,
Cl, CN, CF3 on the benzene ring reacted smoothly with triazole
2a to afford the corresponding products 4ba-4na in moderate to
good yields and the reactions were less affected by electronic
properties. Reactions with naphthyl substituted MBH adducts
1o-1p and heteroaromatic substituted MBH adducts 1q-1r also
successfully provided the desired products 4oa-4ra. However,
when the alkyl-substituted MBH adducts 1s-1t were used, a
slightly reduced yields were obtained. Likewise, the MBH
adducts of cyclohept-2-en-1-one can also be used to synthesize
a variety of seven-membered ring 3,4-fused pyrroles 4ua-4wa in
good yields.
Based on the known N-sulfonyl-1,2,3-triazole chemistry and
the above results, a plausible mechanism for the formation of
the 3,4-fused pyrrole was provided in Figure 3. Initially, the
reaction of N-sulfonyl-1,2,3-triazole 2a with Rh(II) catalyst
generates a rhodium-stablized carbene, along with release of
molecular nitrogen. The azavinyl carbene reacts with the MBH
adduct via an O-H 1,1-insertion followed by tautomerization,
which could lead to an isomeric mixture of enamide intermediate
I.Then intermediate I undergoes intramolecular [3,3]-sigmatropic
rearrangement to afford 3aa (two diastereomers). Under basic
conditions, subsequent intramolecular cyclization and oxidative
aromatization gives rise to the desired 3,4-fused pyrrole 4aa.
[a] All reactions were carried out with 0.2 mmol of 1 and 0.24 mmol of 2 in 1
mL of CHCl3 at 75°C for 2-4 h until consumption of 2 was apparent by TLC
analysis. Then, toluene and DBU (2.0 equiv) were added, and the mixture was
heated at 75°C for 8-12 h. Isolated yields of purified products are shown
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In summary, we have developed a novel and efficient
way for the synthesis of potentially biological active 3,4-
fused pyrroles in good yields via Rh(II)-catalyzed reaction of
triazoles with MBH adducts derived from ɑ, β-unsaturated
cyclic ketones and subsequent rearrangement/aza-Michael
addition/ oxidative aromatization tandem reactions. This
new synthetic method enables the rapid availability of
various 3,4-fused pyrroles from readily available starting
materials under mild reaction conditions, which can be
extended to more complex frameworks. Further exploration
to construct important nitrogen-containing heterocycles are
currently underway in our laboratory.
Figure 3 The proposed reaction pathway.
Table 4 Substrate scope of MBH adductsa
Acknowledgements
This work is supported by the National Natural Science
Foundation of China (No. 21402049).
Conflict of interest
The authors declare no conflict of interest.
Keywords: triazoles • MBH adducts • 3,4-fused pyrroles •
rhodium catalyzed
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10.1002/asia.201800057
Chemistry - An Asian Journal
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
Renmeng Jia, Jiang Meng, Jiaying Leng,
Xingxin Yu* and Wei-Ping Deng*
Page No. – Page No.
Rhodium(II)-Catalyzed Reaction of
1-Tosyl-1,2,3-triazoles with Morita–
Baylis–Hillman adducts: Synthesis of
3,4-Fused Pyrroles
A cascade reaction of rhodium azavinylcarbenes with MBH adducts enables a novel
synthetic approach to 3,4-fused pyrroles. The reaction is applicable to a broad scope
of substrates and shows good compatibility of functional groups.
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