Rhodium(II)-catalyzed intramolecular cycloisomerizations of methylenecyclopropanes with N-Sulfonyl 1,2,3-Triazoles

Article abstract of DOI:10.1002/anie.201402803

A novel rhodium(II)-catalyzed tandem cycloisomerization of methylenecyclopropanes (MCPs) with N-sulfonyl 1,2,3-triazoles is disclosed. The reaction produces a series of highly functionalized polycyclic Nheterocycles via a rhodium imino carbene intermediate. A distinct feature of this divergent synthesis is that different types of substrates control the reaction pathways. Moreover, several interesting transformations of these products to construct diazabicyclo[3.2.1]octane derivatives are also reported. The azavinyl rhodium carbenes derived from N-sulfonyltriazole methylenecyclopropanes were found to be very reactive in the divergent synthesis of N-containing heterocycles. Different types of cycloisomerizations were observed depending on the substrates. Derivatization of the products easily gave a series of diazabicyclo[3.2.1]octane derivatives. Bs=bromobenzenesulfonyl, Ms=methanesulfonyl, Piv=pivalate, Ts=4-toluenesulfonyl.

Full text of DOI:10.1002/anie.201402803

Angewandte
Chemie
DOI: 10.1002/anie.201402803
Nitrogen Heterocycles
Rhodium(II)-Catalyzed Intramolecular Cycloisomerizations of
Methylenecyclopropanes with N-Sulfonyl 1,2,3-Triazoles**
Kai Chen, Zi-Zhong Zhu, Yong-Sheng Zhang, Xiang-Ying Tang,* and Min Shi*
Abstract: A novel rhodium(II)-catalyzed tandem cycloisome-
rization of methylenecyclopropanes (MCPs) with N-sulfonyl
1,2,3-triazoles is disclosed. The reaction produces a series of
highly functionalized polycyclic N heterocycles via a rhodium
imino carbene intermediate. A distinct feature of this divergent
synthesis is that different types of substrates control the reaction
pathways. Moreover, several interesting transformations of
these products to construct diazabicyclo[3.2.1]octane deriva-
tives are also reported.
for years, examples of the intramolecular reaction of the MCP
moiety with metal carbenes are very rare.
N-sulfonyl-1,2,3-triazoles, which can be easily prepared
from copper(I)-catalyzed azide–alkyne cycloadditions
(CuAAC) have recently received much attention.[4] In gen-
eral, they are used as precursors of a-imino metal carbenes
which can trigger many types of useful transformations.[5] For
instance, transannulation of N-sulfonyl-1,2,3-triazoles with
unsaturated compounds such as nitriles, alkynes, allenes,
isocyanates, furans, aldehydes, imines, and indoles produced
a series of useful N heterocycles,[6] which are the most
important class of compounds in the pharmaceutical and
agrochemical industries.[7] In addition, these a-imino metal
M
ethylenecyclopropanes (MCPs), as highly strained but
readily accessible molecules, are important building blocks in
organic synthesis. In the presence of transition metals or
Lewis acids, MCPs can undergo a variety of ring-opening
reactions, thus giving efficient access to enhanced molecular
complexity.[1,2] As an important research branch, transition-
metal-catalyzed intermolecular reactions of carbenes or
nitrenes with MCPs have drawn great attention during the
last decade.[3] For example, Kuznetsova and co-workers found
that diazo compounds could undergo cyclopropanation with
MCPs in the presence of [Rh2(OAc)4] to give polyspirocyclic
cyclopropanes in good yields.[3a] The groups of Meijere and
Kamikawa also reported [4+1] and [3+1+1] cycloadditions,
respectively, of MCPs with Fischer carbenes to generate
cyclopentanone derivatives.[3b,c] Moreover, Yu and co-workers
first reported intermolecular reaction of MCPs with N-
aminophthalimide (precursor of nitrene) to give ring-expan-
sion products.[3d] Later, we also disclosed similar transforma-
tions of MCPs with other nitrenes.[3e,f] Surprisingly, although
intermolecular versions of such reactions have been studied
carbenes can also undergo cyclopropanation,[8] C H inser-
À
tion,[9] O H or N H insertion, and arylation with boronic
acids.[11] Recently, rhodium(II)-catalyzed intramolecular reac-
tions of N-sulfonyl-1,2,3-triazoles have aroused the interest of
chemists and become increasingly popular.[12] For example,
the groups of Murakami and Fokin independently reported
the rhodium(II)-catalyzed denitrogenative rearrangement of
1-(N-sulfonyl-triazol-4-yl)alkanols.[12a,b] Another example was
reported by Davies and co-workers. They disclosed an
intramolecular rhodium(II)-catalyzed cyclization of 4-
alkenyl-1-sulfonyl-1,2,3-triazoles to 2,3-fused pyrroles and
substituted indoles.[12c] The rapid development of the chemis-
try of N-sulfonyl-1,2,3-triazoles motivated us to link these
novel azavinyl carbenes with methylenecyclopropanes.
[10]
À
À
In 2011, the group of Wu discovered a novel cascade
reaction of 2-ethynylaryl methylenecyclopropane with sulfo-
nylazide catalyzed by CuI to generate fused indolines
(Scheme 1).[13] It is believed that the ketenimine A is the
key intermediate. However, if the N-sulfonyl-1,2,3-triazole
moiety is considered a precursor of the a-imino carbene, we
reasoned that the reaction pathway should be quite different
and interesting. In fact, at the beginning of this research, we
found that N-sulfonyl-triazole MCPs (1) could undergo
a tandem cycloisomerization/aza-Diels–Alder process, thus
[*] K. Chen, Z.-Z. Zhu, Prof. M. Shi
Key Laboratory for Advanced Materials and Institute of Fine
Chemicals, East China University of Science and Technology
Meilong Road No. 130, Shanghai, 200237 (China)
Y.-S. Zhang, Dr. X.-Y. Tang, Prof. M. Shi
State Key Laboratory of Organometallic Chemistry
Shanghai Institute of Organic Chemistry
Chinese Academy of Sciences
345 Lingling Road, Shanghai 200032 (China)
E-mail: siocxiangying@mail.sioc.ac.cn
mshi@mail.sioc.ac.cn
[**] We are grateful for the financial support from the Shanghai
Municipal Committee of Science and Technology (11JC1402600),
the National Natural Science Foundation of China (20472096,
21372241, 21361140350, 20672127, 21102166, 21121062,
21302203, and 20732008), the National Basic Research Program of
China (973)-2010CB833302, and the Fundamental Research Funds
for the Central Universities (WJ1014034 and WK1013004).
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/anie.201402803.
Scheme 1. Formation of N-heterocyclic compounds from 2-ethynylaryl
MCPs and N-sulfonyl-triazole MCPs. Ts=4-toluenesulfonyl.
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affording the polycyclic N-heterocycle 2 (Scheme 1). The 1,2-
diamino-containing 2 exists in many medicinally and biolog-
ically important molecules such as biotin,[14b] balanol,[14c] and
oxaliplatin.[14d] In addition, vicinal diamines and their deriv-
atives are widely used as ligands in transition-metal cataly-
sis.[14] In contrast, the cyclobutane moieties in 2 can be very
useful building blocks as they appear in many natural
products[15] such as dictazole,[15c] sceptrin,[15d] and piperarbor-
enines.[15e] Moreover, the four-membered-ring usually gives
the molecule special bioactivities. For example, the cyclo-
butane pyrimidine dimer (CPD) interferes with base pairing
during DNA replication, thus leading to mutations.[16] Given
these facts, herein, we report our preliminary results on this
novel protocol to construct the corresponding products 2.
We initially investigated the cascade reaction of 1-(cyclo-
propylidenemethyl)-2-(1-tosyl-1,2,3-triazol-4-yl)benzene
(1a) using a variety of the rhodium(II) catalysts, solvents, and
temperatures (Table 1). The reaction of 1a catalyzed by
[Rh2(OAc)4] in 1,2-dichloroethane (DCE) at 808C gave the
product 4a (reported by Wu) in 56% yield (Table 1,
entry 1).[13] By changing catalysts to [Rh2(esp)2], [Rh2(oct)4],
and [Rh2(Piv)4] a pair of diastereoisomers, 2a and 3a, were
obtained simultaneously (Table 1, entries 2–4). [Rh2(Piv)4]
was the best catalyst in this transformation and 2a could be
obtained in 61% yield together with 3a in 21% yield. Their
structures have been unambiguously determined by X-ray
diffraction.[17] By decreasing the reaction temperature to
258C, no reaction took place (Table 1, entry 5). Carrying out
the reaction at 608C afforded 2a and 3a in 45 and 20% yield,
respectively, (Table 1, entry 6). When the reaction was con-
ducted at 1008C or 1208C in 1,1,2,2-tetrachloroethane (TCE),
2a and 4a were obtained (at 1008C: 50 and 20% yield,
respectively; at 1208C: 46 and 28% yields, respectively).
However, 3a was not observed, thus indicating that 3a might
be converted into 2a at higher temperature (Table 1, entries 7
and 8). By changing the solvent to 1,4-dioxane, 4a was
isolated as the sole product, presumably because of the
coordinative property of the oxygen atom in 1,4-dioxane
(Table 1, entry 9). To our delight, treatment of 1a in
cyclohexane in a sealed tube at 1208C afforded 2a in 80%
yield (Table 1, entry 10). Furthermore, carrying out the
reaction at 1108C in toluene led to the formation of 2a in
86% yield (Table 1, entry 11). In the absence of the rhodiu-
m(II) catalyst, 4a was isolated in 80% yield as the sole
product from a thermally induced rearrangement (Table 1,
entry 12).
With the best reaction conditions in hand, we next
examined the substrate scope of this reaction and the results
are shown in Table 2. For the substrates 1b–d, the reactions
proceeded smoothly to furnish the desired products 2b–d in
74–81% yields (Table 2, entries 1–3). In addition, in the cases
of substrates 1e–i, the reactions proceeded efficiently to give
the products 2e–i in 71–83% yields (Table 2, entries 4–8).
These results suggest that the electronic property of the
aromatic ring does not have a significant impact on the
reaction outcome. With two MeO groups at the 4- and 5-
positions on the ring, the reaction still proceeded efficiently to
afford 2j in 70% yield (Table 2, entry 9). As for substrates 1k
and 1l, in which R1 = 6-F or 3-F, the reaction proceeded
smoothly to furnish 2k (60%) and 2l (73%), respectively
(Table 2, entries 10 and 11). Other sulfonyl groups such as Bs,
Tris, or Ms were also tested, thus giving the corresponding
products 2m–o in 67–81% yields (Table 2, entries 12–14).
To further evaluate the generality of this method, the
thiophene- or cycloalkane-tethered MCPs 1p and 1q were
Table 1: Optimization of the reaction conditions of the rhodium(II)-
catalyzed tandem reaction of 1a.
Table 2: Substrate scope of rhodium-catalyzed tandem reaction of N-
sulfonyl-triazole MCPs 1.
Entry[a]
Substrate
R1
R2
2
Yield [%][b]
Entry[a]
Catalyst
Solvent
T [8C]
Yield [%][b]
1
2
3
4
5
6
7
8
1b
1c
1d
1e
1 f
1g
1h
1i
1j
1k
1l
1m
1n
1o
4-Me
4-F
4-Cl
5-F
5-Cl
5-CF3
5-Me
5-OMe
Ts
Ts
Ts
Ts
Ts
Ts
Ts
Ts
Ts
Ts
Ts
Bs
Tris
Ms
2b
2c
2d
2e
2 f
2g
2h
2i
2j
2k
2l
2m
2n
2o
74
74
81
76
83
79
77
71
70
73
60
67
74
81
2a
3a
4a
1
2
3
[Rh2(OAc)4]
[Rh2(esp)2]
[Rh2(oct)4]
[Rh2(Piv)4]
[Rh2(Piv)4]
[Rh2(Piv)4]
[Rh2(Piv)4]
[Rh2(Piv)4]
[Rh2(Piv)4]
[Rh2(Piv)4]
[Rh2(Piv)4]
–
DCE
DCE
DCE
DCE
DCE
DCE
TCE
TCE
1,4-dioxane
cyclohexane
toluene
toluene
80
80
80
80
25
–
–
9
12
21
–
20
–
–
–
–
–
–
56
–
–
–
–
37
30
61
–
45
50
46
–
4
5c
6
60
–
7
8
9
10
11
12
100
120
100
120
110
110
20
28
65
–
–
80
9
4-OMe, 5-OMe
10c
11c
12
13d
14
6-F
3-F
H
H
H
80
86
–
[a] Reaction conditions: 1a (0.1 mmol), catalyst (2 mol%), solvent
[a] Reaction conditions: 1 (0.1 mmol), [Rh2(piv)4] (2 mol%), solvent
(1.0 mL). [b] Yield of isolated product. [c] The reaction mixtures were
heated for 24 h. [d] Tris=2,4,6-(iPr)3C6H2SO2. Bs=bromobenzenesul-
fonyl, Ms=methanesulfonyl, Tris=2,4,6-triisopropylbenzenesulfonyl.
(1.0 mL). [b] Yield of isolated product. [c] The reaction did not take place
and the starting material 1a was recovered. esp=a,a,a’,a’-tetramethyl-
1,3-benzenedipropionic acid, oct=octanoate, Piv=pivalate.
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Scheme 4. Control experiments for 1u, 1v, and 3a.
Scheme 2. Further substrate scope study.
products 2a (26% yield) and 2j (17% yield), but also the
crossover cycloaddition product 2w in 42% yield, thus
confirming the intermolecular Diels–Alder reaction (Sche-
me 5a). Furthermore, we also performed a deuterium-label-
ing experiment to show that hydrogen migration does not
exist for this tandem reaction (Scheme 5b).
synthesized and treated under the standard reaction con-
ditions, thus affording the corresponding fused indolines 2p
(73%) and 2q (55%; Scheme 2a,b). It is possible that
thermally induced rearrangements of these two special
substrates are faster than the generation of their rhodium(II)
azavinyl carbene intermediates. As for substrate 1r, which has
a phenyl substituent on the MCP moiety, formal [3+3]
cyclization took place to give 2r in 65% yield (Scheme 2c).
When the N-tethered MCP 1s was used as a substrate, the
tricyclic aldehyde 2s was formed in 70% yield after cyclo-
propanation and detosylation (Scheme 3a). Interestingly, the
reaction of the substrate 1t delivered the trans-a,b-unsatu-
rated imine product 2t in 60% yield (Scheme 3b).[18] The
structures of 2r, 2s, and 2t have been unambiguously
determined by X-ray diffraction.[19] These results have
demonstrated the divergent reaction pathways of MCPs
with azavinyl carbenes.
Scheme 5. Crossover deuterium-labeling experiments.
Based on the above results and the previously reported
literature, a plausible mechanism for this reaction is outlined
in Scheme 6. The N-sulfonyltriazole 1a exists in equilibrium
with its diazoimine tautomer 1a’, which can be efficiently
intercepted by a transition-metal catalyst to give rise to the
highly reactive rhodium(II) azavinyl carbene A. The inter-
mediate A exists in equilibrium with its diazoimine tautomer
A’, and undergoes an electrophilic attack from the MCP to
Scheme 3. Investigations of alkyl-substituted substrates.
To investigate the mechanism of this rhodium(II)-cata-
lyzed tandem reaction, several control experiments were
performed (Schemes 4 and 5). The substrates 1u and 1v,
which have no cyclopropane moiety, could not be converted
into the desired products under the standard reaction
conditions, thus indicating that the strained small ring is
essential in this rhodium(II)-catalyzed tandem reaction
(Scheme 4a). Upon heating in toluene at 1108C overnight,
3a, the diastereoisomer of 2a, could be converted into 2a
quantitatively, thus indicating that retro-Diels–Alder reaction
may occur in this cascade reaction (Scheme 4b). Exposure of
1a and 1j to the reaction conditions produced not only
Scheme 6. A plausible reaction mechanism.
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furnish the intermediate B. Subsequent ring expansion and
elimination of the rhodium(II) catalyst generates the a,b-
unsaturated imine intermediate C, which is very reactive and
induces an intermolecular aza-Diels–Alder reaction to give
polycyclic the N-heterocycles 2a and 3a. When the product
mixture is heated at 1108C, the thermodynamically more
stable product 2a can be isolated as the sole product because
of the retro-Diels–Alder reaction process. For the synthesis of
2r, a similar reaction pathway may take place via the key
intermediate pictured in Scheme 2c. The formal [3+3]
cyclization is more favorable, probably because of the steric
hindrance of the phenyl group on MCP. Moreover, similar
reaction mechanisms for the formation of 2s and 2t are shown
in the Supporting Information.
Scheme 9. Transformation of compound 5a into 9a.
The imino group of the polycyclic N heterocycles could be
easily converted into an amine and aldehyde upon reduction
and hydrolysis, respectively (Scheme 7). As a result, the
corresponding amine 5a and aldehyde 6a were obtained in 90
and 88% yields, respectively.
an easier access to these compounds. Moreover, the structures
of 7a and 9a have been all unambiguously determined by X-
ray diffraction.[22]
In summary, several intramolecular tandem reactions of
MCPs with rhodium(II) azavinyl carbenes have been realized.
Different reaction pathways depending on different types of
substrates have been well investigated. The mechanisms have
been also elucidated by performing control and deuterium-
labeling experiments. A series of interesting annulations of 5a
to structurally more complex polycyclic N heterocycles dem-
onstrates the versatile utilization of this methodology to give
efficient access to enhanced molecular complexity. The
potential application and extension of the substrate scope of
this synthetic methodology are currently underway in our
laboratory.
Scheme 7. Transformation of compound 2a into 5a and 6a.
Further transformations of the polycyclic sulfonamide 5a
were also conducted. In the presence of TFA and selectfluor,
5a underwent hydroamination and fluoroamination, respec-
tively, thus giving the corresponding 2,8-diazabicyclo-
[3.2.1]octane derivatives 7a (85%) and 8a (62%;
Scheme 8). To our delight, upon treatment of 5a with I2 and
K CO , the 3,8-diazabicyclo[3.2.1]octane derivative 9a was
Received: February 25, 2014
Revised: April 14, 2014
Published online: && &&, &&&&
Keywords: carbenes · isomerization · nitrogen heterocycles ·
.
2
3
rhodium · small ring systems
obtained in 70% yield (Scheme 9). This interesting reaction
pathway may contain a cascade iodoamination, retro-Man-
nich reaction,[20] and hydrolysis. Significantly, diazabicyclo-
[3.2.1]octanes, especially 3,8-diazabicyclo[3.2.1]octane deriv-
atives, usually have valuable biological properties.[21] For
example, Azaprocin is an opioid analgesic with approximately
ten times the potency of morphine, and a fast onset and short
duration of action.[21a,b] Therefore, the compounds 7a, 8a, and
9a are all potential drug candidates. Considering that the
synthetic methods to these diazabicyclo[3.2.1]octane deriva-
tives are extremely limited, our synthetic methodology offers
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4
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Angew. Chem. Int. Ed. 2014, 53, 1 – 6
ꢀ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
5
These are not the final page numbers!

.
Angewandte
Communications
Communications
Nitrogen Heterocycles
The azavinyl rhodium carbenes derived
from N-sulfonyltriazole methylenecyclo-
propanes were found to be very reactive
in the divergent synthesis of N-containing
heterocycles. Different types of cycloiso-
merizations were observed depending on
the substrates. Derivatization of the
products easily gave a series of
diazabicyclo[3.2.1]octane derivatives.
Bs=bromobenzenesulfonyl, Ms=meth-
anesulfonyl, Piv=pivalate, Ts=4-tolue-
nesulfonyl.
K. Chen, Z.-Z. Zhu, Y.-S. Zhang,
X.-Y. Tang,* M. Shi*
&&&& — &&&&
Rhodium(II)-Catalyzed Intramolecular
Cycloisomerizations of
Methylenecyclopropanes with N-Sulfonyl
1,2,3-Triazoles
6
www.angewandte.org
ꢀ 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2014, 53, 1 – 6
These are not the final page numbers!