A Rh-catalyzed 1,2-sulfur migration/aza-Diels-Alder cascade initiated by aza-vinyl carbenoids from sulfur-tethered N-sulfonyl-1,2,3-triazoles

Article abstract of DOI:10.1039/c4cc08829h

A novel Rh(ii) catalyzed intramolecular 1,2-sulfur rearrangement/intermolecular aza-Diels-Alder cascade initiated by azavinyl carbenes has been developed, efficiently affording sulfur-containing tetrahydropyridine derivatives or α,β-unsaturated imines wit

Full text of DOI:10.1039/c4cc08829h

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ARTICLE TYPE
RhꢀCatalyzed 1,2ꢀSulfur Migration/azaꢀDielsꢀAlder Cascade Initiated by
azaꢀVinyl Carbenoids from SulfurꢀTethered NꢀSulfonylꢀ1,2,3ꢀtriazoles
Yu Jiang,a XiangꢀYing Tang,*b and Min Shi*ab
Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
5
DOI: 10.1039/b000000x
40
A
novel Rh(II) catalyzed intramolecular 1,2ꢀsulfur
Scheme 1. Previous work and this work.
rearrangement/intermolecular azaꢀDielsꢀAlder cascade
Previous work
initiated by azavinyl carbenes has been developed, efficiently
affording sulfurꢀcontaining tetrahydropyridine derivatives or
10 α,βꢀunsaturated imines with a broad substrate scope.
a) Wang's work
R3
SR3
SR3
SR3
R1
R2
COR4 [Rh]
R1
R2
S
COR4
R1
R1
R2
COR4
R2
COR4
-
N2
[Rh]
-N2
[Rh]
Sꢀcontaining heterocycles are privileged structural motifs in
many natural products and biologically active compounds[1] and
the development of synthetic methods for these compounds has
attracted much attention.[2] 1,2ꢀSulfur migration is an important
15 chemical transformation protocol for organic chemists and this
method has been developed as valuable tools for organic
synthesis in the construction of Sꢀcontaining compounds.[2,3] Thus
far, this method has been extensively used in the synthesis of
many nonaromatic or aromatic heterocycles.[4,5] The most
20 common route of 1,2ꢀsulfur migration usually proceeds through a
thiiranium intermediate. As an important process to produce a
thiiranium intermediate, 1,2ꢀsulfur migration to a carbenoid
center has been reported in recent years.[6a,6b,7] For example, in
2005, Wang and coꢀworkers reported Rhꢀcatalyzed 1,2ꢀsulfur
25 group migration through a thiiranium zwitterion, demonstrating
that sulfur atom has a higher migratory aptitude over other atoms
(Scheme 1a).[6a] Then, Xu’s group reported the similar
transformation of βꢀthio group substituted αꢀdiazo carbonyl
compounds to ketenes also via a thiiranium intermediate.[6b]
30 Although metalꢀcatalyzed 1,2ꢀthio migration is useful and
efficient, the reported examples and reaction modes for the
synthesis of Sꢀcontaining heterocycles are still limited.
b) Miura and Murakami's work
X
H
X
N
N
N
Rh2(Piv)4
1,2-DCE, 80 o
C
NR1
X = C, N
H
R1
R2
N
c) Lin's work
R2
N
Rh2(Oct)4
1,2-DCE, 60 o
N
N
N
C
R1N
R1
This work:
Sulfur-Tethered N-sulfonyl-1,2,3-triazoles (intra- and intermolecular cascade manner)
R1
R1
R2
R2
N
N
R1
Ts
RS
RS
TsN
N
[Rh]
RS
aza-D-A
R1 = R2 = H
R2
RS
heating
N
[Rh]
SR
NTs
Ts
NTs
R = Ar, Alkyl
types of reactions.[14] Concerning about intermolecular reaction
45 manners, due to the αꢀimino rhodium(II) carbene species bearing
both an electrophilic carbenoid carbon and a nucleophilic
nitrogen atom, they can react with many other compounds such
as nitriles, isocyanates, aldehydes, heteroaromatics and so on to
produce various useful Nꢀheterocycles.[15] On the other hand,
50 rhodium(II)ꢀcatalyzed intramolecular reactions of Nꢀsulfonylꢀ
1,2,3ꢀtriazoles have also aroused the interest of chemists and the
novel reaction modes have been disclosed by several groups[14,16]
including ours.[17] For example, in 2014, Miura and Murakami[16d]
reported intramolecular dearomatizing [3+2] annulation of azaꢀ
55 vinyl carbenoids with aryl rings, furnishing 3,4ꢀfused indole
skeletons, in which the key steps involved the benzene ring acting
as the dipolarophile to react with the αꢀimino Rh carbenoid
(Scheme 1b). Subsequently, the group of Lin[16e] reported a
reaction for converting Nꢀpropargylanilines to functionalized
60 indoles through Rh(II)ꢀcatalyzed denitrogenative annulation of Nꢀ
sulfonylꢀ1,2,3ꢀtriazoles (Scheme 1c). Inspired by these previous
findings shown in Scheme 1, we envisaged that if a neighboring
sulfur atom was introduced to the Nꢀsulfonylꢀ1,2,3ꢀtriazole
moiety, the azaꢀvinyl Rh carbene induced 1,2ꢀsulfur migration
65 might be able to take place due to the nucleophilicity of sulfur
atom, giving a new reaction mode of azaꢀvinyl Rhꢀcarbene
chemistry. In fact, we indeed found that thio groupꢀtethered Nꢀ
sulfonylꢀ1,2,3ꢀtriazoles could be converted to tetrahydropyridine
Recently, Nꢀsulfonylꢀ1,2,3ꢀtriazoles, which can be easily
prepared from copper(I)ꢀcatalyzed azideꢀalkyne cycloadditions,
35 have emerged as alternative precursors for the formation of αꢀ
imino metal carbenoids.[8] Thus far, it has been known that they
can undergo a variety of synthetically useful transformations via
typical carbene reaction manners[9ꢀ14] such as cyclopropanation,[11]
CꢀH, OꢀH or NꢀH insertion,[12][13] and carbene induced other
aKey Laboratory for Advanced Materials and Institute of Fine
Chemicals, East China University of Science and Technology, Meilong
Road No. 130, Shanghai, 200237 (China)
bState Key Laboratory of Organometallic Chemistry, Shanghai Institute
of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling
Road,
Shanghai
200032
China.
Eꢀmail:
siocxiangying@mail.sioc.ac.cn; mshi@mail.sioc.ac.cn
† Electronic Supplementary Information (ESI) available: Experimental
procedures, characterization data of new compounds, and CCDC
996223, 1013188 and 1021015. See DOI: 10.1039/b000000x
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DOI: 10.1039/C4CC08829H
derivatives
through
intramolecular
1,2ꢀsulfur
perhaps due to that the corresponding product is not stable upon
migration/intermolecular azaꢀDielsꢀAlder cascade[18] or α,βꢀ 55 heating.[20]
unsaturated imine derivatives through an intramolecular 1,2ꢀ
sulfur migration process depending on the substitution pattern,
Table 2. Reaction Scope: Synthesis of heterocyclic products 2.[a]
R2
N
5
respectively (Scheme 1, this work). Herein, we would like to
report these interesting findings.
We initially utilized 4ꢀ(pꢀtolylthiomethyl)ꢀ1ꢀtosylꢀ1Hꢀ1,2,3ꢀ
triazole 1a (R1 = R2 = H, Scheme 1, this work) as substrate by
carrying out the reaction in 1,2ꢀDCE (1,2ꢀdichloroethane) in the
10 presence of [Rh2(esp)2] to examine the reaction outcomes. The
tetrahydropyridine derivative 2a derived from an intramolecular
1,2ꢀsulfur migration and a subsequent intermolecular azaꢀDielsꢀ
N
R2N
R1S
NR2
Rh2(OAc)4 (1.0 mol%)
1,2-DCE, 80 o
N
SR1
C
R1S
1
2
2f, R3 = 2-Me, 88%, 1 h
2g, R3 = 2-MeO, 73%, 1 h
2h, R3 = 2-F, 83%, 4 h
2i, R3 = 2-Cl, 87%, 4 h
2j, R3 = 2-Br, 81%, 4 h
2a, R3 = 4-Me, 91%, 0.5 h
2b, R3 = 4-iPr, 93%, 0.5 h
2c, R3 = 4-Br, 91%, 3 h
2d, R3 = 4-NO2, 85%, 3 h
2e, R3 = 3-MeO, 94%, 1 h
Ts
N
3
TsN
4
2
S
1
R3
4
1
S
R3
2
3
1
Alder cascade was obtained in 88% yield based on the H NMR
Ts
Ts
Ts
TsN
TsN
N
N
spectroscopy (Table 1, entry 1). Then, we turned our attention to
15 identify the optimized reaction conditions for the current reaction
by screening various rhodium catalysts, solvents, and
temperatures. The results are summarized in Table 1. Changing
catalysts to [Rh2(OAc)4] and [Rh2(Piv)4] produced 2a in 94% and
91% yields, respectively (entries 2 and 3). Using [Rh2(tfa)4] as
20 the catalyst, no reaction occurred (entry 4). [Rh2(OAc)4] was
identified as the best catalyst in this reaction, affording 2a in 91%
isolated yield. Its structure has been unambiguously determined
by Xꢀray diffraction. Its ORTEP drawing and the CIF data are
presented in the Supporting Information.[19] Moreover, the use of
25 toluene and CHCl3 as the solvents afforded 2a in lower yields
TsN
S
N
O
S
S
S
S
S
S
S
O
2k, 90%, 4 h
2l, 71%, 4 h
2m, 86%, 4 h
Ts
Ts
Ts
N
Ts
TsN
TsN
TsN
TsN
N
N
N
Ph
S
S
S
S
S
S
S
S
Ph
2n, 76%, 6 h
2o, 91%, 8 h
2p, 88%, 14 h
2q, 90%, 8 h
Bs
N
Ts
N
Ts
BsN
TsN
TsN
N
CO2Me
S
S
TIPSO
S
( )n
( )n
S
S
S
OTIPS
CO2Me
2r, 83%, 12 h
2s, 62% (n = 3), 12 h
2t, 83%, 1 h
o
(entries 5 and 6). Carrying out the reaction temperature at 50 C,
no reaction could take place (entry 7).
[a] Conditions: 1 (0.20 mmol) and Rh2(OAc)4 (0.002 mol) were heated in DCE (2 mL) at 80 oC for appropriate
time.
Table 1. Optimization of the reaction conditions.
60
Furthermore, Lꢀmenthol and cholesterol derived Nꢀsulfonylꢀ
1,2,3ꢀtriazoles 1u and 1v were also employed in this reaction,
delivering the desired products 2u and 2v in 89% and 84% yields
respectively as a pair of diastereomers (Scheme 2). These results
suggest the potential application of this methodology in the
S
Ts
N
TsN
N
catalyst (1.0 mol%)
solvent, T
S
N
S
N
Ts
1a
2a
entry[a]
catalyst
time (h)
T (oC)
yield (%)[b]
88
solvent
65 linkage with naturally occurring bioactive substances.
Rh2(esp)2
0.5
0.5
0.5
0.5
1
1,2-DCE
1,2-DCE
1,2-DCE
1,2-DCE
Toluene
CHCl3
80
80
80
80
80
80
50
1
2
3
4
5
6
7
94 (91[c]
)
Rh2(OAc)4
Rh2(Piv)4
Rh2(tfa)4
Scheme 2. Reaction of LꢀMenthol and Cholesterol derived Nꢀ
sulfonylꢀ1,2,3ꢀtriazole.
91
N.R.
53
Rh2(OAc)4
Rh2(OAc)4
Rh2(OAc)4
1
14
1,2-DCE
2
N.R.
[a] Unless otherwise specified, all reactions were performed with 1a (0.20 mmol) and catalyst
(0.002 mmol). [b] Yields are determined by 1H NMR using 1,3,5-trimethoxybenzene as an
internal standard. [c] Isolated yields.
30
With this optimal reaction conditions in hand, we next
surveyed the substrate scope of various triazole 1. As shown in
Table 2, as for substrates 1bꢀd, the reactions proceeded smoothly
35 to furnish the desired products 2bꢀd in 85ꢀ93% yields. In addition,
in the cases of substrates 1fꢀj, the reactions proceeded efficiently
to give the desired products 2fꢀj in 73ꢀ88% yields. These results
suggest that the substrates with electronꢀwithdrawing group at the
2ꢀposition on the aromatic ring may be more conducive to the
40 production of 2 compared to that of electronꢀdonating ones.
Introducing a electronꢀdonating MeO group at the 3ꢀposition of
benzene ring afforded the corresponding product 2e in 94% yield
under the standard conditions. The substituents on the sulfur atom
could be heteroaromatic rings such as thienyl, furyl or 2ꢀnaphthyl
70
Next, the further examinations were performed to extend the
substrate scope in which R1 or R2 is not a H atom under the
standard conditions (Scheme 1, this work). We found that α,βꢀ
unsaturated imine derivatives 4 were given instead of the
45 group, providing the desired products 2kꢀm in yields ranging 75 tetrahydropyridine derivatives due to that the following azaꢀ
from moderate to excellent. Furthermore, this reaction could also
tolerate various aliphatic substituents or functional groups such
ester group or protected OH group on the sulfur atom, indicating
a broad substrate scope, giving the desired products 2nꢀ3s in
DielsꢀAlder reaction was shut down, perhaps because of the steric
hindrance. As shown in Table 3, the substrate 3a or 3d bearing a
Me or Bu group at the methylene position (R = Me or Bu) gave
the corresponding imine product 4a or 4d in 81% yield or 75%
50 good yields. Bs (4ꢀbromophenylsulfonyl) substituted Nꢀsulfonylꢀ 80 yield, respectively. The substituent on the sulfur atom could be
1,2,3ꢀtriazole could be also used in this reaction, affording the
corresponding product 2t in 83% yield. As for seleniumꢀtethered
triazole 1w, the reaction gave a complex product mixtures,
bromobenzene as well, giving the desired product 4b in 85%
yield. Meanwhile, substrate 3c bearing two Me groups at the
methylene position also afforded the corresponding product 4c in
2
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83% yield. In addition, as for the dithioacetal substrates 3e, 3f
and 3g, the reactions proceeded smoothly to afford the desired
Based on the above results and the previously reported
literature, a plausible mechanism for this reaction is outlined in
products containing a sixꢀmembered Sꢀheterocycle 4e, 4f and 4g 40 Scheme 4. This reaction begins with a rapid formation of αꢀimino
in good yields. The Zꢀconfiguration of 4a, 4b and 4d was
rhodium(II) carbenoid A upon heating 1 or 3 with Rh catalyst.
Subsequent sulfur 1,2ꢀmigration through intermediate
5
determined based on the Xꢀray crystal structure of 4a.[21]
B
generates the corresponding α,βꢀunsaturated imine product 4.
When R1 and R2 groups are H atom, an intermolecular azaꢀDielsꢀ
45 Alder reaction can be induced to give the corresponding Nꢀ
heterocycle 2 presumably due to that this product is very reactive
to undergo the bimolecular cycloaddition. In the case of 3a, upon
nucleophilic addition to the rhodium carbene, both intermediates
D and D’ would be formed (Scheme 5). However, intermediate D
50 is more stable than D’ probably due to the less steric repulsion
between the transꢀconfigured NTs and methyl group. Therefore,
after ringꢀopening process, (Z)ꢀ4a was formed exclusively from
intermediate D.
Table 3. Reaction Scope: Synthesis of Product 4.[a]
55 Scheme 4. A plausible reaction mechanism.
10
The synthetic utility of α,βꢀunsaturated imine products was
exemplified by further transformations. As shown in Scheme 3,
tetrahydropyridine derivative 5a could be obtained in 82% yield
as a stereoisomeric mixture upon treating 4a with 3.0 equiv of
o
ethoxyethene in 1,2ꢀDCE at 120 C in a sealed tube. Its structure
15 has been fully characterized by spectroscopic data (see
Supporting Information). When 1.2 equiv of ethoxyethene was
used, 1,4ꢀdihydropyidine derivative 6a could be obtained in 54%
yield presumably derived from the elimination of ethanol from 5a.
The control experiments indicated that in the presence of extra
20 ethoxyethene, 5a is stable under the standard conditions (Scheme
3, eq a and b). The reason of this phenomenon may be due to the
partial decomposition of ethoxyethene by ambient water at high
temperature during the reaction proceeding to generate ethanol,
which may inhibit the release of ethanol from 5a under otherwise
25 identical conditions (see Supporting Information for details).
Scheme 5. A plausible explanation for the exclusive formation of
(Z)ꢀ4a.
60
Scheme 3. Transformations of 4a and the control experiments.
For the potential utility of this protocol, the reaction has been
also carried out on a 1.0 g scale. As shown in Scheme 6, as for
triazole substrate 1a, the reaction proceeded smoothly to give the
65 desired product 2a in 88% yield. Carrying out the reaction of 3a
on a 1.0 g scale under the standard conditions produced 4a in
66% yield presumably due to the partial decomposition of this
imine product in silica gel column chromatography during the
purification.
70
Scheme 6. Gram scale reaction of 1a and 3a.
30
Moreover, in the presence of 1,4ꢀdiaza[2.2.2]bicyclooctane
(DABCO) (20 mol%), 4a could be transformed to the dimeric
cyclic product 7a in 76% yield as 10:1 diastereomeric ratio
through a sequential isomerization and formal azaꢀDielsꢀAlder
process (see Supporting Information for the detailed mechanism).
35 The structure of 7a was further determined by the Xꢀray
diffraction. Its ORTEP drawing and the CIF data are presented in
the Supporting Information.[22]
In summary, we have developed a novel and efficient synthetic
75 protocol to easily access Sꢀcontaining tetrahydropyridine
derivatives from the rhodiumꢀcatalyzed cascade of sulfurꢀtethered
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Nꢀsulfonylꢀ1,2,3ꢀtriazole derivatives. The reaction involves an
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intramolecular 1,2ꢀsulfur migration/intermolecular azaꢀDielsꢀ
Alder cascade initiated by azaꢀvinyl Rh carbenoid. Further
investigation indicated that α,βꢀunsaturated imine derivatives can
be readily produced when R1 or R2 is not H atom, and a series of
novel Sꢀcontaining heterocycles could be also synthesized upon
further transformation. This chemistry can be used to the
naturally occurring bioactive substances as well. These new
findings subsequently enrich the azaꢀvinyl Rh carbene chemistry
5
10 at the present stage. The potential application and extension of
the substrate scope of this novel synthetic methodology are
currently underway in our laboratory.
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We are grateful for the financial support from the National Basic
15 Research Program of China (973)ꢀ2015CB856603, and the
National Natural Science Foundation of China (20472096,
21372241, 21361140350, 20672127, 21102166, 21121062,
21302203 and 20732008).
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DOI: 10.1039/C4CC08829H
S-containing heterocycles
Yu Jiang, Xiang-Ying Tang*, and Min
Shi* __________ Page – Page
Rh-Catalyzed 1,2-Sulfur Migration/aza-
Diels-Alder Cascade Initiated by aza-
Vinyl Carbenoids from Sulfur-Tethered
N-Sulfonyl-1,2,3-triazoles
A novel Rh(II) catalyzed intramolecular 1,2-sulfur migration/intermolecular aza-
Diels-Alder cascade of sulfur-tethered N-sulfonyl-1,2,3-triazoles has been
developed, efficiently affording sulfur-containing tetrahydropyridine derivatives.
This journal is © The Royal Society of Chemistry [year]
Journal Name, [year], [vol], 00–00 | 5