Rhodium(II)-Catalyzed Intramolecular Transannulation of 4-Methoxycyclohexa-2,5-dienone Tethered 1-Sulfonyl-1,2,3-triazoles: Synthesis of Azaspiro[5.5]undecane Derivatives

Article abstract of DOI:10.1002/adsc.201900290

A Rh(II)-catalyzed denitrogenative intramolecular transannulation using 4-methoxycyclohexa-2,5-dienone tethered N-sulfonyl-1,2,3-triazoles as substrates has been developed, affording diversified 3-methoxy-1-tosyl-1-azaspiro[5.5]undecanes in moderate to good yields under mild conditions. This new synthetic method proceeded through an oxonium ylide generated from trapping a rhodium(II)-carbene by methoxy group, a methoxy group migration, and C?N bond formation, providing an interesting synthetic strategy for the construction of spirocyclic frameworks. (Figure presented.).

Full text of DOI:10.1002/adsc.201900290

Title: Rhodium(II)-Catalyzed Intramolecular Transannulation of 4-
Methoxycyclohexa-2,5-dienone Tethered 1-Sulfonyl-1,2,3-
Triazoles: Synthesis of Azaspiro[5.5]undecane Derivatives
Authors: Min Shi, Cheng-Zhi Zhu, and Yin Wei
This manuscript has been accepted after peer review and appears as an
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the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
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To be cited as: Adv. Synth. Catal. 10.1002/adsc.201900290
Link to VoR: http://dx.doi.org/10.1002/adsc.201900290

10.1002/adsc.201900290
Advanced Synthesis & Catalysis
.
UPDATE
DOI: 10.1002/adsc.201900290
Rhodium(II)-Catalyzed Intramolecular Transannulation of 4-
Methoxycyclohexa-2,5-dienone Tethered 1-Sulfonyl-1,2,3-Triazoles:
Synthesis of Azaspiro[5.5]undecane Derivatives
Cheng-Zhi Zhu,a Yin Wei,b Min Shi*a,b
a
Key Laboratory for Advanced Materials and Institute of Fine Chemicals, School of Chemistry & Molecular Engineering,
East China University of Science and Technology, 130 Mei Long Road, Shanghai 200237 China.
b
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Center for Excellence in
Molecular Synthesis, Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032 China.
Fax: (+86)-21-6416-6128; e-mail: mshi@mail.sioc.ac.cn
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
Thus far, tandem RCM reactions were frequently applied
as efficient synthetic methods for the construction of
spirocyclic frameworks and the elegant examples have been
reported by Tanner[3a] and Harrity,[3b] respectively (Scheme 2-
1, eq. a). On the other hand, radical translocation-cyclization
cascade was another useful strategy reported by Tokuyama
and his co-workers in the total synthesis of Histrionicotoxin[1a]
(Scheme 2-1, eq. b).
Abstract. A Rh(II)-catalyzed denitrogenative intramolecular
transannulation using 4-methoxycyclohexa-2,5-dienone tethered
N-sulfonyl-1,2,3-triazoles as substrates has been developed,
affording
diversified
3-methoxy-1-tosyl-1-
azaspiro[5.5]undecanes in moderate to good yields under mild
conditions. This new synthetic method proceeded through an
oxonium ylide generated from trapping a rhodium(II)-carbene by
methoxy group, a methoxy group migration, and C-N bond
formation, providing an interesting synthetic strategy for the
construction of spirocyclic frameworks.
Keywords: Rh(II)-catalyzed; transannulation; N-sulfonyl-1,2,3-
triazoles; oxonium ylide.
The 1-azaspiro[5.5]undecane skeleton is
a privileged
structural motif in many biologically active and medicinally
valuable molecules. For example, Histrionicotoxin (HTX)
analogues, a kind of alkaloids isolated from the skins of the
brightly-colored "poison dart" frogs of Central America,
contain an essential 1-azaspiro[5.5]undecane core and possess
activity as a noncompetitive blocker of nicotinic acetylcholine
receptors (Scheme 1).[1] In addition, perhydrohistrionicotoxin
also has significant biological activities in medicinal
chemistry.[1] Thus, the rapid construction of
a novel
azaspiro[5.5]bicyclic system from simple starting materials
was of considerable interest in both of synthetic and medicinal
chemistry.[2]
Scheme 2. Previous work and our working hypothesis of this
work.
Recently, the N-sulfonyl-1,2,3-triazoles, prepared through
copper(I)-catalyzed azide-alkyne cycloaddition (CuAAC),[4] have
been utilized to generate α-imino rhodium(II) carbene precursors
in a series of novel carbene-induced transformations, providing an
efficient protocol for the synthesis of nitrogen-containing
heterocycles.[5] To date, the research groups of Fokin,
Gevorgyan,[6] Davies,[7] Murakami,[8] Sarpong,[9] our group[10] and
Scheme 1. Natural products containing 1-azaspiro[5.5]undecane
units.
1
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10.1002/adsc.201900290
Advanced Synthesis & Catalysis
others[11] have been intensively illustrating the vast synthetic
potential of these carbenoid intermediates. Notably, an active
ylide would be generated if the carbene was trapped by a
heteroatom, such as sulfur, nitrogen, bromine or oxygen atom,[12]
which could set up a stage for the subsequent transformations.
Boyer and co-workers have recently reported a rhodium(II)-
catalyzed denitrogenative transformation of 1-sulfonyl-1,2,3-
triazoles with pendent allyl and propargyl ether motifs to oxonium
ylides that undergo [2,3]-sigmatropic rearrangement to give
substituted dihydrofuran-3-imines in 2014[12c] (Scheme 2-2,
previous work). Encouraged by these brilliant works, herein we
wish to report a Rh(II)-catalyzed intramolecular transannulation
reaction of 4-methoxycyclohexa-2,5-dienone tethered 1-sulfonyl-
1,2,3-triazoles 1 through an oxonium ylide formation, C-O bond
cleavage, methoxy migration and C-N bond formation process,
leading to the rapid construction of 1-azaspiro[5.5]undecane
derivatives (Scheme 2-2, this work).
corresponding product 2a in 66% yield (entry 11), and this
result provided the possibility for the exploration of
asymmetric variant of this reaction.
Table 1. Optimization of the reaction conditions of Rh(II)-
catalyzed intramolecular transannulation reaction of 1a.
Scheme 3. Synthesis of 4-methoxycyclohexa-2,5-dienone
tethered triazoles 1. CuTc = copper(I) thiophene-2-carboxylate.
With the optimal reaction conditions in hand, we next
investigated the substrate scope and generality of this new
spirocyclization reaction, and the results are shown in Table 2. As
illustrated, introducing methyl group, trifluoromethyl group or
halogen atom as the substituent at the α-position of the carbonyl
group (substrates 1b-1f), the reactions proceeded smoothly,
affording the desired products 2b-2f in moderate to good yields
ranging from 63% to 79%. We also attempted to introduce more
functional groups at the α-position of the carbonyl group.
However, when a methoxy group was introduced at the α-position
of the carbonyl group, the corresponding N-sulfonyl-1,2,3-triazole
product could not be obtained, but some unidentified oily by-
products were isolated. In addition, when an ester group or a
heteroaromatic group was introduced at the α-position of the
carbonyl group, the corresponding dehydroxylation product could
not be obtained due to that these intermediates were not stable
under reduction with Et3SiH and BF3·OEt2 (see Scheme S3 in the
Supporting Information). A variety of aryl groups could be
introduced at the α-position of the carbonyl group by a Suzuki-
The 4-methoxycyclohexa-2,5-dienone tethered N-sulfonyl-
1,2,3-triazoles 1 could be easily obtained in six steps as shown
in Scheme 3 (see Scheme S1 in the Supporting Information for
the details). When N-sulfonyl-1,2,3-triazole 1a was treated
with 5 mol% Rh2(OAc)4 in dry 1,2-DCE (1,2-dichloroethane)
at 80 oC, we found that the desired 3-methoxy-1-tosyl-1-
azaspiro[5.5]undeca-2,7,10-trien-9-one 2a was obtained in
70% yield after 2 hours (Table 1, entry 1). The structure of 2a
has been unequivocally assigned by X-ray diffraction. The
ORTEP drawing is shown in Table 1 and the CIF data are
presented in the Supporting Information. Replacing Rh2(OAc)4
with Rh2(Oct)4 gave 2a in higher yield up to 81% (entry 2).
No reaction occurred when 1a was treated with Rh2(tfa)4
(entry 3). The use of other rhodium(II) catalysts such as
Rh2(Piv)4 and Rh2(esp)2 resulted in 2a in lower yields (entries
4 and 5). When the reaction was carried out without a catalyst,
none of the desired product could be detected, and the
substrate 1a was recovered, indicating that rhodium(II)
catalyst played an essential role in this reaction (entry 6).
Miyaura
cross
coupling
reaction
of
3-bromo-4-
hydroxybenzaldehyde and arylboronic acids (see Supporting
Information). As shown in Table 2, these α-aryl group substituted
triazoles 1g-1l could produce the corresponding products 2g-2k in
56-68% yields under the standard conditions regardless of
whether electron-neutral or electron-rich or electron-deficient
substituent was introduced on the benzene ring, suggesting that
the electronic property of aromatic ring did not have significant
impact on the reaction outcome. The methyl group could be
introduced on the meta-position of phenyl ring, giving the desired
product 2l in 61% yield. Naphthyl group was also tolerated,
furnishing the desired product 2m in 66% yield. When the two α-
After
a
quick solvent screening, we found that
similar result as that of 1,2-
dichloromethane led to
a
dichloroethane (entry 7), and toluene was substantially less
effective than that of 1,2-dichloroethane (entry 8). The use of
tetrahydrofuran and acetonitrile as the solvents provided poor
results under otherwise identical conditions (entries 9 and 10).
Therefore, Rh2(Oct)4 was the most suitable catalyst for this
reaction and 1,2-dichloroethane (DCE) was identified as the best
solvent of choice. The use of
a
chiral rhodium(II)
tetracarboxylate catalyst [Rh2(S-DOSP)4] afforded the
2
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10.1002/adsc.201900290
Advanced Synthesis & Catalysis
positions of the carbonyl group were occupied by two methyl
groups, the reaction also took place smoothly to give the
corresponding product 2n in 67% yield. Unfortunately, substrates
1o-1q having substituents at the β-position of the carbonyl group
were not tolerated in this transformation. In these cases, none of
the desired products 2o-2q could be obtained and the starting
materials were hydrolyzed during the reaction since the
corresponding by-product TsNH2 could be detected. We assumed
that the dienone skeleton played an essential role in this reaction
through the coordination with rhodium metal center, and the
coordination probably shortened the distance between the
rhodium carbene and the nucleophilic oxygen atom, allowing the
intramolecular reaction to take place smoothly. Nevertheless, the
steric bulkiness due to the substituent at the β-position would
impair this coordination and block out the nucleophilic attack of
oxygen atom to the rhodium carbene (Scheme 4). For substrate 1p
having a fluorine atom, the electronic effect may also dramatically
affect the reaction proceeding.
Scheme 5. Further examination of the substrate scope and the
preliminary asymmetric trial.
On the basis of the above results, a plausible reaction
mechanism is illustrated in Scheme 6 by using 1a as a model
substrate. Upon treatment with rhodium(II) catalyst, N-sulfonyl
triazole 1a underwent a denitrogenation process to generate the
corresponding α-imino rhodium carbene A, which could be
further trapped by the methoxy group to produce an oxonium
ylide B.[13] After release of the rhodium catalyst, an intermediate
C was formed. The intermediate C underwent an intramolecular
isomerization to give an intermediate D, which subsequently
underwent an intramolecular nucleophilic attack to cleave the C-O
bond, affording the corresponding 1-azaspiro[5.5]undecane 2a.
Table 2. Substrate scope for the reaction.[a]
Scheme 6. A plausible mechanism for the formation of 2a.
In summary, we have developed a step-economical and
practically useful synthetic method for the preparation of 1-
Scheme 4. A plausible transition state to form oxonium ylide.
azaspiro[5.5]undecane derivatives based on
a
novel
rhodium(II)-catalyzed intramolecular transannulation
reaction of 4-methoxycyclohexa-2,5-dienone tethered N-
sulfonyl triazoles for the first time. A variety of functional
groups can be tolerated although the substituent at the -
position of the carbonyl group can block out this
transannulation reaction. This new cascade reaction in the
rhodium(II)-catalyzed cyclization of N-sulfonyl triazoles
goes through the formation of an oxonium ylide intermediate,
a methoxy group migration, and C-N bond formation to give
To further clarify the substrate scope of this reaction, we
utilized N-sulfonyl triazole 3 bearing an iPrO group as a substrate
to carry out the reaction, but found that the desired spirocyclic
product could not be obtained under the standard conditions and
complex product mixtures were formed, presumably due to
steric bulkiness of isopropoxy group (Scheme 5). Moreover, the
examination of its asymmetric variant was conducted by using
[Rh2(S-DOSP)4] as the catalyst for the transformation of
substrate 1b, giving the corresponding product 2b in 76% yield
along with low ee value (Scheme 5).
the spiroheterocycles
2 in moderate to good yields. Further
application of this methodology to the synthesis of
biologically active alkaloid natural products are currently
underway.
Experimental Section
General Procedures for the Synthesis of 2
3
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10.1002/adsc.201900290
Advanced Synthesis & Catalysis
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Under argon atmosphere, Rh2(Oct)4 (0.05 mmol, 0.05 equiv.) was
added to a solution of 1-sulfonyl-1,2,3-triazole 1 (1.0 mmol, 1.0
equiv.) in dry 1,2-dichloroethane (15.0 mL) in a Schlenk tube.
The reaction mixture was stirred for about 2 h at 80 oC until 1 was
completely consumed by TLC monitoring. Then, the solvent was
removed under reduced pressure and the residue was purified by a
silica gel flash column chromatography (eluent: petroleum
ether/EtOAc, 8/1~4/1) to give the desired product 2.
Supporting Information Available
Detailed descriptions of experimental procedures and their
spectroscopic data as well as the crystal structures are presented in
the Supporting Information. CCDC 1822731 (2a) contains the
supplementary crystallographic data for this paper. These data can
be obtained free of charge from The Cambridge Crystallographic
Data Center via www.ccdc.cam.ac.uk/data_request/cif.
Acknowledgements
We are grateful for financial support from the National Basic
Research Program of China [(973)-2015CB856603], the
Strategic Priority Research Program of the Chinese Academy of
Sciences (Grant No. XDB20000000) and sioczz201808, and the
National Natural Science Foundation of China (Nos. 20472096,
21372241, 21572052, 20672127, 21421091, 21372250, 21121062,
21302203, 20732008, 21772037, 21772226 and 21861132014),
and the Fundamental Research Funds for the Central Universities
222201717003.
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4
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10.1002/adsc.201900290
Advanced Synthesis & Catalysis
UPDATE
Rhodium(II)-Catalyzed
Intramolecular
Transannulation of 4-Methoxycyclohexa-2,5-dienone
Tethered 1-Sulfonyl-1,2,3-Triazoles: Synthesis of
Azaspiro[5.5]undecane Derivatives
Adv. Synth. Catal. Year, Volume, Page – Page
Cheng-Zhi Zhu, Yin Wei, Min Shi*
5
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