Ruthenium(ii)-catalyzed intermolecular annulation of alkenyl sulfonamides with alkynes: Access to bicyclic sultams

Article abstract of DOI:10.1039/d0cc00093k

A ruthenium-catalyzed allylic C(sp³)-H activation strategy has been employed to develop an intermolecular coupling of alkenyl sulfonamides with alkynes. This protocol features the diastereoselective construction of [3.3.0] and [4.3.0] bicyclic sultams in one step.

Full text of DOI:10.1039/d0cc00093k

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COMMUNICATION
Ruthenium(II)-Catalyzed Intermolecular Annulation of Alkenyl Sul-
fonamides with Alkynes: Access to Bicyclic Sultams
Received 00th January 20xx,
Accepted 00th January 20xx
Lei-Lei Qian,a,b Xiang-Ting Min, Yan-Cheng Hu, Bing-Xue Shen, Sa-Na Yang,a,b Boshun Wan,a
a,b
a
a,b
a
and Qing-An Chen*
DOI: 10.1039/x0xx00000x
3
A ruthenium-catalyzed allylic C(sp )−H activation strategy has been employed to develop an intermolecular coupling of
alkenyl sulfonamides with alkynes. This protocol features the diastereoselective construction of [3.3.0] and [4.3.0] bicyclic
sultams in one step.
Introduction
Intramolecular Cyclization Strategies
a) Chiacchio's method: [3+2] annulation (Ref. 4b)
Bicyclic sultams are distributed in
pharmaceutical ingredients such as piroxicam, meloxicam,
hydrochlorothiazide and brinzolamide (Figure 1). As stable lactam
equivalents, these compounds could be used as anti-inflammatory,
antihypertensive, carbonic anhydrase inhibitor and so on.
a
variety of active
R1
R1
N
N
H
HO
Ph
N
R2

N
R2
1
,2
O
S
S
O2
O2
Ph
b) Tozer's method: [4+2] Diels-Alder annulation (Ref. 4c)
O2
1
O2
S
N
S

Furthermore, bicyclic sultams also serve as chiral auxiliaries in
R2
R2
N
3
R1
R1
organic synthesis. In this context, considerable efforts have been
dr 6:1
devoted to their synthesis over the past decades, including
c) Chemler's method: [4+2] annulation (Ref. 6c)
4
5
cycloaddition,
nucleophilic substitution,
electrophilic
6
7
8
9
Cu(I)
addition, Heck couplings, alkene metathesis, etc. However,
only limited methods are able to create core bicyclic framework in
Ar
H
Ar
N
N
S
S
O2
O2
4
b
4c,6c
one step. For example, intramolecular [3+2], [4+2],
and
d) Hanson's method: [2+2+1] annulation (Ref. 7d)
[
2+2+1]7 annulations have been demonstrated to construct
d
Co2(CO)8
N
R
O
N
R
bicyclic sultams (Scheme 1a-d).
S
S
O2
O2
OH
O
OH
O
N
H
N
This work: Intermolecular Cyclization Strategy
Forming Azabicycles in One Step
Cl
e)
N
N
N
S
H
H
O
S
NH
N
N
Ph
Ph
Ph
S
O O
S
Me
S
Me
H2N
( )n
SO2
N
O
O
O
Ru(II)
O
O
+
SO2NH2
(
)n
Ph
Piroxicam
Meloxicam
Hydrochlorothiazide
[O]
H
NHEt
O
O
Ru-Catalyzed Intermolecular coupling of alkenyl sulfonamides with alkyne
OMe
NH
H2NO2S
N
NH
SO2
N
S
S
O
S
Scheme 1. General strategies for constructing bicyclic sultams
O
O
O
in one step.
Brinzolamide
Supidimide
Camphorsultam
Transition-metal-catalyzed direct C−H annulations with
nitrogen atom is arguably one of the most efficient strategy to
Figure 1. Representative bicyclic sultams.
Despite these advances, from the viewpoint of step- and access N-heterocycles.10 For example, intramolecular
atom-economy, it would be highly demanded to develop an allylic/benzylic C−H aminations of unsaturated sulfamate
1
1
12
intermolecular annulation to elaborate bicyclic sultams. To the esters and N-sulfonamides have been well studied. Notably,
best of our knowledge, the bimolecular assembly of such Rovis and co-workers disclosed
Rh(III)-catalyzed
intermolecular annulation of N-alkenyl sulfonamides with
a
important motif still remains underexploited.
1
3
alkynes for the synthesis of azabicycles. Inspired by these
1
3,14
precedents
and our continuing interests in developing new
we envisioned that alkenyl sulfonamides
1
5
annulations,
a. Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023,
China, E-mail: qachen@dicp.ac.cn, Homepage: http://www.lbcs.dicp.ac.cn
possibly could undergo allylic C−H activation and alkyne
insertion to yield bicyclic sultams under ruthenium catalysis
Scheme 1e).
b.
University of Chinese Academy of Sciences, 100049, Beijing, China
Electronic
Supplementary
Information
(ESI)
available:
See
(
DOI: 10.1039/x0xx00000x
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including -F, -Cl, and -Br were all well tolerated, affording the
corresponding products in 69-81% yields (3ca-3ea).
Trifluoromethoxy derived alkyne was readily transformed into
View Article Online
DOI: 10.1039/D0CC00093K
Initially, 1,2-diphenylethyne (1a) and but-3-ene-1-
sulfonamide (2a) were selected as model substrates to test our
hypothesis (Table 1). The expected annulation of 1a and 2a
3
fa in 56% yield. Electron-withdrawing substituents such as -
CO Et (3ga) and CF (3ha) were compatible with the process,
2
3
indeed occurred using [Ru(p-cymene)Cl
and Cu(OAc) ·H O as oxidant, albeit with a low yield of 3aa
entry 1). The relative stereochemistry of 3aa was
2 2
] as catalyst precursor
albeit with slightly decreased yields. Remarkably, bulky 2-
naphthyl alkyne was also a suitable substrate. The process
could be further extended to various meta-substituted alkynes,
and the electronic properties of the substituents had minimal
influence on the reaction (3ja-3ma). The annulation of 2-F
derived alkyne with 2a led to the desired bicyclic sultam 3na in
a relatively low yield, which was presumably ascribed to the
steric hindrance.
2
2
(
1
6
unequivocally determined by X-ray diffraction analysis.
A
screening of the solvents and temperature indicated that the
best result was obtained when the reaction was conducted in
o
DCE at 80 C (entries 2-10). Moreover, the influences of base
and acid additives were surveyed.
additive resulted in an apparent improvement on the reactivity
entries 11-13). Gratifyingly, the yield of 3aa was further
The employment of HOAc as
(
Table 2. Construction of [3.3.0] azabicyclic sultamsa
enhanced to 74% upon increasing the catalyst loading and the
amount of 1a (entries 14-15).
[Ru(p-cymene)Cl2]2 (10 mol%)
Ar
AgSbF6 (50 mol%)
Ar
Ar
+
SO2NH2
Ar
SO2
Cu(OAc)2 H2O (2.0 equiv.)
HOAc (1.0 equiv.), DCE, 80 o
N
Table 1. Optimization of the reaction conditionsa
C
H
3
1
2a
Me
[
Ru(p-cymene)Cl2]2
AgSbF6
Ph
Ph
Ph
+
SO2NH2
Ph
SO2
Cu(OAc)2 H2O
Additive
N
SO2
H
Me
SO2
1a
2a
3aa
N
H
N
H
3aa: 66%
X ray of 3aa
3ba: 58%
o
Yield (%)b
Entry
Solvent
T ( C)
120
120
120
120
120
140
100
80
Additive
None
None
None
None
None
None
None
None
None
None
F
Cl
Br
1
2
3
4
5
6
7
8
9
Dioxane
PhCl
7
8
F
SO2
Cl
SO2
Br
SO2
N
N
H
N
H
H
DCE
18
5
3ca: 81%
3da: 81%
3ea: 69%
F3CO
EtO2C
F3C
2
Et O
DMSO
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
NR.
5
F3CO
SO2 EtO2C
SO2 F3C
SO2
N
N
N
H
H
H
3
fa: 56%
3ga: 32%
3ha: 26%
24
30
27
21
16
30
42
60
74
Me
F
60
SO2
SO2
SO2
N
H
N
N
H
H
F
Me
1
1
1
1
0
1
2
3
40
3ia: 60%
3ja: 43%
3ka: 48%
Cl
Br
80
2 3
K CO
F
80
PivOH
HOAc
HOAc
HOAc
SO2
SO2
SO2
N
N
N
80
H
H
H
Cl
Br
F
3
la: 45%
3ma: 47%
3na: 20%
1
4c
80
aReaction conditions: 1 (0.30 mmol), 2a (0.60 mmol), [Ru(p-
cymene)Cl
0.60 mmol), HOAc (0.30 mmol), 80 C, 16 h.
5c,d
2 2 6 2 2
] (0.03 mmol), AgSbF (0.15 mmol), Cu(OAc) ·H O
1
80
o
(
aConditions: 1a (0.10 mmol), 2a (0.10 mmol), [Ru(p-cymene)Cl
]
2 2
(
0.005 mmol), AgSbF
6
(0.025 mmol), Cu(OAc)
2
·H
2
O (0.20 mmol),
When alkenyl sulfonamide 2b with longer carbon chain was
b
additive (0.10 mmol), solvent (2 mL), 16 h; Determined by HPLC with employed as substrate, the annulation could proceed
c
naphthalene as internal standard; [Ru(p-cymene)Cl
2
]
2
(0.01 mmol), efficiently to deliver [4.3.0] azabicyclic sultam 3ab in 53% yield
d
AgSbF
6
(0.05 mmol), DCE (4 mL); 1a (0.20 mmol).
(
Table 3). The halide substituents, regardless of their positions,
were all amenable to the protocol (3bb, 3cb, 3fb, 3gb), and
even 2-F substituted alkyne also led to product 3hb in an
acceptable yield (53%). In the cases of electron-donating 4-Me
and electron-withdrawing 4-CO Et derived alkynes, the
2
reactions afforded the corresponding sultams (3db, 3eb) in
With the optimal reaction conditions established, we
subsequently explored the substrate generality (Table 2).
Alkyne 1b bearing electron-donating (4-Me) substituent on
phenyl ring reacted with homoallylic sulfonamide 2a smoothly
to furnish bicyclic sultam 3ba in 58% yield. The halide groups
2
| J. Name., 2012, 00, 1-3
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4
6% and 38% yield, respectively. Treatment of 2-naphthyl equilibrium with intermediate E. Side-product 4aa (Eq. 1) could
View Article Online
DOI: 10.1039/D0CC00093K
alkyne with standard conditions resulted in the formation of be obtained via an enhanced protodemetalation of ruthenium
3
1
7
ib in a moderated yield (51%).
complex C or D. A 4π-conrotatory electro-cyclization of E
yields a five-membered π-allyl ruthenium G via model F1. The
high diastereoselectivity can be rationalized from the
requirements of the Woodward–Hoffmann rules (Disrotatory
model F2 is disfavored). Intermediate G undergoes ligand
exchange and reductive elimination to produce bicyclic sultam
Table 3. Construction of [4.3.0] azabicyclic sultamsa
[
Ru(p-cymene)Cl2]2 (15 mol%)
AgSbF6 (75 mol%)
Ar
SO2NH2
Ar
Ar
+
Ar
Cu(OAc)2 H2O (2.0 equiv.)
SO2
SO2
SO2
N
TFA (1.0 equiv.), DCE, 80 o
C
1
2b
3 H
3
aa. The resulting Ru(0) species is ultimately oxidized by
Cu(OAc) to regenerate the Ru(II) catalyst. In the presence of
excess oxidant Cu(OAc) , cyclometallated ruthenium complex
aa (Eq. 2) could be generated from intermediate H through
Br
Cl
2
2
5
SO2
Br
Cl
N
SO2
H
N
N
H
oxidation and subsequent 1,3-Ru shift. Therefore, the
observation of Ru complex 5aa supports the proposed
mechanism.
H
3
ab: 53%
3bb: 63%
3cb: 61%
Me
EtO2C
F
II
3aa
H
Ru OAc
Ru
NH
[Ru0]
Me
EtO2C
F
SO2
SO2
Ph
SO2
Ph
2
SO NH2
N
N
N
H
H
H
CuII
H
3
db: 46%
3eb: 38%
3fb: 53%
H
Ph
Ph
Ph
G
H
Br
CuI
Ph
Ph
Ru
Ph
Ru
F
Br
RuIIOAc
Ph
II
[
Ru (OAc)2]
A
L
L
E
SO2NH2
SO2
SO2
Ph
N
N
SO2
1a
SO2NH2
F1: conrotatory
SO2NH2
F2: disrotatory
H
F
H
N
H
3
gb: 52%
3hb: 48%
3ib: 51%
(favored)
(disfavored)
aReaction conditions: 1 (0.30 mmol), 2b (0.60 mmol), [Ru(p-
cymene)Cl (0.045 mmol), AgSbF (0.225 mmol),
Cu(OAc) ·H O (0.60 mmol), TFA (0.30 mmol), 80 C, 16 h.
HOAc
Ru-OAc
OAc
Ru
OAc
Ru
Ph
Ph
2
]
2
2
6
Ph
Ph
2a
SO2NH2
o
SO2NH2
SO2NH2
2
H
B
C
D
In order to isolate some potential reaction intermediates for
proposed mechanism, HOAc was used as solvent to promote
the protodemetalation (Eq. 1). Besides sultam 3aa, the control
experiment also generated a skipped diene 4aa as side-
product which was not observed under the standard
conditions. These results revealed that a migratory insertion of
alkyne 1a into π-allyl ruthenium complex is probably involved
in the process. An interestingly cyclometallated ruthenium
complex 5aa was isolated when increase the loading of
Scheme 2. Proposed mechanism.
Conclusions
In conclusion, we have successfully developed a direct
synthesis of bicyclic sultams via ruthenium-catalyzed
intermolecular coupling of alkenyl sulfonamides with alkynes,
involving
reactions/amination progress. The high diastereoselectivity for
3.3.0] and [4.3.0] bicyclic sultams resulted from steric factors
a
ruthenium(II)-catalyzed tandem cyclization
2 2
ruthenium precursor [Ru(p-cymene)Cl ] (Eq. 2). This Ru
[
1
13
1
complex has been fully characterized by H NMR, C NMR, H-
during 4π-conrotatory electrocyclization. The alkenyl
sulfonamide acted as a ternary-composition for cycloaddition
with alkynes in this protocol. Further studies on the biological
activity of these bicyclic sultams are ongoing in our laboratory.
1
3
1
13
C HMQC, H- C HMBC and HRMS (See Supporting
Information).
Ph
Ph
Ph
[
Ru(p-cymene)Cl2]2 (10 mol%)
AgSbF6 (50 mol%)
Ph
Ph
1a (0.3 mmol)
SO2
+
SO2
Ph
+
NH2 (1)
Cu(OAc)2 H2O (2.0 equiv.)
N
Conflicts of interest
There are no conflicts to declare.
H
SO2NH2
a (0.6 mmol)
HOAc (2 mL), 80 o
C
2
3aa: 26%
4aa: 15%
Ph
Ph
SO2
[
Ru(p-cymene)Cl2]2 (50 mol%)
AgSbF6 (250 mol%)
Acknowledgements
Financial support from Dalian Institute of Chemical Physics, the
National Natural Science Foundation of China (21572225,
1a (0.3 mmol)
NH
Ru
+
Ph Ph
(2)
Cu(OAc)2 H2O (4.0 equiv.)
SO2NH2
a (0.6 mmol)
DCE (8 mL), 80 o
C
2
5aa: 10% yield
2
1702204, 21772194), Liaoning Revitalization Talents Program
On the basis of these observations and previous report,13
a
(XLYC1807181), and the "Thousand Youth Talents Plan" is
plausible mechanism was shown in Scheme 2. First, allylic acknowledged.
3
C(sp )−H bond of 2a is activated by an in-situ formed cationic
Notes and references
Ru(II) catalyst, generating a π-allyl ruthenium complex B.
Subsequent a migratory insertion of alkyne 1a into ruthenium
complex B gives vinyl Ru(II) C. A vinyl-to-allyl 1,3-Ru shift of
intermediate C furnishes the bis(allyl)ruthenium species D in
1
For selected reviews on sultams, see: (a) A. Scozzafava, T.
Owa, A. Mastrolorenzo, C. T. Supuran, Curr. Med. Chem.,
2
003, 10, 925; b) M. Feng, B. Tang, S. H. Liang, X. Jiang, Curr.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
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4
| J. Name., 2012, 00, 1-3
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Journal Name
COMMUNICATION
Graphical Abstracts (Table of Contents Entry)
View Article Online
DOI: 10.1039/D0CC00093K
Ar2
Ru cat.
( ) n
SO2
Ar1
Ar2
+
SO2NH2
)n
Ar1
(
Cu(OAc)2
N
n = 1, 2
H
High diastereoselective formation two cycles and three new bonds in one step
A ruthenium-catalyzed allylic C(sp3)−H activation strategy
has been employed to develop an intermolecular coupling of
alkenyl sulfonamides with alkynes. This protocol features the
diastereoselective construction of [3.3.0] and [4.3.0] bicyclic
sultams in one step.
This journal is © The Royal Society of Chemistry 20xx
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