Visible-light photoredox-catalyzed dual C-C bond cleavage: Synthesis of 2-cyanoalkylsulfonylated 3,4-dihydronaphthalenes through the insertion of sulfur dioxide

Article abstract of DOI:10.1039/c9cc10057a

An efficient novel visible-light photoredox-catalyzed dual carbon-carbon bond cleavage of methylenecyclopropanes and cycloketone oximes for the synthesis of 2-cyanoalkylsulfonated 3,4-dihydronaphthalenes through the insertion of sulfur dioxide is established. This dual cleavage of carbon-carbon bonds involves a radical pathway and goes through a sequence of iminyl radical formation, carbon-carbon bond cleavage, sulfur dioxide insertion, sulfonyl radical addition, another carbon-carbon bond cleavage, and intramolecular cyclization.

Full text of DOI:10.1039/c9cc10057a

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Visible-Light Photoredox-Catalyzed Dual C-C Bond Cleavage:
Synthesis of 2-Cyanoalkylsulfonylated 3,4-Dihydronaphthalenes
through the Insertion of Sulfur Dioxide
Received 00th January 20xx,
Accepted 00th January 20xx
Yu Liu,* Qiao-Lin Wang, Zan Chen, Hua Li,* Bi-Quan Xiong, Pan-Liang Zhang and Ke-Wen Tang*
DOI: 10.1039/x0xx00000x
www.rsc.org/
An efficient novel visible-light photoredox-catalyzed dual carbon- organic moleculars.14-16 In 1991, Zard et al.14a developed the first
carbon bond cleavage of methylenecyclopropanes and radical carbon-carbon bond cleavage of cyclobutanone
cycloketone oximes for the synthesis of 2-cyanoalkylsulfonated sulphenylimines or carbonxymethyl oximes to prepare alkylnitriles.
3,4-dihydronaphthalenes through the insertion of sulfur dioxide is Afterwards, many organic chemists, such as Uemura,14b-c
established. This dual cleavage of carbon-carbon bonds reaction Selander,14d-e Xiao,14f-j Guo,15a-c Yu,15d-e Wu,15f-g Li’s groups15h and
involves a radical pathway and goes through a sequence of iminyl other groups16 have reported the similar ring-opening of
radical formation, carbon-carbon bond cleavage, sulfur dioxide cyclobutanone oximes derivatives. Most of these methods
insertion, sulfonyl radical addition, carbon-carbon bond cleavage, employed cyanoalkyl radicals, which came from ring-opening of
and intramolecular cyclization.
cyclobutanone oximes, to directly react with other reaction
partners. However, the methods, which used cyanoalkyl radicals to
16e-f
Sulfur-containing derivatives are important synthons in organic
synthesis and drug synthesis.1-2 Sulfones, a kind of useful
organosulfur derivatives, have already been widely used in chemical
industry, agrochemicals, pharmaceuticals, organic synthesis and
inflaming retarding materials.3-4 Due to the extensive application of
sulfones, the approaches for the construction of sulfones have
attracted organic chemists’ attention and many novel strategies
have been established.5-6 Among them, the insertion of sulfur
dioxide was the most convenient way for the synthesis of sulfones.
DABSO [DABCO·(SO2)2],7 sodium sulfites8a-c and thiourea dioxide8e-f
were usually used as sulfur dioxide sources to prepare sulfones.
Alkylnitriles were an important class of organic skeletons
encountered in many nitrile-containing pharmaceuticals and natural
products.9 Moreover, cyanoalkyl groups could easily be
transformed into other functional groups.10 Thus, the development
of efficient and convenient ways to access alkylnitriles has become
interesting. Typical strategies to synthesize alkylnitriles included
dehydrogenation of amines,11a-c dehydration of aldoximes11d-g or
amindes,12a-c cyanation of alkyl halides.12d-g Recently, the
functionalization of α-C-H bonds in inert alkylnitriles has also been
developed.13 The cleavage of carbon-carbon σ-bond in
cyclobutanone oximes has also emerged as a convenient route to
import cyanoalkyl groups, which bear longer aliphatic chains, into
capture SO2
and then formed sulfonyl radicals, were very few
(eq 1, Scheme 1).
MCPs (Methylenecyclopropanes) were usually used to react
with diverse free radicals,17 such as CF3,17a SCF3,17b alkyl,17c acyl,17d
α-carbonyl17e and sulfonyl17f-h-containing radicals. In the reaction
between MCPs and sulfonyl radicals, the sulfonyl radicals usually
came from sulfonyl chlorides and sodium sulfinates. However,
strategies for ring-opening and cyclization of MCPs with
cyanoalkylsulfonyl radicals, which formed from cyclobutanone
oximes and sulfur dioxide sources, are lacking.
Visible-light-catalysis, as a convenient and simple tool, is widely
used in organic synthesis because of its safety, mild reaction
conditions, availability, and high efficiency.18 Herein, we develop a
visible-light photoredox-catalyzed difunctionalization of carbon-
carbon σ-bond to construct 2-cyanopropylsulfonyl-substituted 3,4-
dihydronaphthalenes from MCPs, cyclobutanone oximes and K2S2O5,
which features the cleavage of two carbon-carbon σ-bonds and the
formation of one new carbon-carbon bond and two carbon-sulfur
bonds in one-pot (eq 2, Scheme 1).
O
O
R1
S
X
X
OR
O
S
O
CF3
CN
N
R2
R2
R1
R1
OR
1 R2
S
(1)
(2)
K
2S2O
5 (1.1 equiv)
Ir(ppy)3 (2 mol%),
R2
Ir(dtbbpy)(ppy)2PF6 (1 mol%)
DMF, white LED light, Ar, rt, 12 h
O
O
R
ROH
/MeCN = 3:1, 2 mL
N2, 15 W blue LED light, rt, 20 h
CN
ref.16e
ref. 16f
OR
Ru(bpy)3Cl2 (5 mol %)
K2S2
2,6-lutidine (3 equiv)
MeCN, 80 oC, 18 h, Ar
5 W blue LED light
N
O
5 (2 equiv)
R1
3
O
S
R
R4
R5
R2
+
CN
R1
R2
a. Department of Chemistry and Chemical Engineering, Hunan Institute of Science
and Technology, Yueyang 414006, China
E-mail: lyxtmj_613@163.com and tangkewen@sina.com
† Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
O
R3 R4
R5
Scheme 1. In situ SO2‑capture reactions of cycloketone oxime esters
We chose 1-(benzyloxy)-2-(cyclopropylidenemethyl)benzene 1a
and cyclobutylidenemethyl 4-(trifluoromethyl)benzoate 2a as
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model substrates to clarify the standard reaction conditions. To our of substituted cycloketone oxime esters 2 were examined in the
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surprise, the reaction employing Ru(bpy)3Cl2 as photocatalyst, presence of MCPs 1a under the standard DcOoIn:d10it.i1o0n3s9./CT9hCeCr1e0s0u5l7tAs
K2S2O5 as sulfur dioxide source, 2,6-lutidine as base, CH3CN as revealed that 3-substituted cyclobutanone oximes 2b-j bearing
solvent at 80 oC and irradiated by a 5 W blue LED light for 18 h could benzyl, benzyloxy, aryl and naphthalen-1-ylmethyl groups were all
afford the product 4-((8-(benzyloxy)-3,4-dihydronaphthalen-2- suitable substrates. The corresponding products 3ab-aj could be
yl)sulfonyl)butanenitrile 3aa in 81% yield. Various sulfur dioxide obtained in moderate yields. Employing 3,3-disubstituted
sources, cyclobutanone O-benzoyl oximes, photocatalysts, solvents, cyclobutanone oximes 1k and 1l in the reaction could provide the
visible-light sources, temperatures and reaction time were sulfonated product 3ak and 3al in 79% and 72% yields, respectively.
successively examined, and the optimized conditions were as The 2-substituted cycloketone oxime ester 2m was examined and
follows: 1-(benzyloxy)-2-(cyclopropylidenemethyl)benzene 1a (0.2 the target product 3am could be obtained in 69% yield. Then, our
mmol), cyclobutylidenemethyl 4-(trifluoromethyl)benzoate 2a (0.3 attention was turned to research the scope of MCPs 1 in the
mmol, 1.5 equiv), Ru(bpy)3Cl2 (0.01 mmol, 5 mol %), 2,6-lutidine presence of cycloketone oxime esters 2a, Ru(bpy)3Cl2, K2S2O5, 2,6-
(0.6 mmol, 3 equiv), K2S2O5 (0.4 mmol, 2 equiv), CH3CN (2 mL) at 80 lutidine and CH3CN. A variety of mono-substituted MCPs, which
oC and irradiated by a 5 W blue LED light for 18 h (See Table S1 in bearing one substituent at ortho-, meta- or para-position on the
Supporting Information, SI).
Table 1. Scope of cycloketone oxime esters (2) and MCPs (1)a
aryl ring, were examined. All of them could undergo the dual
carbon-carbon bond cleavage/sulfonylation reaction smoothly and
assembled the corresponding 2-cyanoalkylsulfonylated 3,4-
dihydronaphthalenes 3 in moderate yields (3aa-na). The reaction
yields indicated that both hindrance and electricity of the
substituents had obvious influence on the transformation: the
reactivity order is ortho- < meta- < para- and electron-withdrawing
< electron-donating. However, the meta-substituted MCP 1e gave
the product 3ea and 3ea’ (3 : 1) in 83% yield. Subsequently, di-
substituted MCPs 1o-r and poly-substituted MCP 1s were also
explored and all of them were suitable for this reaction (products
3oa-sa). Halogen substituted MCPs 1p-s were suitable for this
transformation, which provided opportunities for further
modification of the products (products 3pa-sa). Additionally,
phenyl-substituted MCP 1t was also good candidate for this
reaction. However, four-membered substrate 1u could not install
the target product 3ua. The substrate 1v, which connected a phenyl
group and a methyl, could react well with 2a to delivere the
sulfonylated product 3va in 72% yield. The naphthyl-substituted
MCP 1w could also delivere the product 3wa under the standard
conditions (product 3wa). Finally, a series of MCPs 1x-aa connecting
two aryl ring at the terminal of carbon-carbon double bond also
worked well and afforded the ring-opening and cyclization products
3xa-3aaa in good yields. However, 1-Cbz-3-azetidinone, oxetan-3-
one and cyclopentanone derived O-acyl oximes 2n, 2o and 2p could
not give the target products 3 under the standard conditions.
Ru(bpy)3Cl2 (5 mol %)
K2S2O
OR
N
R1
5 (2 equiv)
3
R4
O
S
R
2,6-lutidine (3 equiv)
MeCN, 80 oC, 18 h, Ar
5 W blue LED light
R2
R5
CN
+
R1
R2
O
R5
R3 R4
2, R = 4-CF3C6H4CO
3
1
t
3aa
3ab
R = H,
, 81%
3af
R = 4- BuC6H4,
, 85%
R = Bn,
R = OBn,
R = Ph,
, 80%
3ac
R
O
S
3ag
R = 4-FC6H4,
R = 4-ClC6H4,
R = 4-BrC6H4,
, 78%
, 76%
CN
3ah
, 71%
3ad
, 85%
O
OBn
3ai
, 67%
3ae
R = 4-MeC6H4,
, 82%
O
S
OPh
O
Ph
Ph
S
S
CN
CN
O
OBn
O
O
OBn
OBn
CN
3al
, 72%
3aj
, 71%
3ak
, 79%
R1 = OMe,
, 82%
O
S
3ba
O
S
O
R1 = Br,
, 75%
CN
3ca
CN
O
R1 = CN,
, 68%
OBn
3da
R1
OBn
Bn
3am
, 69%
OMe
O
S
BnO
CN
O
S
O
O
S
O
O
CN
CN
3ea
3ea'
3ea 3ea'
/
= 3 : 1, 83%
MeO
3fa
, 85%
R1
F
O
O
S
O
O
S
O
S
CN
MeO
CN
CN
O
Br
F
R1 = OBn,
3ga
, 86%
3pa
, 78%
3oa
, 80%
R1 = OMe,
3ha
, 89%
R1
=
Bu,
t
3ia
, 87%
R1 = Ph,
R1 = Cl,
, 86%
, 80%
Cl
3ja
O
S
O
3ka
O
S
O
R1 = CF3,
R1 = NO2,
, 78%
3ma
CN
3la
CN
CN
Br
, 75%
Br
R1 = CN,
, 74%
3na
3ra
, 75%
3qa
, 77%
To gain further understanding of the reaction mechanism, three
radical trapping experiments were carried out. The yields of MCPs
1a with cycloketone oxime esters 2a and K2S2O5 were very low
when these reactions were carried out by using TEMPO,
hydroquinone or 1,1-diphenylethene as radical inhibitors (eqs 1−3,
O
O
O
S
O
O
O
CN
CN
S
CN
S
O
, 70%
O
Br
3sa
3ta
3ua
, 0%
, 80%
R1
O
S
O
S
O
S
O
Scheme
tetramethylpiperidine-1-oxyl) in the transformation could afford 4-
((2,2,6,6-tetramethylpiperidin-1-yl)oxy)butanenitrile (eq 1,
2).
Additionally,
using
TEMPO
(2,2,6,6-
CN
CN
O
O
R2
3va
3wa
, 67%
, 72%
R1 = H, R2 = C6H5,
R1 = F, R2 = 4-FC6H4,
R1 = Cl, R2 = 4-ClC6H4,
R1 = Br, R2 = 4-BrC6H4,
, 84%
3xa
4
N
N
N
O
Boc
N
3ya
, 80%
3za
R
R
O
O
R
O
, 78%
3aaa
2p
2n
2o
Unsuccessful substrates
Scheme 2). The trapping product 4 could be detected by GC-MS.
Using 1,1-diphenylethene in the sulfonylation reaction could give
cyanoalkyl group-trapping product 6,6-diphenylhex-5-enenitrile 5
, 71%
a
Reaction conditions: 1 (0.2 mmol), 2a (0.3 mmol, 1.5 equiv),
K2S2O5 (0.4 mmol, 2 equiv), Ru(bpy)3Cl2 (5 mol %), 2,6-lutidine
(0.6 mmol, 3 equiv), CH3CN (2 mL) at 80 C under an argon
atmosphere and 5 W blue LED irradiation for 18 h. b most of the
and
cyanoalkylsulfonyl
group-trapping
product
4-((2,2-
o
diphenylvinyl)sulfonyl)butanenitrile 6 in 11% and 27% yields,
respectively (eq 3, Scheme 2). These experimental results suggested
that this transformation definitely contained a radical process.
Additionally, the cyano group could be transformed into a series of
other functional groups, such as carboxyl,14g,15b,16a amide group,16a
substrate 1 was decomposed.
Base on the optimal conditions, we initially investigated the
scope of MCPs 1 and cycloketone oxime esters 2 (Table 1). A series
2 | J. Name., 2012, 00, 1-3
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ester group,16a tetrazole.15b The cyano group in the sulfonylated pathway and goes through a sequence of iminyl radiVciaewl fAortricmleaOtniolinne,
product 3aa could be converted into ester group in the presence of C-C bond cleavage, sulfur dioxide insertion, DsuOlfI:o1n0y.1l0r3a9d/iCca9lCaCd1d00it5io7An,
ZnCl2 and n-butyl alcohol (eq 4, Scheme 2).
another C-C bond cleavage, and cyclization. Both the cyanoalkyl
radical and cyanoalkylsulfonyl radical were trapped by radical
inhibitors. The further research and application of this dual C-C
bond cleavage reaction are currently undergoing in our laboratory.
OR
N
(1)
O
N
standard conditions
TEMPO (3 equiv)
3aa
+
+
+
NC
OBn
1a
4%
R = 4-CF3C6H4CO
4, 21%, detected by GC-MS
2a
OR
Conflicts of interest
N
standard conditions
BHT (3 equiv)
O
S
(2)
(3)
CN
CN
There are no conflicts to declare.
O
R = 4-CF3C6H4CO
OBn
OBn
1a
2a
OR
3aa
, 5%
Ph
Acknowledgements
N
Ph
5
, 11%
standard conditions
1,1-diphenylethene (3 equiv)
We thank the Hunan Provincial Innovation Foundation For
Postgraduate (CX20190921), Natural Science Foundation of Hunan
Province (No. 2018JJ3208) and National Natural Science Foundation
of China (No. 21602056, 51874132 and 21805081) for financial
support.
+
3aa
+
O
OBn
1a
3%
Ph
Ph
S
CN
R = 4-CF3C6H4CO
O
2a
6
, 27%
O
O
ZnCl2 (1 equiv)
O
S
S
CN
nBuOH (2 mL)
120 oC, 16 h
(4)
OnBu
O
OBn
O
OBn
Notes and references
7
, 73%
3aa
1
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Scheme 2. Control experiments
According to the literature14-19 and above results, we proposed
the mechanism for the visible-light photoredox-catalyzed dual
cleavage of C-C bonds. Initially, [Ru(bpy)3]2+ was transformed into
[Ru(bpy)3]2+* photoexcited under the irradiation of visible-
light.17f,18c Subsequently, the reduction of cycloketone oxime 2a by
[Ru(bpy)3]2+* provided iminyl radical A, which underwent cleavage
of carbon-carbon bond to deliver cyanoalkyl radical B. Next, the
intermediate B trapped sulfur dioxide, which came from K2S2O5, to
give cyanoalkylsulfonyl radical C. Both the cyanoalkyl radical B and
cyanoalkylsulfonyl radical C could be trapped by 1,1-diphenylethene
to give products 5 and 6, respectively. Then, the addition of
cyanoalkylsulfonyl radical C to the carbon-carbon double bond in
substrate 1a afforded the radical D, which went through another
cleavage of carbon-carbon bond to install the radical E. The
intramolecular cyclization of the intermediate E assembled the
radical F. Finally, the radical F underwent SET by [Ru(bpy)3]3+ and
deprotonation by 2,6-lutidine to provide the target product 3aa,
and [Ru(bpy)3]3+ was reverted to ground-state [Ru(bpy)3]2+.
2
3
R
= 4-CF3C6H4CO
O
O
O
S
R
O
K2S2O5
N
N
S
O
1a
4
NC
NC
CN
B
C
OBn
K2SO3
2a
A
D
-
R
CO2
Ph
Ph
Ph
Ph
CN
CN
SET
O
S
[Ru(bpy)3]2+
*
6
5
[Ru(bpy)3]3+
Ph
Ph
O
O
Ph
Ph
O
hv
S
S
O
O
F
+
SET
H
CN
[Ru(bpy)3]2+
CN
-H
intramolecular cyclization
OBn
3aa
OBn
5
E
Scheme 3. Possible reaction mechanism
In summary, we have developed a facile and convenient route
to diverse 2-cyanoalkylsulfonated 3,4-dihydronaphthalenes via
visible-light photoredox-catalyzed dual C-C bond cleavage of
Methylenecyclopropanes and cycloketone oxime esters by the
insertion of sulfur dioxide. This reaction undergoes a radical
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6
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