Dual gold and photoredox catalysis: visible light-mediated intermolecular atom transfer thiosulfonylation of alkenes

Article abstract of DOI:10.1039/C6SC05093J

Regioselective difunctionalization of alkenes has attracted significant attention from synthetic chemists and has the advantage of introducing diverse functional groups into vicinal carbons of common alkene moieties in a single operation. Herein, we report an unprecedented intermolecular atom transfer thiosulfonylation reaction of alkenes by combining gold catalysis and visible-light photoredox catalysis. A trifluoromethylthio group (SCF₃) and other functionalized thio groups together with a sulfonyl group were regioselectively introduced into alkenes in the most atom economical manner. A detailed mechanism study indicated that a synergistic combination of gold catalysis and photoredox catalysis is crucial for this reaction.

Full text of DOI:10.1039/C6SC05093J

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Dual gold and photoredox catalysis: Visible light-mediated
intermolecular atom transfer thiosulfonylation of alkenes
Haoyu Li,a Cuicui Shan,a Chen-Ho Tunga and Zhenghu Xua,b
Received 00th January 20xx,
Accepted 00th January 20xx
Regioselective difunctionalization of alkenes has attracted tremendous attentions from synthetic chemists, which has the
advantage of introducing diverse functional groups onto vicinal carbons of common alkene moieties in a single operation.
Herein, we report an unprecedented intermolecular atom transfer thiosulfonylation reaction of alkenes by combining gold
catalysis and visible-light photoredox catalysis together. A trifluoromethylthio group (SCF3) and other functionalized thio
groups together with sulfonyl group were regioselectively introduced into alkenes in the most atom economic manner. A
detailed mechanism study indicated that a synergistic combination of gold catalysis and photoredox catalysis is crucial for
this reaction.
DOI: 10.1039/x0xx00000x
www.rsc.org/
incorporation of SCF3 group into pharmaceuticals could greatly
improve their ability to cross lipid membranes.5 Because of this,
the introduction of an SCF3 group into small molecules has
Introduction
Regioselective difunctionalization of alkenes has the advantage
of introducing diverse functional groups onto vicinal carbons
of common alkene moieties in a single operation and has
attracted much attention from synthetic chemists.1 Of the
many catalytic processes that have been developed, a majority
require stoichiometric amounts of an external strong oxidant,
such as PhI(OAc)2, Selectfluor (eqn (1))2 and are typically
attracted much attention in synthetic chemistry.6,7 Current
methods for the construction of C-SCF3 bond involve
electrophilic trifluoromethylthio reagents6 or the nucleophilic
AgSCF3 reagent7. Sulfonyl groups are similar in molecular size
and charge distribution to carboxyl or phosphate groups, and
the sulfonyl group has been introduced into bioactive
molecules to improve their activity.8 A sulfonyl group has two
receptors for hydrogen bonds and this can enhance the
binding affinities of drug molecules with target proteins.
Sulfones can be easily transformed into other functional
groups, such as alkenes, through Julia olefination.9 We
questioned whether both SCF3 and sulfonyl groups could be
introduced simultaneously into organic compounds in a single
step. Such a transformation has not been described to date.
This report describes a dual gold and photoredox catalytic
initiated by
a transition metal-catalyzed intramolecular
addition. Fully intermolecular difunctionalization of alkenes is
more challenging, because of the regiochemical issue (eqn (2)).
Recently Stevenson developed elegant visible light-mediated
atom transfer radical addition reactions converting
haloalkanes and α-halocarbonyl compounds to alkenes.3 Such
neutral redox reactions are very attractive, because they are
atom-economic and require no additional oxidants.
approach
thiosulfonylation of alkenes.
combination of visible light-mediated photoredox
to
the
intermolecular
atom
transfer
A
catalysis10 and transition-metal-catalysis is possible to bring
two distinctive catalytic systems together and achieve
unprecedented new reactions.11 Recently, the use of gold(I)
The trifluoromethylthio (SCF3) group is a key structural unit in
many pharmaceutical and agrochemical products, such as
tiflorex, toltrazuril and vaniliprole.4 It is well known that SCF3
groups induce in a molecule even higher lipophilicity than
complexes in photoredox catalysis has gained considerable
attention.12,
13
This photoredox catalytic cycle triggers the
conversion of Au(I) to Au(III) under mild conditions - a
conversion which previously had only been achieved with
stoichiometric quantities of strong oxidants.14 In 2013, Glorius
reported a first dual gold and photo-redox catalyzed reaction,
which achieved intramolecular oxy- and aminoarylation of
alkenes with aryldiazonium salts (Scheme 1A).12b Toste et al.
took advantage of the visible light-mediated Au(I)/Au(III) cycle
to produce arylative ring expansion reactions and carbon-
phosphorus cross-coupling reactions (Scheme 1B).12d,e This
trifluoromethyl
substituents
and
consequently
the
a.Key Lab for Colloid and Interface Chemistry of Education Ministry, School of
chemistry and Chemical Engineering, Shandong University, Jinan 250100, People’s
Republic of China. E-mail: xuzh@sdu.edu.cn
b.State Key Laboratory of Organometallic Chemistry Shanghai Institute of Organic
Chemistry, Chinese Academy of Sciences Shanghai 200032, PR China..
† Electronic Supplementary Information (ESI) available: CCDC Number: 1494115 for
3n and 1494114 for 3s. See DOI: 10.1039/000000x/
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Table 1. Optimization of reaction conditionsa
visible light-mediated single electron oxidative reaction has
been utilized to access gold(III) complexes from gold(I)
species.12k Recently Hashmi reported an aryldiazonium salts
mediated Au(I) to Au (III) transformation upon irradiation with
blue LED in the absence of a photosensitizer12q
. In all these
reactions,12 the same aryldiazonium salts were used. The
development of new gold/photoredox catalysis mode is highly
desirable. To achieve the proposed trifluoromethyl-
thiosulfonylation reaction in the most atom-economic manner,
a difunctionalization reagent PhSO2SCF3 (2a) is required. This
can be easily prepared from PhSO2Na and AgSCF3 (For details,
see supporting information (SI)). We envisioned that the
reaction of PhSO2SCF3 with a cationic gold catalyst in the
presence of a photocatalyst would generate an LAuSCF3
species and a benzenesulfonyl radical, which can then add to
the alkene forming a new alkyl radical.3a This radical may
oxidize LAuSCF3 to an Au(II) intermediate, which is further
oxidized to an Au(III) derivative by the RuIII catalyst.
Subsequent reductive elimination forms the target difunctional
product, regenerating the Au(I) catalyst (Scheme 1C). This
Entry
Variation from the “standard” conditions
Yield (%)b
1
2
None
AuCl instead of IPrAuCl
94 (87)
0.
3
PPh3AuCl instead of IPrAuCl
IMesAuCl instead of IPrAuCl
PPh3AuNTf2 instead of IPrAuCl and AgSbF6
IPrAuSbF6 instead of IPrAuCl and AgSbF6
CH3CN instead of DCE
56
72
67
88
5
4
5
6b
7
8
CH3OH instead of DCE
4
9
Ru(phen)3Cl2 instead of Ru(bpy)3Cl2
Ir[dF(CF3)ppy]2(dtbbpy)PF6
67
0
10
11
12
fac-Ir(ppy)3 instead of Ru(bpy)3Cl2
IPrAuCl (5 mol%), AgSbF6 (7.5 mol%), Ru(bpy)3Cl2 (1.2
mol%)
0
64
a
Reaction conditions: a mixture of 1a (0.4 mmol), 2a (0.2 mmol), IPrAuCl (10
mol%), AgSbF6 (15 mol%), Ru(bpy)3Cl2 (2.5 mol%), in DCE (1 mL) was stirred at rt
reaction provided
a
new approach to introduce
b
under irradiation with a 100 w blue LED at N2 atmosphere. Ru(bpy)3(PF6)2
trifluoromethylthio (SCF3) group at the α position of styrenes.
C
instead of Ru(bpy)3Cl2. Determined by 19F NMR using (trifluoromethyl)benzene
as the internal standard. The number in parentheses is the isolated yield. IPr =
1,3-bis(2,6-diisopropyl-phenyl)imidazol-2-ylidene, ppy = 2-phenylpyridine.
and visible light irradiation are all necessary for the reaction
(Table S2, entries 2-5). In the absence of silver salt, the
reaction led to a dramatic decrease of yields (NMR yields <
5%), showing that the formation of a cationic gold species is
highly important (Table S2, entry 4). Other gold catalysts such
as AuCl, Ph3PAuCl and Gagosz catalyst (Ph3PAuNTf2) are all less
effective than IPrAuCl (entries 2-5). Silver free system using
IPrAuSbF6 and Ru(bpy)3(PF6)2 led to slightly lower 88% yield
(entry 6), so silver is not necessary in this reaction. Reactions in
other solvents such as acetonitrile and methanol led to only
traces of products, and no solvent addition products,
indicating that a carbocation mechanism is not involved
(entries 7, 8). Other iridium photocatalysts including
Ir[dF(CF3)ppy]2(dtbbpy)PF6 and fac-Ir(ppy)3 were also tested, no
product was observed in the reaction system (entries 10-11).
Trying to lower catalysts loading also led to a lower reaction
yield (entry 12).
Scheme 1. Dual gold and photoredox catalytic reactions
With these optimized conditions established, the scope of
the dual gold and visible light-mediated alkene
difunctionalization reaction was explored. As summarized in
table 2, a wide range of styrene type alkenes were applicable
and moderate to good isolated yields of product were
Results and discussion
To validate this concept, styrene (1a), and PhSO2SCF3 (2a) were
selected as model substrates to test the feasibility of this
hypothesis. After
a detailed optimization of reaction
conditions, the proposed alkene trifluoromethylthio-
sulfonylation product (3a) was achieved in 94% yield using the
standard conditions: a mixture of IPrAuCl (10 mol%), AgSbF6
(15 mol%), Ru(bpy)3Cl2 (2.5 mol%) in DCE (1mL) was stirred
under irradiation for 1-3 hrs with 100 w blue LED in a N2
atmosphere (Table 1, entry 1). The dual catalytic nature of this
reaction was investigated by control experiments, which
confirmed that the gold catalyst, the Ru(II) photosensitizer,
achieved
(3a-3l). Substrates bearing different electron-
withdrawing or electron-donating groups at different positions
in the aromatic ring were all compatible with this reaction. A
series of functional groups such as ester, cyano,
trifluoromethyl, halogen were all well tolerated under the
reaction conditions. In particular, the alkene 1m, containing an
alkyne moiety, was also applicable to this reaction giving the
corresponding alkene difunctionalized product
(3m) in
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Table 3. Substrate scope of alkene thiosulfonylation reactionsa
moderate yield. Notably, dienes such as isoprene were also
amenable to this transformation, giving as the major product
in 55% yield, the 1,4-addition product (3n), whose structure
was confirmed by single X-ray analysis.
Ru(bpy)3Cl2 (2.5 mol%)
IPrAuCl (10 mol%)
AgSbF6 (15 mol%)
SR'
SO2Ph
R
+
PhSO2SR'
R
DCE, rt, N2
visible light
1
2
Table 2. Substrate scope of alkene trifluoromethylthiosulfonylation reactionsa
Alkene scope:
SC4H9
SO2Ph
SC4H9
SO2Ph
SC4H9
SC4H9
R
PhO2S
PhO2S
Ru(bpy)3Cl2 (2.5 mol%)
SCF3
R
IPrAuCl (10 mol%)
AgSbF6 (15 mol%)
4m, 51%
4n, 55%
SO2Ph
4i, R = Br, 57%
4j, R = Me, 70%
4a, R = H, 84%
+
PhSO2SCF3
R
R
4b, R = CN, 71%
DCE, rt, N2
visible light
4k, R = OMe, 41%
4c, R = COOMe, 40%
4d, R = CF3, 48%
1a
2a
3a
SC4H9
SO2Ph
SC4H9
4e, R = Br, 66%
4f, R = F, 68%
SCF3
SCF3
SCF3
SO2Ph
SO2Ph
R
SO2Ph
4g, R = Me, 60%
4h, R = OAc, 52%
Cl
SO2Ph
R
3m, 31%
4l, 71%
4o, 45%b (d.r.>20:1)
48%c (d.r.>20:1)
SC4H9
3i, R = Br, 69%
3j, R = Me, 86%
3a, R = H, 87%
3b, R = CN, 69%%
3c, R = COOMe, 76%
SC4H9
SC4H9
SO2Ph
3k, R = OMe, 76%
SO2Ph
3d, R = CF3, 67%
3e, R = Br, 90%
3f, R = F, 77%
SCF3
SO2Ph
Br
SO2Ph
SCF3
4p, 51%d
PhO2S
4q, 57%
(d.r.>20:1)
4r, 56%
(d.r.=14:1)
3g, R = Me, 63%
Cl
(d.r.=12:1)
3n, 55%
SCF3
3h, R = OAc, 70%
3l, 72%
SCF3
Scope of PhSO2SR
SCF3
SMe
SBn
SPh
SO2Ph
SO2Ph
SO2Ph
SO2Ph
SO2Ph
SO2Ph
Br
3o, 67%b (d.r.=9:1)
61%c (d.r.=9:1)
3q, 63%
(d.r.>20:1)
3p, 65%d
5a, 90%
5b, 66%
5c, 92%
(d.r.=7:1)
Me
Br
F3CS
SCF3
SO2Ph
SO2Ph
S
CO2Et
SO2Ph
S
S
SO2Ph
SO2Ph
3r, 56%
3s, 52%
(d.r.=10:1)
(d.r.=9:1)
5d, 84%
H9C4S
5e, 65%
5f, 53%
a
O
S
Standard conditions were employed. Isolated yields were reported.
H9C4S
O
S
O
O
Diastereoselectivities were determined by GC-Mass. b from (E)-alkene. c from (Z)-
alkene. d from (Z)-alkene : (E)-alkene = 7 : 3.
Cl
5g, 72%
5h, 56%
Internal alkenes, including acyclic and cyclic alkenes were
also suitable substrates. Most of the reactions exhibited
excellent diastereoselectivities. Interestingly, trans-alkenes
and cis-alkenes afforded the same major products (4o) in
a
Standard conditions were employed. Isolated yields were reported.
Diastereoselectivities were determined by GC-Mass. b from (E)-alkene. c from (Z)-
alkene. d from (Z)-alkene : (E)-alkene = 7 : 3.
similar yields with similar diastereoselectivities
，which is very
products in good yields (4a-4r). A large variety of alkyl and
important feature and also advantage of this reaction. The
relative configuration of the seven-membered product 3s was
unambiguously characterized by single X-ray crystallography.
However, the reactions of aliphatic alkenes were unsuccessful
under the same conditions.
aromatic thio groups can be easily introduced into a styrene
molecule, giving difunctional products generally in very good
yields (5a-5h).
The sulfonyl group (-SO2-) is a useful synthon for further
transformations. For instance, the reaction of compound 4a
with TMSCN or allylsilane in the presence of aluminum
Organosulfur compounds are ubiquitous in the
pharmaceutical industry, material science, and food
chemistry.15 The construction of C-S bonds is important but
also challenging,16 because a sulfur atom could coordinate
with metal catalysts such as Au leading to catalyst inactivation.
When we applied the above dual catalysis system to the
general thiosulfonylation reaction of alkenes using PhSO2SC4H9
chloride provided the sulfur migration substitution products
6
and 7 in good yields (eqn (3, 4)). This reaction might go
through a neighboring group participating SN1 type of reaction.
(−1.64 V, vs SCE) as the reagent, which might be more
challening because of its lower oxidative potential comparing
with PhSO2SCF3 (−1.11 V, vs SCE, Figure S5, SI), to our delight,
the reactions were very successful (Table 3). Various alkenes
including styrenes, internal alkenes and dienes all enter into
this thiosulfonylation reaction giving the corresponding
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Control experiments were conducted to explore the out (Figure S3). Upon laser excitation by 355 nm light, the
mechanism of this reaction. The reaction of 1,1- ground state absorption at 450 nm was obviously bleached
diphenylethylene under standard conditions, vinyl sulfone and characteristic absorption band at 360 nm was
10) was isolated in 86% isolated yield (scheme 2b). These detected. This is ascribed to the reductive state of bipyridine in
∼
9
a
∼
(
results clearly indicate formation of the benzenesulfonyl Ru(bpy)3(SbF6)2 (Figure S4-a, SI).18 When PhSO2SCF3 was
radical in the reaction system. The 19F NMR spectrum of the introduced into a solution of Ru(bpy)3(SbF6)2, the transient
crude mixture from the reaction contained an additional signal absorption spectra made almost no difference (Figure S4-b.
at -26 ppm, which was later determined to be from IPrAuSCF3 SI). The lifetime of the excited state of Ru(bpy)3(SbF6)2 slightly
(
8
). This compound could be independently synthesized by the decreased from 493 to 473 ns from the kinetics probed at 450
reaction of IPrAuCl and AgSCF3, which is sufficiently stable to nm. However, when IPrAuSbF6 was added into a solution of
be isolated by column chromatography (Scheme 2a). Ru(bpy)3(SbF6)2, a new absorption appeared at 530 nm. This
stoichiometric reaction between IPrAuCl, 2a and the radical is characteristic of gold nanoparticles. At the same time, the
scavenger ( ) afforded vinyl sulfone (10) in 81% isolated yield lifetime of the excited state of Ru(bpy)3(SbF6)2 decreased from
and in 32% yield (Scheme 2c). This benzenesulfonyl radical 493 to 394 ns (Figure S4-c. SI). All these results suggested that
could also be generated by PhSO2Cl (11) in the presence of the electron transfer between IPrAuSbF6 and the excited
visible light,3a and the reaction between 11, and 2a afforded 3MLCT state of Ru(bpy)3(SbF6)2 occurred, giving the active
A
∼
9
8
8,
the target product (3a) in 98% yield (Scheme 2d). In contrast, IPrAu(0) species which might aggregate to form gold
without this gold intermediate, the direct atom transfer radical nanoparticles19. The reductive IPrAu(0) catalyst formed in situ
addition adduct 12 was obtained in 81% yield (Scheme 2e). is highly reactive20 and might react with PhSO2SCF3 providing
This experiment demonstrated that IPrAuSCF3 is the possible IPrAuSCF3 (
reaction intermediate.17
8) and a benzenesulfonyl radical.
a)
b)
CH3CN
AgSCF3
IPrAuCl
IPrAuSCF3
8, 90%
Ru(bpy)3Cl2 (2.5 mol%)
IPrAuCl (10 mol%)
AgSbF6 (15 mol%)
Ph
Ph
SO2Ph
Ph
+
PhSO2SCF3
Ph
10
9
2a
(1 equiv)
DCE, rt, N2
visible light
86 %
(2 equiv)
Ru(bpy)3Cl2 (10 mol%)
AgSbF6 (1 equiv)
c)
d)
Ph
Ph
Ph
Ph
SO2Ph
IPrAuCl
PhSO2SCF3
+
+
IPrAuSCF3
visible light, N2, DCE
9
2a
(1 equiv)
10
8
32
(1 equiv)
(1 equiv)
81 %
SCF3
Ru(bpy)3Cl2 (2.5 mol%)
visible light, N2, DCE
Ph
PhSO2Cl
+
IPrAuSCF3
+
+
SO2Ph
Scheme 3. Proposed mechanism
Ph
8
11
2a
(2 equiv)
3a
On the basis of the above results and previous reports,12
a
98 %
(1.2 equiv)
(1 equiv)
e)
tentative proposed mechanism is shown in Scheme 3.
2+
Cl
Ru(bpy)3Cl2 (2.5 mol%)
visible light, N2, DCE
Ph
PhSO2Cl
SO2Ph
Irradiation of Ru(bpy)3 generates a long-lived photoexcited
state Ru (bpy)32+*, which undergoes an single-electron transfer
Ph
11
2a
12
81 %
reaction with cationic IPrAu(I) to initiate the catalytic cycle and
3+
provide Ru(bpy)3 and the highly active IPrAu(0) which can
Scheme 2. Control experiments
reduce PhSO2SCF3 to form IPrAu(I)SCF3
benzenesulfonyl radical, which added to styrene affords an
alkyl radical. This radical is able to oxidize to the Au(II)
, which is further oxidized to the Au(III)
(
8
)
and
a
Stern-Volmer fluorescence quenching experiments to gain
insight into the photoredox catalytic cycle were performed
(For details, see the supporting information (Figure S1-2, SI).
8
intermediate
A
2+
2+
) by Ru (bpy)33+, generating Ru(bpy)3 thereby
Reductive
delivers the product
The photoluminesecence of Ru (bpy)3 was quenched by
intermediate (
B
IPrAuSbF6 with a rate constant of 8.85 × 102 Lmol-1. In contrast,
PhSO2SCF3 (-1.11 V vs SCE) and styrene cannot serve as an
emission quencher. The cyclic voltammogram of IPrAuSbF6
contains a reversible reduction peak at -0.11 V vs SCE (Figure
S5, SI), indicating that this cationic gold catalyst is easily
completing the photoredox catalytic cycle.
elimination of the Au(III) intermediate
B
and regenerates the Au(I) catalyst. This alkyl radical directly
reacted with another equivalent of PhSO2SCF3 could also
afford the target product in a radical chain mechanism. In our
reaction, when the internal alkenes were employed as reaction
substrates, excellent diastereoselectivities were observed and
both trans- and cis-alkenes gave the same diastereomer, which
2+
reduced by the excited state of the photocatalyst Ru (bpy)3
III/*II
(E1/2
= −0.81 V vs SCE).10b To characterize this electron
transfer reaction further, a flash-photolysis study was carried
4 | J. Name., 2012, 00, 1-3
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4
5
C. Hansch, A. Leo, S. H. Unger, K. H. Kim, D. Nikaitani and E. J.
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(a) J. F. Giudicelli, C. Richer and A. Berdeaux, Br. J. Clin.
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is not common in pure radical reaction. The IPrAu(I)SCF3 (8)
approached the in situ formed alkyl radical from the less
sterically hindered side, which might contribute to the
excellent diastereoselectivity of this reaction. The proposed
dual gold photoredox catalytic cycle maybe the major
pathway, although the radical chain reaction couldn’t be
excluded. This gold catalytic cycle from Au(0) to Au(III) is
similar to reported nickel participating photoredox catalytic
cycles.
6
(c) C. Zhang and D. A. Vicic, J. Am. Chem. Soc., 2012, 134
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In summary, we have reported an intermolecular atom
transfer thiosulfonylation reaction of alkenes. Both
trifluoromethylthio group and other functionalized thio groups
can be introduced into alkenes with excellent regioselectivity
and diastereoselectivity. These reactions are promoted by a
synergistic combination of gold catalysis and visible light
photoredox catalysis. Detailed control experiments and
reaction mechanism study indicate that the gold catalyst goes
through four different valencies from Au(0) to Au(III), which is
unprecedented in previously reported Au-catalyzed
transformations. This new dual gold and photocatalysis mode
holds potential for the applications to other important
transformations.
8
9
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Acknowledgements
We are grateful for financial support from the Natural Science
Foundation of China and Shandong province (no. 21572118 &
JQ201505), the fundamental research and subject construction
funds (No 2014JC008, 104.205.2.5) and Zhong-Ying Tang
scholar award of Shandong University. We thank Prof. Dr. Di
Sun who carried out the X-ray crystallographic analysis.
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6 | J. Name., 2012, 00, 1-3
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