Nickel-catalyzed directed sulfenylation of sp2 and sp3 C-H bonds

Article abstract of DOI:10.1039/c5cc01970b

Directed sulfenylation of both sp² and sp³ C-H bonds was achieved through nickel catalyzed directed C-S bond formation, giving the desired product in good to excellent yield (up to 90%). Other metal cations, including Cu, Fe, Pd, Rh, Ru and Co, gave almost no reaction under identical conditions, which highlighted the unique reactivity of this Ni system.

Full text of DOI:10.1039/c5cc01970b

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Nickel-Catalyzed Directed Sulfenylation of sp2 and sp3
C-H Bonds
Cite this: DOI: 10.1039/x0xx00000x
Xiaohan Ye, Jeffrey L. Petersen and Xiaodong Shi
Received 00th January 2012,
Accepted 00th January 2012
DOI: 10.1039/x0xx00000x
www.rsc.org/
Directed sulfenylation of both sp2 and sp3 C-H bonds was
achieved through nickel catalyzed directed C-S bond
formation, giving the desired product in good to excellent
yield (up to 90%). Other metal cations, including Cu, Fe, Pd,
Rh, Ru and Co, gave almost no reaction under identical
conditions, which highlighted the unique reactivity of this Ni
system.
performed using a broad substrate scope with good yields observed
(Scheme 1C).7
A) C-S formation through cross-coupling
[M]= Pd, Rh, Ir, Cu, Fe
SPh
X
[M]
+
PhSH or PhSSPh
ref 4
B) Cu- catalyzed C-H sulfenylation: Challenging for sp3 C-H
O
O
During the last decade, transition metal catalysed C-H
functionalization has been applied as an efficient approach for
complex molecule synthesis.1 Among all reported methods, the
chelation assisted directing group strategy has gained rising
attention for site-selective C-H activation.2 Generally, ,the
chelating effect enhances the metal reactivity, especially
towards less reactive sp3 C-H bonds.3 Due to the significance
of the organosulfur compounds in chemical and biological
research, selective C-H sulfenylation received more and more
attentions. Transition metal catalyzed C-S bond formation is a
challenging task, due to the coordination ability of sulfur atom
towards various metal cations (potential poisoning of the
catalyst). Thus, new approaches that can efficiently construct
C-S bonds are always highly desirable.
Previously, the cross coupling approach between aryl-halide
and thiol/disulfide has been achieved for the sp2 C-S bond
construction under special conditions (solvents, catalyst and ligand)
with limited reaction scope.4 Directed C-H sulfenylation offers high
efficiency and better atom economy (by avoiding the usage of aryl
halides), though challenges still arise. These issues are manifested
by the strong coordination between metal and sulfur, potentially
Q
Q
Q
Q
Cu(OAc)2 0.5 equiv
N
H
N
+ PhSSPh
H
K2CO3, DMSO
120 oC, Air
SPh
H
N
Q
95%
Daugulis, ref 6
O
O
Q
Cu(OAc)2 1.0 equiv
N
H
+
<15%
poor reactivity
toward sp3 C-H
PhSSPh
N
H
H
H
K2CO3, DMSO
120 oC, Air
H
SPh
C) This work: Nickel-catayzled sp2 and sp3 C-H sulfenylaiton
O
Ni cat. 20 mol%
LiOtBu 5 euqiv.
O
R1
R1
R1
R2
RSH
or
RSSR
Q
+
N
H
N
H
up to 90% yield
DMF(0.5M), 120 o
C
CH3
SR
R = aryl or alkyl
< 10% yield
< 10% yield
< 10% yield
Other tested metal (Pd, Cu, Rh, Ru, Fe):
NaOtBu or KOtBu:
Other tested solvents (DMSO, MeCN, DCE):
Scheme 1. Catalytic C-H sulfenylation
To explore the possibility of sp3 C-H sulfenylation, we
turned our attention to nickel complexes. Nickel catalysis is
known for its versatile reactivity including rapid single electron
inhibiting C-H activation and or catalyst turnover.5 Very recently, transfer (SET).8 During the past several years, nickel catalysis
Daugulis and co-workers reported a successful example of sp2 C-H
has received increasing attentions due to the promising
reactivity toward directed sp3 C-H functionalization. This is
sulfenylation using 8-aminoquioline (Q) moiety as the chelate
directing group with Cu(OAc)2 as catalyst (up to 50% loading).6
evidenced through several examples reported in literature for C-
However, under their optimal conditions, sp3 C-H sulfenylation did
not occur (< 15% yield) when using 1 equiv. of Cu(OAc)2 (Scheme
C and C-N formation.9 To explore the feasibility of directed C-
H sulfenylation, we prepared various amide 1 (containing
different directing groups) and charged them with nickel
catalyst precursor under different conditions. The results are
summarized in Figure 1.
1B).
Moreover, disulfides were required as the sulfur
source/oxidant, decreasing atom economy with limited scope.
Herein, we report the successful C-H sulfenylation of both sp3 and
sp2 C-H bonds using a Ni-based catalyst and thiols as the sulfur
source. Additionally, directed sp3 C-H sulfenylation could be
This journal is © The Royal Society of Chemistry 2012
J. Name., 2012, 00, 1-3 | 1

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DOI: 10.1039/C5CC01970B
O
O
Interestingly, reaction parameters in the optimal conditions
seemed crucial. First, under the identical conditions, other
tested metal complexes, including Cu(OAc)2, CuI, Pd(OAc)2,
[Rh(COD)Cl]2, RuCl3, Fe(OTf)3, gave little reactivity with
<10% C-H sulfenylation product obtained (entry 2). Similarly,
DMF and LiOtBu were both critical for the reaction
performance (entries 3-5); Ni(OTf)2 gave the best results when
compared with other nickel salts (entries 6-7). The reaction
could not reach a total completion without argon protection
(entry 8), suggesting the decomposition of nickel catalysts
under air atmosphere over time. Finally, the addition of
previously reported assisting ligands (dppbz and MesCOOH,
entries 9 and 10) did not show improvement. Considering the
strict reliance on DMF as the optimal solvent and lithium base,
it suggested the formation of Ni-DMF complexes under the
reaction conditions, which served as the actual catalyst in
promoting the reaction. Decreasing nickel catalyst loading or
reducing the amount of disulfide caused lower yields due to
uncompleted reaction over time (entries 11-12). Interestingly,
thiophenol also gave 15% yield under optimal conditions,
suggesting the importance of oxidant involved in the catalytic
NiCl2(DME), Base
Air, 120 oC
DG
DG
+
PhSSPh
2 equiv.
N
H
N
H
1
2a
H
SPh
F
F
DG:
H
5
CF3
N
N
N
N
N
1
Q
Ph
F
F
1a
1b
1c
1d
cat.
NiCl2(DME) 20%
DG
1a
conditions
DMF, LiO-tBu (5 eq), 12 h
alternation from above conditions
results
convn. 58%; 2aa:50%
convn. < 5%; 2a: < 5%
convn. < 10%; 2a: < 5%
convn. 10%; 2ab: < 5%
convn. < 5%; 2ac: < 5%
convn. 100%; 2ad: 0%
NiCl2(DME) 50% 1a-1c solvent: DMSO, DCE or CH3CN
NiCl2(DME) 50% 1a-1c base: Cs2CO3, NaOtBu, KOtBu
NiCl2(DME) 20%
NiCl2(DME) 20%
NiCl2(DME) 20%
1b
1c
1d
DMF, LiO-tBu (5 eq), 12 h
DMF, LiO-tBu (5 eq), 12 h
DMF, LiO-tBu (5 eq), 12 h
Figure 1. Ni-catalyzed sp3 C-H sulfenylation
As shown in Figure 1, substrates with various literature-
reported directing groups were prepared, including quinoline
(1a), pyridine (1b), 10 Yu-Wasa auxiliary (1c) 11 and 1,2,3- cycle. Inspired by this result, coupling with thiophenol was
triazole (1d).12 In Daugulis’ previous report, DMSO was
explored. As shown in entry 14, reaction of thiophenol could
not reach a full conversion (56%) under air and significant
revealed to be the optimal solvent for sp2 C-H sulfenylation.
product decomposition was observed. To our delight, electron-
deficient benzenethiol exhibits better performance with 83%
yield (100% conversion). To the best of our knowledge, this is
the first example that successfully achieved sp3 C-H
sulfenylation with disulfide or thiol in excellent yields. With
this optimal condition in hand, we embarked on the evaluation
One plausible reason was the inherent redox-stabilization
ability of DMSO towards thiol-disulfide interconversion. 13
However, with nickel catalyst, no sp3 C-H activation was
observed using DMSO as solvent under various conditions.
Interestingly, the only condition giving the desired sp3 C-H
sulfenylation was the reaction of the quinoline directing group
modified substrate 1a in DMF with LiOtBu as the base (50%
yield, 58% conversion). Notably, both the choice of solvent
and base are crucial: using other solvents (DMSO, DCE or
MeCN) with LiOtBu or using other bases (Cs2CO3, KOtBu or
NaOtBu) in DMF gave significantly lower reactivity.
Moreover, the quinoline substrate 1a gave significantly better
result than other directing groups.14 Based on these preliminary
results, we conducted detailed condition screening. As shown
in Table 1, under the optimal conditions with Ni(OTf)2 as
catalyst precursor, LiOtBu as base, DMF as solvent and with
argon protection, the desired sp3 C-H sulfenylation product 2a
was obtained in 86% isolated yields.
of the reaction substrate scope
.
Table 2. Reaction scope of Ni catalyzed sp3 C-H sulfenylation.a,b
O
O
Ni(OTf)2 20 mol%
LiOtBu 5 euqiv.
R1
R2
RSSR
or
RSH
R1
R2
Q
+
N
H
N
H
DMF (0.5M), 120 o
C
N
SR
2 or 3
H
Q
1
With PhSSPh, Ar (Condtion A)
O
O
O
O
Q
N
Q
Q
Q
N
H
Bu
N
H
N
H
H
Ph
SPh
2a, 86%
O
SPh
2b, 74%
SPh
2c, 87%
SPh
2d, 75%
O
O
O
n-Pr
n-Pr
n-Pr
Q
Q
Q
Q
N
H
N
H
N
H
N
H
Table 1. Selected conditions on Ni catalyzed sp3 C-H sulfenylation.
a
Ph
Ph
Bu
SPh
2e, 71%
SPh
SPh
SPh
2h, 72%
O
O
2f, 75%
2g, 88%
O
Ni(OTf)2 20%, LiOtBu 5 eq.
DMF, 120 oC, Ar
Q
Q
O
Ph
+
O
PhSSPh
2.5 equiv.
Q
N
H
N
PhS
O
Q
Q
N
N
H
Ph
H
N
H
Ph
H
Q
N
H
1a
2a
H
SPh
SPh
2i, 63% (85%brsm)
entry
1
Variations from the “standard” conditions
yield (convn.)
88% (100%)
2j, 80%
m:d=2:1
no conversion
none
2
Other catalysts (100%), including Cu(OAc)2, CuI,
Pd(OAc)2, [Rh(COD)Cl]2, RuCl3, Fe(OTf)3 et al.
Other solvents, including DMSO, CH3CN, DMA
NaOtBu as base
With ArSH, Air (Conditon B)
O
<5% (<10%)
O
O
S
O
Q
N
H
Q
N
H
Q
Q
3
4
5
<20% (<30%)
<5% (<5%)
9% (15%)
N
H
N
H
S
S
S
KOtBu as base
6
7
8
9
10
11
12
NiCl2(DME) 20 % as cat.
Ni(acac)2 20 % as cat.
Under air, no argon
Air, Ni(OTf)2 + dppbz
Air, Ni(OTf)2 + MesCOOH
1.5 equiv PhSSPh
84% (95%)
82% (91%)
75% (82%)
70% (82%)
78% (88%)
56% (67%)
52% (50%)
F
Cl
F3C
F
3b, 78%
3a, 80%
3c, 42%(81% brsm)
3d, 75%
O
O
O
Q
N
H
Q
N
H
Q
N
H
Et
S S
Et
HS
S
S
S
Ph
100% [Ni];
no conversion
10% Ni(OTf)2
13
14
15
PhSH 2.5 equiv.
PhSH under Air
o-FPhSH, under Air
15% (20%)
50% (56%)b
83% (100%)b
CH3
3g, 37%(77% brsm)
Cl
CF3
3f, 70%
3e, 81%
a
Reaction conditions: Condition A: 1a (0.3 mmol), PhSSPh (2.5 equiv.), Ni(OTf)2 (20
a
mol%), LiOtBu (5 equiv.) in dry DMF (0.6 mL), Ar, 120 oC. Condition B: 1a (0.3
mmol), Ni(OTf)2 (20 mol%), ArSH (4 equiv.), LiOtBu (7 equiv.) in dry DMF (0.6 mL),
Air, 120 oC; b Isolated yield.
Reaction conditions: 1a (0.2 mmol), PhSSPh (2.5 equiv.), Ni(OTf)2 (20 mol%), Base
b
(5 equiv.) and additive (if applicable) in dry DMF (0.4 mL), Ar; ArSH (4 equiv.),
LiOtBu (7 equiv.) was used; The yield was determined by 1H NMR using 1,3,5-
c
trimethoxybenzene as internal standard.
2 | J. Name., 2012, 00, 1-3
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DOI: 10.1039/C5CC01970B
As shown in Table 2, the quinoline directing group
First, both EWG and EDG substituted benzenes were
effectively promoted sp3 C-H bond activation and furnished the suitable for this reaction. Good regioselectivity was observed
sulfenylation products in good yields. In general, the reaction for the meta-substituted benzenes (4c and 4d) with
targeted on methyl C-H (CH3) over methylene (CH2), even with sulfenylation occurring on the less hindered C-H bond.
the presence of benzylic CH2 (2d). Similarly, 1-methyl- Interestingly, a reversed regioselectivity was obtained with m-
cyclobutane derivatives gave the desired sulfenylation product Cl and m-F substituted benzene (4e and 4f), giving the C-S
with 2i without C-H sulfenylation on the ring. Notably, bond formation at the adjacent C-H bond (confirmed by X-ray
substrates with cyclopropane on the side chain could also crystallography).
The exact reason of this unusual
tolerate this transformation (2e). Modest selectivity was regioselectivity is currently under investigation. The selectivity
observed when two methyl groups were present (formation of between mono- and di-sulfenylation was poor as other reported
mixture of mono and disulfenylation, 2j).
cases. In those cases, the di-sulfenylation products were
Considering the obvious practical advantages, we explored achieved with good yields (4m-4o) with increasing amount of
various thiols (instead of disulfides) as the sulfur source. Most thiophenol/LiOtBu. Notably, this strategy was also suitable for
EWG substituted thiolphenols gave good yields (3a, 3b, 3d- di-sulfenylation for meta-substituted benzene (4k and 4l)
3f). Lower yields were observed with electron rich thiolphenols though with the presence of steric hindrance. Thiophene was
(3g) and ortho-CF3 thiolphenols (3c). Reactions with alkyl also suitable for this reaction with C-S products formed in good
thiol or disulfide did not proceed under this condition, even yield (4i). The scope of thiols was also evaluated. Besides
with 100% nickel catalyst precursor loading. Nevertheless, thiophenol, both electron-rich and electron-deficient
even with some limitation, this method provides the first benzenethiol were tolerated, giving promising yields. Notably,
successful example to achieve sp3 C-H sulfenylation.
with halides present on the benzene ring, the C-S bond
formation occurred over oxidative addition (5h, 5j).
Diphenylselenium (5m) were examined and gave the desired
products in good yields. A gram-scale synthesis was carried
out as shown in Scheme 2, which showcased the robust nature
of this new method. The challenging aliphatic thiols showed
almost no reactivity under standard condition. Remarkably,
using aliphatic disulfide and 50% NiCl2(DME), the reactions
proceeded well and the desired products (5n-5p) were produced
Table 3. Reaction scope for sp2 C-H sulfenylation.a, f
O
O
NiCl2(DME) 10 mol%,
Q
LiOtBu 5 euqiv.
Q
N
H
N
RSH
+
H
DMF (0.5M), 100 oC, Air
H
SR
1
4
O
Me
O
CF3
O
O
F3C
Q
Q
Q
Me
Q
Q
Q
N
N
N
N
H
H
H
H
SPh
SPh
4a, 89%
SPh
SPh
4b, 85%
SPh
SPh
4c, 78%
Me
in good yields.
These results clearly highlighted the
4d, 65%
significantly improved reactivity of this newly discovered
catalytic system in C-H sulfenylation.
O
O
O
O
Q
Cl
Q
F
Q
N
H
N
H
N
H
N
H
Me
Cl
SPh
4g, 91%
SPh
SPh
4h, 90%
SPh
O
O
NiCl2(DME) 10 mol%,
LiOtBu 5 euqiv.
4e, 81%
4f, 80%
Q
Q
O
O
O
O
N
N
H
+
PhSSPh
H
F3C
Q
Q
Q
DMF (0.5M), 100 oC, Air
S
N
H
N
H
N
H
SPh
N
H
SPh
H
SPh
4l, 72%b
SPh
SPh
4k, 77%b
SPh
4a
83% yield, 1.47 g
1 (5 mmol)
4i, 72%
4j, 82%
SPh
O
SPh
O
O
Scheme 2 Gram-scale syntheses.
Q
Q
Q
N
H
N
H
N
H
To understand the reaction mechanism, we first performed
the radical trapping experiment (Scheme 3A). TEMPO (3 eq.)
did not influence the reaction efficiency. This result suggested
a single electron transfer (SET) process was likely not involved.
Mercury poisoning at the starting pointing (t=0) and/or at the
reaction point (t=25 min) showed no quenching of reactions
(See SI), indicating a homogenous nickel catalytic process. The
competition experiment between different arenes gave
exclusively sulfenylation on electron-deficient aromatic ring
(Scheme 3B). This result strongly suggests that C-H bond
cleavage might be dependent on acidity.
F3C
SPh
4n, 81%b
SPh
4m, 83%b
MeO
SPh
4o, 77%b
4e x-ray
Me
O
5a, R = o-Me, 86%
5b, R = o-F, 84%
5i, R = p-Me, 90%
5e, R = m-F, 84%
Q
5f, R = m-CF3, 75%c
5g, R = m-OMe, 80%
5h, R = m-Cl, 72%
5j, R = p-Br, 83%
N
H
R
5c, R = o-CF3, 73%c
5d, R = m-Me, 88%
5k, R = p-CF3, 65%c
5l, R = p-OMe 85%
S
5a
Me
Me
O
Me
O
O
Me
O
Q
Q
Q
Q
N
H
N
H
N
H
N
H
S
Pr
S
Bu
SePh
5m, 81%d
S
Et
5n,, 70%d,e
5o, 72%d,e
5p, 73%d,e
a Reaction conditions: 1a (0.3 mmol), ArSH (2.2 equiv.), NiCl2(DME) (10 mol%),
LiOtBu (5 equiv.) in dry DMF (0.6 mL), Air, 100 oC; ArSH (4.0 equiv.),
b
A) Radical scavenger experiments
NiCl2(DME) (15 mol%), LiOtBu (7 equiv.) was used, 110 oC; 120 oC;
c
d
SPh
O
O
Disulfide 1.5 equiv. was used; e 50 mol% NiCl2(DME) was used; f Isolated yield.
NiCl2(DME) 10mol%
LiOtBu 5 equiv.
Q
Q
N
N
+
H
H
PhSSPh
DMF(0.5M), 100 oC
Although the exact reason for significantly better results
using the combination of DMF and LiOtBu is unclear, this new
condition could presumably be extended to the sp2 C-H
sulfenylation. Furthermore, the application of thiophenol as the
sulfur source greatly extended the reaction scope. After a brief
screening, a general condition was revealed with air-stable
Me
Me
90% yield
89% yield
No additive
3 equiv. TEMPO
B) Competition experiment
O
SPh
Q
O
Me
NiCl2(DME) 10mol%
LiOtBu 5 equiv.
N
H
F
Q
N
H
+
PhSSPh
0.5 euqiv
O
o
DMF(0.5M), 100 oC
Air, 5h
NiCl2(DME) as catalyst precursor (10 mol%) at 100 C under
Q
F
N
H
only Product
86%
ambient pressure (open flask). Under these mild conditions,
good to excellent yield of sp2 C-H sulfenylation was achieved.
The substrate scope is summarized in Table 3.
Scheme 3. Mechanism investigations
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VJieowuArrtnicalelONnlainme e
DOI: 10.1039/C5CC01970B
Presumably, the disulfide performed as a true oxidant in
promoting either Ni(I)/Ni(III) or Ni(II)/Ni(IV) catalytic cycle
under disulfide/Ar condition.15 However, the thiol/air system
gave faster reaction kinetic than disulfide reactions. Thus, it is
clear that these transformations likely proceed through different
mechanism under these two different conditions. Detailed
mechanistic investigations are currently undergoing in our lab.
F.-J. Chen and B.-F. Shi, Angew. Chem. Int. Ed., 2013, 52, 13588-13592;
(f) L. Grigorjeva and O. Daugulis, Org. Lett., 2014, 16, 4684-4687; (g)
Wang, Y. Kuninobu and M. Kanai, Org. Lett., 2014, 16, 4790-4793; (h)
X. Wu, Y. Zhao, G. Zhang and H. Ge, Angew. Chem. Int. Ed., 2014, 53,
3706-3710; (i) L.-S. Zhang, G. Chen, X. Wang, Q.-Y. Guo, X.-S. Zhang,
F. Pan, K. Chen and Z.-J. Shi, Angew. Chem. Int. Ed., 2014, 53, 3899-
3903; (j) X. Ye and X. Shi, Org. Lett., 2014, 16, 4448-4451; (k) S.-Y.
Zhang, Q. Li, G. He, W. A. Nack and G. Chen, J. Am. Chem. Soc., 2015,
137, 531-539
Conclusions
4
(a) J. F. Hartwig, Acc. Chem. Res., 2008, 41, 1534-1544; (b) I. P.
Beletskaya and V. P. Ananikov, Chem. Rev., 2011, 111, 1596-1636; (c)
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Liu, Chem. Soc. Rev., 2015, 44, 291-314; (f) D. Zhang, X. Cui, Q. Zhang
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For selected examples of C-H sulfenylation/selenation see: (a) M.
Iwasaki, M. Iyanaga, Y. Tsuchiya, Y. Nishimura, W. Li, Z. Li and Y.
Nishihara, Chem. Eur. J. 2014, 20, 2459-2462; (b) X.-B. Yan, P. Gao,
H.-B. Yang, Y.-X. Li, X.-Y. Liu and Y.-M. Liang, Tetrahedron, 2014,
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Biomol. Chem., 2014, 12, 9519-9523.; (d) M. Iwasaki, W. Kaneshika, Y.
Tsuchiya, K. Nakajima and Y. Nishihara, J. Org. Chem., 2014, 79,
11330-11338; (e) M. Iwasaki, Y. Tsuchiya, K. Nakajima and Y.
Nishihara, Org. Lett., 2014, 16, 4920-4923; (f) C. Shen, P. Zhang, Q.
Sun, S. Bai, T. S. A. Hor and X. Liu, Chem. Soc. Rev., 2015, 44, 291-
314. (g) C. Lin, D. Li, B. Wang, J. Yao and Y. Zhang, Org. Lett., 2015
ASAP. DOI: 10.1021/acs.orglett.5b00337
In summary, we have developed a general synthesis of
substituted sulfide carboxylic acid derivatives from directed C-H
sulfenylation. The efficient C-S bond formation was enabled through
homogenous nickel catalysis with C-H bond activation on both sp2
and sp3 carbon atoms. Furthermore, this study revealed a new
efficient and economic approach towards sulfur containing product
formation (using thiol directly), highlighting the potential application
of the former in biological and pharmaceutical sciences. Such
investigation is currently underway in our laboratory.
5
Acknowledgements
We thank the NSF (CHE-1362057, CHE-1228336, CHE-1336071,
EPSCoR RII-1003907)) and NSFC (21228204) for financial support.
Notes and references
a
C.Eugene Bennett Department of Chemistry, West Virginia University,
6
7
West Virginia 26506, United States.
@mail.wvu.edu
E-mail: Xiaodong.shi
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T. J. Wallace, J. Am. Chem. Soc. 1964, 86, 2018−2021.
Complete conversion of starting materials was observed with 1,2,3-
triazole modified substrate 1d, though rather complex reaction mixtures
were observed. Investigation on other triazole-directing groups are
currently undergoing in the group.
15
For the plausible reaction mechanism, see SI.
4 | J. Name., 2012, 00, 1-3
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