Synthesis of ortho-phenolic sulfilimines via an intermolecular sulfur atom transfer cascade reaction

Article abstract of DOI:10.1021/acs.orglett.0c01032

To expand the toolbox for the synthesis of ortho-phenolic sulfilimines, sigmatropic rearrangements were introduced to the field of sulfilimine chemistry. Herein we report a N-H sulfenylation/[2,3]-sigmatropic rearrangement cascade reaction. This mild reaction enables commercially available thiols to serve as the sulfenylation reagent and generates water as the sole byproduct. Moreover, the reaction has a wide substrate scope and can be conducted on a gram scale with excellent reaction efficiency.

Full text of DOI:10.1021/acs.orglett.0c01032

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Letter
Synthesis of ortho-Phenolic Sulfilimines via an Intermolecular Sulfur
Atom Transfer Cascade Reaction
Feng Xiong,*,⊥ Yingying Zuo,⊥ Yinan Song,⊥ Linxing Zhang, Xinhao Zhang,* Shaojian Xu,
and Yan Ren*
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ABSTRACT: To expand the toolbox for the synthesis of ortho-phenolic sulfilimines, sigmatropic rearrangements were introduced to
the field of sulfilimine chemistry. Herein we report a N−H sulfenylation/[2,3]-sigmatropic rearrangement cascade reaction. This
mild reaction enables commercially available thiols to serve as the sulfenylation reagent and generates water as the sole byproduct.
Moreover, the reaction has a wide substrate scope and can be conducted on a gram scale with excellent reaction efficiency.
n recent years, there has been increasing interest in
Scheme 1. Strategies for the Formation of Sulfilimine
Derivatives
I
developing synthetic methods to prepare sulfilimines
(sulfimides),1 which are valuable building blocks in organic
synthesis2 and serve as functional groups in biologically active
agents.3 Recently, Yoshida reported that sulfilimines can
stabilize benzyl cations for the subsequent cross-coupling
reaction.4 Hudson and coworkers identified an interesting
biologically relevant role of sulfilimine bonds in collagen IV
networks (Figure 1).5 The potential effect of sulfilimine cross-
lysts.9h−k Therefore, the development of a mild and efficient
method for the synthesis of sulfilimines is still highly desirable.
Sigmatropic rearrangements triggered by the cleavage of X−
Y (X, Y = C, O, N, S, I) bonds serve as an efficient strategy for
synthesizing complex molecules,10,11 especially those contain-
Figure 1. Sulfilimine and sulfoximine derivatives in biologically active
agents.
linking in Goodpasture disease has attracted attention in
medicine as well.6 In addition, the sulfoximine group, which
could be easily obtained by oxidation of the sulfilimine group,
has been considered a widely neglected opportunity in
medicinal chemistry (Figure 1).7 Sulfilimines are typically
prepared by the imidation of thioethers (Scheme 1a).8,9
However, most of these methodologies suffer from the use of
hazardous reagents9c−e,g and expensive transition-metal cata-
Received: March 21, 2020
https://dx.doi.org/10.1021/acs.orglett.0c01032
© XXXX American Chemical Society
Org. Lett. XXXX, XXX, XXX−XXX
A

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Letter
ing heteroatoms.12,13 O−NHAc (oxyacetamide) has been
proven to be a multitasking functional group.14,15 The
potential of the O−N bond of oxyacetamide to participate in
sigmatropic rearrangements was observed in a few case-
s,14c,e,g,15g and we envision that the strategy can be applied in
the synthesis of structurally diverse sulfilimines.
With the optimum conditions in hand, various aryloxyamide
substrates were tested for this cascade reaction (Scheme 2).
a
Scheme 2. Substrate Scope of Aryloxyamides
Previously, we developed a biocompatible method for the
synthesis of sulfilimines that required prefunctionalized
sulfenylation reagents.14c From a green and sustainable
synthetic standpoint, the use of commercially available thiols
as the sulfenylation reagent is more attractive.16 Herein we
report a transition-metal-free regioselective transformation for
the construction of ortho-phenolic sulfilimines via direct the
C−H/S−H cross-coupling of N-phenoxyacetamide with thiols
(Scheme 1b). This reaction makes full use of the excellent site
selectivity, the oxidative O−N bond, and the amination
functionality of the oxyacetamide moiety (O−NHAc) at room
temperature.
Our initial study began with N-phenoxyacetamide 1a and 4-
chlorothiophenol 2a in the presence of CsOAc in THF at
room temperature under air for 16 h. To our delight, we
obtained an interesting ortho-phenolic sulfilimine product 3aa
in 23% yield (Table 1, entry 1). Next, we screened a series of
a
Table 1. Optimization of the Reaction Conditions
entry
additive
reaction time (h)
solvent
yield (%)
1
2
3
4
5
6
7
8
CsOAc
PivOH
NaOAc
Et3N
16
16
16
16
16
16
16
16
16
16
16
3
THF
THF
THF
THF
PhCH3
DCE
MeOH
CH3CN
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
DMSO
23
0
0
0
0
CsOAc
CsOAc
CsOAc
CsOAc
CsOAc
CsOAc
CsOAc
CsOAc
CsOAc
CsOAc
CsOAc
0
trace
51
96
9
b
10
11
12
13
14
15
16
17
74
a
Reaction conditions: 1 (0.2 mmol), 2a (0.4 mmol), and CsOAc (1
c
96
equiv) in DMSO (1 mL) at room temperature for 10 h. Yields of
isolated products are given.
28
76
95
6
10
10
10
10
The electronic effects of the substituents on the aromatic ring
were found to significantly affect the reaction. N-Phenox-
yacetamides with electron-donating groups, such as methyl
(3ab) and tert-butyl (3ac), afforded the corresponding
products in excellent yields ranging from 92 to 98%, whereas
electron-withdrawing groups, such as bromo (3ae) and ester
(3af), gave the products in good yields ranging from 66 to
84%. The naphthyl-substituted substrate not only gave a good
yield but also resulted in high regioselectivity, which
functionalized only the ortho-C−H at the C-1 position
(3ag). Substituents at the ortho position (3ah) gave the
corresponding products in lower yield than substituents at the
meta (3ai, 3ai′) and para positions (3ab). In addition, for
meta-substituted substrates with two different ortho sites, two
regioisomers (3ai/3ai′, 3aj/3aj′) with ratios of 2.1:1 and 2.6:1
were obtained, indicating that steric hindrance might play an
important role in the reaction. The dual-substituted substrate
(3ak) was also well tolerated. Notably, when the acetyl group
was replaced by benzoyl (3al) or the bulkier pivaloyl group
(3am), the reaction also proceeded smoothly in 75 and 72%
yields, respectively.
d
92
trace
trace
e
CsOAc
a
Reaction conditions: 1a (0.2 mmol), 2a (0.4 mmol) and additive (1
equiv) in solvent (1 mL) at room temperature under air. Yield as
determined by 1H NMR spectroscopy using 1,4-dimethoxybenzene as
b
c
an internal standard. 0.5 equiv of CsOAc was used. 2.0 equiv of
d
e
CsOAc was used. Isolated yield. Under N2.
additives, such as PivOH, NaOAc, and Et3N, but did not
obtain better results (entries 2−4). Surprisingly, solvent has a
significant effect on this reaction; whereas DMSO greatly
promoted this process, other solvents, such as PhCH3, DCE,
and MeOH, were not effective, and all of the starting material
N-phenoxyacetamide (1a) remained. An equivalent amount of
CsOAc is sufficient for this transformation when changing the
amount of CsOAc. The reaction time screening indicated that
10 h is enough for this transformation. When the cascade
reaction was conducted without a base (entry 16) or under a
nitrogen atmosphere (entry 17), almost no product 3aa was
obtained, which indicates that the base and O2 are essential in
this transformation.
Subsequently, the scope of thiols in this reaction was
explored (Scheme 3). To our delight, a variety of thiols with
B
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a
a b
,
Scheme 3. Substrate Scope of Thiols
Scheme 4. Substrate Scope of Disulfides
a
Reaction conditions: 1a (0.2 mmol), 2 (0.3 mmol), and CsOAc (1
equiv) in DMSO (1 mL) at room temperature for 10 h. Yields of
b
isolated products are given. The reaction temperature is 40 °C.
Scheme 5. Gram-Scale Synthesis
a
Reaction conditions: 1a (0.2 mmol), 2 (0.4 mmol), and CsOAc (1
equiv) in DMSO (1 mL) at room temperature for 10 h. Yields of
isolated products are given.
ortho, meta, or para substituents were able to react smoothly
with N-phenoxyacetamide, affording the desired ortho-phenolic
sulfilimines in good to excellent yields (3ba−ia). A reverse
electronic effect of the substituents was observed. The
electron-deficient thiols gave the desired products in higher
yield than the electron-rich thiols. Notably, heteroaryl-bearing
thiols (3ja, 3ka) also worked well in the reaction and gave the
corresponding products in good yields.
Scheme 6. Control Experiments
Encouraged by the successful coupling of thiols with N-
phenoxyacetamide, we then extended this transformation to
disulfides (Scheme 4). An electron-deficient diaryl disulfide
(3aa) gave the desired product in a higher yield than electron-
rich diaryl disulfides (3ba, 3da). Notably, the electron-rich
diaryl disulfides could be almost fully transformed into the
corresponding products when the reaction temperature was 40
°C (3ba, 3da). We were pleased to find that dialkyl disulfides
(3ma, 3na) also worked for this reaction, although the yields
were very low.
Considering the mild reaction conditions and the high atom
economy of this protocol, we performed gram-scale reactions
between 1a and 2a or 2b, affording the corresponding products
in 90 (3aa) and 86% (3ba) yields, respectively (Scheme 5).
Therefore, this protocol could serve as an efficient and
practical method for the synthesis of various ortho-phenolic
sulfilimines and has the potential to be applied in the green
chemical industry.
N-phenoxyacetamide (1a) under standard conditions (Scheme
6b). Then, the treatment of di(p-chlorophenyl) disulfide (2o)
with N-phenoxyacetamide (1a) led to 3aa in 96% yield,
indicating that di(p-chlorophenyl) disulfide might be an
intermediate in this transformation (Scheme 4). To further
explore the mechanism, the reaction of N-phenoxyacetamide
(1a) with 4-chlorothiophenol (2a) was examined without
CsOAc (Table 1, entry 16) or air (Table 1, entry 17), and the
expected product 3aa was not observed. Moreover, the
reaction of N-phenoxyacetamide (1a) with 4-chlorothiophenol
(2a) was tested in the presence of TEMPO, and the coupling
product 3aa decreased only slightly to 84%, indicating that a
radical process was not involved this reaction system (Scheme
6c).
We conducted detailed control experiments to understand
the mechanism of this cascade reaction. When N−H was
replaced by N−Me, no product was obtained, which suggested
that N−H was essential for this reaction (Scheme 6a).
Additionally, 4-chlorothiophenol (2a) was completely con-
verted into di(p-chlorophenyl) disulfide (2o) in the absence of
C
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On the basis of the aforementioned observations and
together with previous reports on sp2 C−H sulfenylation, a
plausible mechanism was proposed and studied by density
functional theory (DFT) calculations (Figure 2). Initially, the
Experimental procedures, characterization data, and
NMR spectra of all compounds (PDF)
AUTHOR INFORMATION
■
Corresponding Authors
Feng Xiong − School of Life Sciences, Nanjing University,
Nanjing 210093, China; Department of Chemistry, The
University of Hong Kong, Hong Kong SAR, China;
orcid.org/0000-0002-5750-5371; Email: xiongfeng06@
163.com
Xinhao Zhang − State Key Laboratory of Chemical
Oncogenomics, Peking University Shenzhen Graduate School,
Shenzhen 518055, China; orcid.org/0000-0002-8210-
2531; Email: zhangxh@pkusz.edu.cn
Yan Ren − Hygiene Sector, Joint Laboratory for Infectious
Disease Prevention and Control, Longhua District Center for
Disease Control and Prevention, Shenzhen 518109, China;
Email: 437316459@qq.com
Authors
Figure 2. Free-energy profile of the intermolecular sulfur atom
transfer cascade reaction. Free energies and enthalpies (in
parentheses) are given in kilocalories per mole.
Yingying Zuo − State Key Laboratory of Chemical
Oncogenomics, Peking University Shenzhen Graduate School,
Shenzhen 518055, China
Yinan Song − Department of Chemistry, The University of Hong
Kong, Hong Kong SAR, China
Linxing Zhang − State Key Laboratory of Chemical
Oncogenomics, Peking University Shenzhen Graduate School,
Shenzhen 518055, China
Shaojian Xu − Hygiene Sector, Joint Laboratory for Infectious
Disease Prevention and Control, Longhua District Center for
Disease Control and Prevention, Shenzhen 518109, China
N−H bond of N-phenoxyacetamide (1a) was deprotonated by
AcO− to form the intermediate INT1. Under standard
conditions, 4-chlorothiophenol (2a) was oxidized to di(p-
chlorophenyl) disulfide (2o). Subsequently, the anionic
intermediate INT1 underwent nucleophilic substitution to
di(p-chlorophenyl) disulfide (2o) via transition state TS1 with
a 15.2 kcal/mol barrier, leading to the formation of a N−S
bond (intermediate INT2). Next, cleavage of the O−N bond
and electrophilic [2,3]-δ-rearrangement of intermediate INT2
proceeded to give intermediate INT3 with a 22.0 kcal/mol
barrier (transition state TS2).14c Finally, the intermediate
INT3 easily underwent tautomerization to produce 3aa. The
DFT studies indicated that the rate-limiting step of this
reaction is the electrophilic [2,3]-δ-rearrangement (TS2), and
the free-energy barrier is 25.9 kcal/mol, which is energetically
feasible under standard conditions. The substituent effects of
aryloxyamides (Scheme 2) and disulfides (Scheme 4) were also
studied by DFT calculations and found to be consistent with
the experimental results (Table S1 in the Supporting
Information).
In conclusion, we developed a novel strategy for the
synthesis of ortho-phenolic sulfilimines under mild conditions.
The reaction shows excellent chemoselectivity and a broad
substrate scope for N-aryloxyamides, aryl/heteroaryl thiols, and
diaryl/dialkyl disulfides. Moreover, this atom-economical
cascade reaction uses commercially available thiols as a sulfur
source and generates water as the sole byproduct. Importantly,
the reaction can be conducted on a gram scale with excellent
reaction efficiency. The further application of the atom transfer
cascade in other useful transformations is underway in our
laboratory.
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.orglett.0c01032
Author Contributions
⊥F.X., Y.Z., and Y.S. contributed equally to this work.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We are grateful to the National Natural Science Foundation of
C h i n a ( 2 1 9 3 3 0 0 4 ) , t h e S h e n z h e n S T I C
(JCYJ20170412150343516, JCYJ20170818085512379), and
the Shenzhen San-Ming Project (SZSM201809085) for
financial support.
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ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.orglett.0c01032.
■
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