in situ Formation of RSCl/ArSeCl and Their Oxidative Coupling with Enaminone Derivatives Under Transition-metal Free Conditions

Article abstract of DOI:10.1002/adsc.201900940

The reaction of diorganyl disulfides or diselenides with PhICl₂ in DMF at room temperature led to the in situ formation of the reactive organosulfenyl chloride (RSCl) or selenenyl chloride (ArSeCl), which reacted with enaminone compounds to afford a series of α-thioenaminones or α-selenylenaminones, respectively, including the bioactive inhibitor for Cdc25B and its analogue, via the intermolecular oxidative C(sp²)-S/Se cross coupling reactions under metal-free conditions. (Figure presented.).

Full text of DOI:10.1002/adsc.201900940

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DOI: 10.1002/adsc.201900940
in situ Formation of RSCl/ArSeCl and Their Oxidative Coupling
with Enaminone Derivatives Under Transition-metal Free
Conditions
Zhenhua Shang,a Qingyu Chen,a Linlin Xing,b,* Yilin Zhang,c Laura Wait,d and
Yunfei Dub,*
a
College of Chemical and Pharmaceutical Engineering, Hebei University of Science and Technology; Hebei Research Center of
Pharmaceutical and Chemical Engineering, Shijiazhuang 050018, People’s Republic of China
Tianjin Key Laboratory for Modern Drug Delivery & High-Efficiency, School of Pharmaceutical Science and Technology,
b
Tianjin University, Tianjin 300072, People’s Republic of China
E-mail: duyunfeier@tju.edu.cn; xinglinlin@tju.edu.cn
C. Eugene Bennett Department of Chemistry, West Virginia University, Morgantown, West Virginia 26506-6045, United States
School of Chemistry and Molecular Biosciences, The University of Queensland, St Lucia, Queensland 4068, Australia
c
d
Manuscript received: July 28, 2019; Revised manuscript received: September 1, 2019;
Version of record online: ■■■, ■■■■
Supporting information for this article is available on the WWW under https://doi.org/10.1002/adsc.201900940
might also be attributed to the fact that they could be
Abstract: The reaction of diorganyl disulfides or
diselenides with PhICl2 in DMF at room temper-
ature led to the in situ formation of the reactive
organosulfenyl chloride (RSCl) or selenenyl
conveniently converted into multifunctional com-
pounds through asymmetric hydrogenation.[4] Further-
more, α-thioenamine compounds are also potential
scaffolds found in pharmaceutical and bioactive
chloride (ArSeCl), which reacted with enaminone
molecules.[5] For example, compound I,[5a,b] which is
compounds to afford a series of α-thioenaminones
known as an inhibitor for Cdc25B dual specificity
or α-selenylenaminones, respectively, including the
bioactive inhibitor for Cdc25B and its analogue, via
protein phosphatase, possesses a thioenamine scaffold
in its structure. In addition, thioenamino peptide II,[5c]
the intermolecular oxidative C(sp2)-S/Se cross cou-
a potential new type of β-turn mimic, also bears a
pling reactions under metal-free conditions.
thioenamine moiety in its cyclic peptide molecule
(Figure 1).
Keywords: Diorganyl disulfide/diselenide; PhICl2;
Hence, tremendous effort has been devoted to the
construction of the α-thioenamine skeleton, which
Organosulfenyl/Organoselenenyl chloride; Enamine;
Oxidative coupling
combines structural diversity with interesting biolog-
ical activities.[4,6] Among these strategies, one of the
most straightforward methods is by the means of direct
Enaminones and their analogues play important roles C(sp2)-S bond formation through CÀ H bond function-
in numerous organic transformations due to the fact alization of the alkene moiety in the enamine
that this class of compounds possess both electrophilic substrates. The transition metal-free CÀ H bond func-
and nucleophilic reactive sites in their structures,
which enables the construction of various molecules
with enriched structural diversity.[1] On the other hand,
there has been long-standing interest in the construc-
tion of CÀ S/Se bonds because of their important
applications in organic synthesis[2] and the broad
biological properties associated with S or Se-contain-
ing compounds.[3] As a result, α-chalcogenylenaminone
compounds and their analogues, known as significant
and useful polyfunctionalized olefins, have attracted
considerable attention from organic chemists to ex-
plore their synthetic method and application. This
Figure 1. Representative Pharmaceutically Active Agents Pos-
sessing Thioenamine Scaffold
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Scheme 1. Existing Strategies for Oxidative CÀ S/Se Bond Formation
tionalization of enamines has recently witnessed workers reported that stoichiometric AgOAc and 2
notable advances.[7] In the last few decades, several equiv. of disulfides were required for the radical
delicate methods for the introduction of a thio group coupling reaction to afford the sulfenylated enamide
through direct C(sp2)-S bond formation have been (Scheme 1, eq 5).[6k] By using TBHP as an oxidant, our
developed.[6a,c–f,i–r,7] For example, Kostyuk and co- group[6a] reported an oxidative coupling of enaminone
workers[6q] reported their synthesis of sulfenylated and disulfides catalyzed by TBAI (Scheme 1, eq 6),
enamine derivatives by treatment of enamines with while Yu group[6r] developed a similar protocol using
arylsulfenyl chloride in the presence of Et3N. Besides Cu(OAc)2 as the catalyst (Scheme 1, eq 3).
that, both arenethiols and disulfides have been widely
Although these reactions have their own merits,
employed as the thio source for this type of sulfenyla- there are several problems that need to be addressed,
tion reactions. For instance, Lei group[6c] has demon- such as the inevitable use of metal oxidants or catalyst,
strated that the radical-radical cross coupling between lack of atom economy, and the requirement of high
enamines and thiophenols could be achieved under reaction temperature or a relatively longer reaction
electrochemical oxidative conditions. In addition to time for almost all of these transformations. Further-
electrochemical condition, conventional methodologies more, it is also known that organoselenium compounds
which use a variety of oxidants to achieve the are promising pharmaceutical reagents owing to their
oxidative coupling process have also been documented. unique biological properties, specifically their anti-
For examples, Wan[6m] and Prabhu group[6i] revealed cancer and antitumor activity.[3d] However, these
their metal-free cross coupling reactions of enaminones strategies were seldom feasible in the installation of
with arenethiols using air/KIO3 or DMSO/I2 system, selenyl group through C(sp2)-Se bond formation to
respectively (Scheme 1, eq 1 & 2). Alternatively, Loh achieve these compounds. Although Deng[6k] and our
and coauthors[6d] developed a palladium-catalyzed CÀ S group[6a] have realized the introduction of the selenyl
bond formation of enamines with thiols using Cu group (Scheme 1, eq 5 & 6), the desired selenylation
(OAc)2 as an oxidant. When disulfides were used as products were achieved in unsatisfactory yield (28%
reaction partners, both silver salts and TBHP could and 28–42% respectively).
serve as oxidants (Scheme 1, eq 4). Deng and co-
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Recently, we have successfully developed a one-pot reaction under an ice-bath rather than at room temper-
protocol to achieve regioselective intramolecular chal- ature gave similar results (entry 10). Additionally, the
cogenylacyloxylation of alkynes which is promoted by sources of hypervalent iodine(III) oxidants dramati-
in situ generated organosulfenyl chloride (RSCl) or cally affected the outcome of the reaction, since other
selenenyl chloride (RSeCl).[8] Inspired by this work, hypervalent iodine reagents including PIFA, PhIO and
we are interested to understand whether this one-pot PIDA gave either poor or no conversion under
strategy could be applied in the introduction of thio otherwise identical conditions (entries 11–13).
and selenyl functional groups to enaminone and its
Subsequently, to verify the broad substrate scope of
analogues. Based on our findings, herein, we report a the transformation, a variety of enamines were
novel metal-free CÀ H bond functionalization of the prepared and subjected to the optimized conditions. As
enamine compounds to afford the α-chalcogenylen- shown in Table 2, all these enamines underwent
amines in good to excellent yields in the presence of smooth reactions at room temperature within 30 min to
the in situ generated ArSCl or ArSeCl from the give the sulfenyl substituted products. Substrates 1b–d
reaction between the inactivated disulfides or disele- with either an electron-donating or -withdrawing group
nides and PhICl2.
including methyl, methoxy, and bromide on the
To test our hypothesis on the sulfenylation of aromatic ring of enamine 1, proved to be well tolerated
enamine by the in situ generated organosulfenyl under the standard conditions, delivering the corre-
chloride, enamine 1a was initially employed to react sponding products in good yields. To our delight, the
with PhSSPh and hypervalent iodine oxidant under reaction worked equally well with both methyl and
various conditions (Table 1). To our delight, subjecting sterically hindered tert-butyl alkyl R1 functional
groups, leading to the desired products 2e–f in 82%
and 78% yield, respectively. In addition, the reaction
could be further extended to substrate 1g with a
Table 1. Optimization of the Reaction Conditions[a]
heteroaryl ring thiophene linked to the alkene moiety.
The R2 group substituted on the amine moiety was also
investigated. Both enamines 1h and 1i containing a
phenyl or benzyl protecting group on the amine were
[b]
°
Entry Oxidant (equiv)
Solvent
Temp. ( C) Yield (%)
suitable for this CÀ S bond formation strategy. It was
also found that not only esters, but also a wide range
of electron-withdrawing groups such as cyano, ketone
and amide substituted enamines, were all good reaction
partners. All these enamines 1j-n with R1 group being
phenyl, p-chlorophenyl or methyl were found to be
tolerable under the standard conditions to furnish the
corresponding products 2j–n in 78–82% yield. Inter-
estingly, cyclic enamine 1o was still a facile substrate,
albeit with lower efficiency (51%) when compared to
the linear reactants.
After the thorough exploration of the reaction scope
of enamines, we then came to investigate the reactivity
of variously substituted diphenyl disulfides. The
electronic nature of substituents on diphenyl disulfides
did not have a great influence on the yields of the
reaction. For instance, both disulfides bearing an
electron-donating methyl group as well as an electron-
withdrawing chloro-substituted phenyl ring exhibited
1
2
3
4
5
6
7
8
PhICl2 (1.0 equiv.) CH3CN
PhICl2 (0.8 equiv.) CH3CN
PhICl2 (0.6 equiv.) CH3CN
PhICl2 (0.5 equiv.) CH3CN
PhICl2 (0.6 equiv.) DMF
PhICl2 (0.6 equiv.) DCM
PhICl2 (0.6 equiv.) CH3OH
PhICl2 (0.6 equiv.) THF
rt
rt
rt
rt
rt
rt
rt
rt
46
65
81
59
86
80
ND
trace
NR
87
9
PhICl2 (0.6 equiv.) CF3CH2OH rt
10
11
12
13
PhICl2 (0.6 equiv.) DMF
PIFA (0.6 equiv.) DMF
PhIO (0.6 equiv.) DMF
PIDA (0.6 equiv.) DMF
0
rt
rt
rt
ND
15
NR
[a] Reaction conditions: 1a (0.5 mmol), PhSSPh (0.3 mmol),
and oxidant in dry solvent (5 mL) at rt for 30 min.
[b] Isolated yields based on the enamine substrates.
the solution resulting from the reaction of PhSSPh high reactivity in this conversion, giving products 2p–
(0.6 equiv.) and PhICl2 (1.0 equiv.) to enamine 1a r in high yields. It is noteworthy that a heterocyclic
(1.0 equiv.) delivered the desired sulfenylated enamine disulfide underwent the sulfenylation process with a
2a in a yield of 46%. As we can see, loading a reduced similar efficiency, affording product 2s with 79%
amount of oxidant from 1.0 equiv. to 0.6 equiv. yield. In addition, the method was also applicable to
resulted in improved conversions (entries 1–3). How- alkyl disulfide, albeit the corresponding product 2t
ever, further decrease in the oxidant amount led to a was obtained in a slightly lower yield. Most strikingly,
slight drop in the reaction yield (entry 4). Afterward, a when we tried to install a selenyl group into the
series of solvents including DMF, DCM, methanol, enamine skeleton, we found that the outcome of
THF, and CF3CH2OH were tested and only DMF reactions was improved significantly under this meth-
provided superior result (entries 5–9). Conducting the od, despite the fact that initial attempts by other
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Table 2. PhICl2/PhSSPh-Mediated Synthesis of Chalcogenyl Enamine.[a]
[a] Reaction conditions: 1 (0.5 mmol), PhSSPh (0.3 mmol), and PhICl2 (0.3 mmol) in DMF (5 mL) at rt for 30 min.
[b] Isolated yields based on the enamine substrates.
researchers ended up with relatively low yields. When 75% in 3 steps (Scheme 2). To our delight, the
enamines with a phenyl, thiophene or a methyl R1 enaminone skeleton 4, prepared from commercial
group were applied in the selenylation procedure, the available naphthoquinone 3 according to literature
corresponding products 2u–w were obtained in a yield procedure,[9] can be converted to sulfenylated enami-
of 64–82%. Furthermore, substrates bearing phenyl or none 2aa through this one-pot method in an excellent
benzyl protecting amine groups gave similar results to yield. The following NH2 protection by acetic anhy-
the substrates with free NH2 group and were converted dride fulfilled the efficient synthesis of biologically
to selenyl products 2x and 2y in 63% and 77% yield, active 5aa. In addition, the selenyl analogue 5ab was
respectively. Moreover, the phenylselenyl group was also achieved in the same route with a high overall
successfully introduced to the cyano-substituted enam- yield of 85%.
ine 1z as well in a yield of 78%.
Indole and its derivatives are important scaffolds
To further demonstrate the practical use of this that have been widely found in bioactive natural
synthetic methodology, the bioactive molecule naph- products, pharmaceuticals and functional materials.[10]
thoquinone 5aa was synthesized in an overall yield of Encouraged by the results above, we next turned our
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Scheme 2. Application of the Synthetic Methodology to the Synthesis of Bioactive Molecule and Its Selenyl Analogue
attention to the functionalization of indole compound, 2a was obtained in 60% yield. The reaction of
a particular type of enamine compound, by this enamine 1a with disulfide in the presence of TEMPO
approach (Scheme 3). To our delight, the desired or BHT under the standard conditions provided a good
sulfenylated and selenylated indole were delivered yield of the sulfenylated enamine 2a, which excluded
smoothly under the standard conditions in a yield of a free-radical pathway for this reaction.
87% and 92%, respectively.
Based on the results from the control experiments
The resulting sulfenylated enamine could be further as well as the previous report,[8] a plausible mechanism
converted to other building block by a known was put forward as depicted in Scheme 6. The whole
method.[11] For example, by treatment with I2 and process mainly consisted of two steps, the first of
DBU, enamine 2a was conveniently converted to the which was the formation of active species phenyl-
sulfenylated azirine derivative 8 via intramolecular sulfenyl chloride. The diphenyl disulfides reacted with
azirination (Scheme 4). Although azirines bearing PhICl2 to form the sulfonium salt B through release of
various substitution pattern have been reported,[12] the PhI from intermediate A, and the dissociation of
synthesis of sulfenylated azirine from sulfenylated intermediate B gave rise to 2 molecules PhSCl. The
enamine has been seldom documented.
second step fulfilled the installation of sulfenyl group,
To probe the mechanism of the CÀ S(Se) formation which was initiated by the nucleophlic attack of the
process, a couple of control experiments were con- enamine electrons to the sulfonium center of the PhSCl
ducted (Scheme 5). First, the active species PhSeCl to afford the intermediate C. The intermediate C
was isolated from the reaction of diphenyl diselenide tautomerized to give the final product 2a.
and PhICl2. Subsequently, the resulting PhSeCl solid
In summary, a new CÀ H functionalization of
was subjected to enamine solution in DMF at room enamines involving in situ generation of organosulfen-
temperature and the corresponding selenylated product yl chloride (RSCl) or selenenyl chloride (ArSeCl) from
the reaction between diorganyl disulfides or disele-
Scheme 3. Synthesis of Sulfenylated and Selenylated Indole
Scheme 4. Further Derivatization of Sulfenylated Enamine 2a
Scheme 5. Control Experiments
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Scheme 6. Proposed Mechanism
2046; i) P. Zhou, B. Hu, L. Li, K. Rao, J. Yang, F. Yu, J.
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nides and PhICl2 was developed. This method not only
provides an alternative approach that is simple and
mild for the direct thiolation of enamines, but also
achieves a significantly improved yield of selenation
through C(sp2)-Se bond formation, affording a variety
of sulfenylated and selenenylated enamines including
indole derivatives. Furthermore, the synthetic method
was also applicable to a highly efficient synthesis of an
inhibitor for Cdc25B dual specificity protein phospha-
tase and its selenyl analogue.
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Experimental Section
To a solution of diorganyl disulfide/diselenide (0.6 mmol) in
DMF (8 mL), was added PhICl2 (0.6 mmol) at rt. The mixture
was stirred in dark for 15 min to give an orange solution. Then
the above solution was added dropwise to a solution of enamine
1 or iodole 6 (1.0 mmol) in DMF and stirred for another 30 min
until complete consumption of the starting material (monitored
by TLC). Then reaction mixture was treated with water (50 mL)
and extracted with DCM (100 mL×3). The organic phases was
combined and washed with brine (50 mL), dried over anhydrous
Na2SO4 and concentrated in vacuo. Then the residue was
purified by flash column chromatography to afford the desired
compound 2/7.
Acknowledgements
We acknowledge the National Natural Science Foundation of
China (#21472136) for financial support.
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in situ Formation of RSCl/ArSeCl and Their Oxidative
Coupling with Enaminone Derivatives Under Transition-
metal Free Conditions
Adv. Synth. Catal. 2019, 361, 1–8
Z. Shang, Q. Chen, L. Xing*, Y. Zhang, L. Wait, Y. Du*