molecules
Article
Diphenyl Diselenide-Assisted Radical Addition Reaction of
Diphenyl Disulfide to Unsaturated Bonds upon Photoirradiation
Yuki Yamamoto 1 , Qiqi Chen 2 and Akiya Ogawa 1,2, *
Citation: Yamamoto, Y.; Chen, Q.;
Ogawa, A. Diphenyl
Diselenide-Assisted Radical Addition
Reaction of Diphenyl Disulfide to
Unsaturated Bonds upon
Photoirradiation. Molecules 2023, 28,
2450. https://doi.org/10.3390/
molecules28062450
Academic Editor: Huan-Ming Huang
Received: 1 February 2023
Revised: 2 March 2023
Accepted: 2 March 2023
Published: 7 March 2023
Copyright: © 2023 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
Molecules 2023, 28, 2450. https://doi.org/10.3390/molecules28062450
1 Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University,
Osaka 599-8531, Japan
2 Department of Applied Chemistry, Graduate School of Engineering, Osaka Metropolitan University,
Osaka 599-8531, Japan
* Correspondence: ogawa@omu.ac.jp
Abstract: The addition reaction of interelement compounds with heteroatom–heteroatom single
bonds to unsaturated bonds under photoirradiation is an important method for the efficient and atom-
economical construction of carbon–heteroatom bonds. However, in practice, the desired addition
reaction is sometimes unable to proceed as expected due to the low efficiency of the desired addition
reactions or the preferential polymerization of unsaturated compounds. In this study, by combining
an interelement compound with homologous heteroatom compounds as a catalyst, we succeeded in
suppressing the polymerization of the unsaturated compounds and in attaining a highly selective
carbon–heteroatom bond formation through the desired addition reaction. In this paper, we have
examined in detail whether such a “catalytic radical reaction” proceeds for unsaturated compounds
and found that the dithiolation of some unsaturated compounds (i.e., vinylic ethers, styrenes, and
isocyanides) could proceed with the assistance of (PhSe)2 under light. The developed methods in
this study are expected to have strong implications in the fields of radical chemistry, heteroatom
chemistry, synthetic organic chemistry, and catalyst chemistry as atom-economical methods for
carbon–heteroatom bond formation.
Keywords: dichalcogenide; radical addition; radical substitution; homologous heteroatom catalyst;
unsaturated compounds
1. Introduction
Associated with “catalytic radical reaction”, two main methods are known so far. The
first method is a radical chain reaction using a peroxide or azo compound as a radical
initiator, which can be regarded as a catalyst [1–4]. The second method is a radical reaction
that proceeds via an electron transfer process from a metal or functional dye used as a
catalyst upon irradiation with visible light [5–10].
In addition to these methods, if typical element radicals can catalyze another rad-
ical reaction, it is expected to be “the third” catalytic radical reaction. For this pur-
pose, in this work, we focused on the utilization of interelement compounds bearing a
heteroatom–heteroatom single bond. Homolysis of these bonds under photoirradiation
or in the presence of radical initiators can generate heteroatom-centered radicals [11–13].
Although their characteristic features were attractive and utilized for the construction of
functional molecular scaffolds in recent decades, their catalytic use, as described above, has
been very limited [14–22].
During the course of our investigation, we have previously demonstrated that pho-
toinduced radical addition reactions of interelement compounds to a series of unsaturated
compounds proceed efficiently by the combination of interelement compounds [23–27]. In
particular, we have succeeded in regioselectively introducing multiple hetero-functional
groups into various unsaturated compounds. For example, when group 16 interelement
https://www.mdpi.com/journal/molecules
Molecules 2023, 28, x FOR PEER REVIEW 2 of 12

compounds proceed efficiently by the combination of interelement compounds [23–27].

Molecules 2023, 28, 2450
In particular,proceed
compounds we have succeeded
efficiently by in
theregioselectively
combination ofintroducing
interelementmultiple
compounds hetero-func-
[23–27].
2 of 12
tional groups into various unsaturated compounds. For example, when
In particular, we have succeeded in regioselectively introducing multiple hetero-func- group 16 interele-
ment
tionalcompounds such as unsaturated
groups into various organic disulfide or diselenide
compounds. were used
For example, whenindependently,
group 16 interele- the
photoinduced
ment compounds radical
suchaddition to alkenes
as organic disulfidebarely proceeded
or diselenide to afford
were the corresponding
used independently, the
compounds such as organic disulfide or diselenide were used independently, the photoin-
adducts in trace
photoinduced yieldsaddition
radical (Schemeto1).alkenes
In sharp contrast,
barely the photoinduced
proceeded to afford theradical addition
corresponding
duced radical addition to alkenes barely proceeded to afford the corresponding adducts in
to alkenes
adducts inproceeds regioselectively
trace yields (Scheme 1). Inwhen
sharpthecontrast,
reaction theis carried out by mixing
photoinduced radicaldisulfides
addition
trace yields (Scheme 1). In sharp contrast, the photoinduced radical addition to alkenes
and diselenides. The results can be explained by referring to the kinetic data
to alkenes proceeds regioselectively when the reaction is carried out by mixing disulfides of each step
proceeds regioselectively when the reaction is carried out by mixing disulfides and dise-
in
andthis reaction: The
diselenides. Thehighly
resultsreactive PhS• (kPhS•by
can be explained /kPhSe• = ca. 10~50)
referring [28] selectively
to the kinetic data of each attacked
step
lenides. The results can be explained by referring to the kinetic data of each step in this
the terminal
in this position
reaction: of alkenes,
The highly reactiveand the (kthus
PhS• PhS•/kformed carbon
PhSe• = ca. 10~50)radicals were selectively
[28] selectively attacked
reaction: The highly reactive PhS• (kPhS• /kPhSe• = ca. 10~50) [28] selectively attacked
trapped by (PhSe)
the terminal 2, which
position has a higher
of alkenes, and thecarbon
thus radical-trapping
formed carbon radicalsability (k (PhSe) /k
were (PhS) = ca.
selectively
2 2
the terminal position of alkenes, and the thus formed carbon radicals were selectively
160) [29,30].
trapped by (PhSe)2, which has a higher carbon radical-trapping ability (k(PhSe) /k(PhS) = ca. 2 2
trapped by (PhSe)2 , which has a higher carbon radical-trapping ability (k(PhSe)2 /k(PhS)2 = ca.
160) [29,30].
160) [29,30].

Scheme 1. Regioselective thioselenation of alkenes using a (PhS)2/(PhSe)2-mixed system.

Scheme 1.
Scheme 1. Regioselective thioselenation
thioselenation of
of alkenes
alkenes using
using aa (PhS)
(PhS)22/(PhSe)
/(PhSe)22-mixed
-mixedsystem.
system.
The concept of the “heteroatom mixed system” could be applied to a variety of un-
The
The concept
saturated compounds
concept of
ofthe “heteroatom
thesuch mixed
as alkenes,
“heteroatom system”
alkynes,
mixed could
allenes,
system” be be
applied to atovariety
vinylcyclopropanes,
could applied of unsatu-
and
a variety isocya-
of un-
rated
nides, compounds
as shown
saturated such as
in Scheme
compounds alkenes,
such2as alkynes,
[29,31–34]. allenes, vinylcyclopropanes,
In the photoinduced
alkenes, alkynes, and isocyanides,
thioselenation reactions,
allenes, vinylcyclopropanes, as
1,1-
and isocya-
shown
addition
nides, asinshown
Scheme
for in2Scheme
[29,31–34].
isocyanide, In the photoinduced
1,2-addition
2 [29,31–34]. for
In alkyne thioselenation
and
the photoinduced reactions,reactions,
allene,thioselenation
1,4-addition 1,1-addition
for conjugate
1,1-
for isocyanide,
diene,
additionandfor 1,2-addition
1,5-addition
isocyanide, for alkynefor
for1,2-addition andalkyne
vinylcyclopropane allene, 1,4-addition
successfully
and for conjugate
proceeded
allene, fordiene,
with excellent
1,4-addition and
regi-
conjugate
1,5-addition
oselectivity. for vinylcyclopropane
Furthermore,
diene, and 1,5-addition forthe successfully
photoinduced
vinylcyclopropane proceeded
addition with excellent
to alkyne
successfully withregioselectivity.
and isocyanide
proceeded was regi-
excellent also
Furthermore,
attained by the photoinduced
combining (PhS) addition
and (PhTe) to , alkyne and
affording isocyanide
the was
corresponding
oselectivity. Furthermore, the photoinduced addition to alkyne and isocyanide was also
2 2 also attained
thiotellurationby
combining
products. (PhS)
attained by combining
2 and (PhTe) , affording the corresponding thiotelluration products.
(PhS)22 and (PhTe)2, affording the corresponding thiotelluration
products.

Scheme 2. Regioselective introduction of chalcogen functional groups

groups to
to unsaturated
unsaturated compounds.
compounds.
Scheme 2. Regioselective introduction of chalcogen functional groups to unsaturated compounds.
It
It is
is known
known thatthatthe
thereaction
reactionofofa aconjugate
conjugatediene
dienewith
with(PhS) 2 causes
(PhS) polymerization
2 causes polymerizationof
the diene, resulting
of theIt diene,
is known in
resulting a lower yield
in reaction
that the a lower of of
yield the desired 1,4-dithiolation
of the desired
a conjugate diene 1,4-dithiolationproduct.
with (PhS)2 causes product.Nonetheless,
Nonethe-
polymerization
when
less,
of the this
when reaction was in
thisresulting
diene, reaction conducted
was in thein
conducted
a lower yield ofpresence
the of 301,4-dithiolation
thepresence
desired ofmol% (PhSe)
30 mol% 2 as
(PhSe) the
2 as additive,
product. the
theNonethe-
additive,
polymerization of the dienes was completely suppressed, and the conjugate
less, when this reaction was conducted in the presence of 30 mol% (PhSe) 2 as the additive, addition of
(PhS)2 to the dienes proceeded efficiently under photoirradiation for 10 h (Scheme 3) [35].
The thioselenation of conjugate diene was complete in about 2 h, and with continued
photoirradiation, the thioselenation products gradually transformed into the corresponding
dithiolation product because allyl selenide is unstable to near-ultraviolet light. These results
 the polymerization of the dienes was completely suppressed, and the conjugate addition
of (PhS)2 to the dienes proceeded efficiently under photoirradiation for 10 h (Scheme 3)
[35]. The thioselenation of conjugate diene was complete in about 2 h, and with continued
Molecules 2023, 28, 2450 photoirradiation, the thioselenation products gradually transformed into the correspond- 3 of 12
ing dithiolation product because allyl selenide is unstable to near-ultraviolet light. These
results strongly suggest the possibility of “the third” catalytic radical reaction. In some
cases, wesuggest
strongly have also
theinvestigated
possibility ofthese
“the types
third”of replacements
catalytic radical with “stoichiometric”
reaction. reac-
In some cases, we
tions; however, the substrate scope and the limitations of the “catalytic” system remain
have also investigated these types of replacements with “stoichiometric” reactions; however,
unexplored.
the substrate scope and the limitations of the “catalytic” system remain unexplored.

Scheme 3. (PhSe)22-assisted
-assisted dithiolation
dithiolation of
of conjugate
conjugate dienes
dienes with
with (PhS)
(PhS)22under
underphotoirradiation.
photoirradiation.

Hence, in this study, in order to explore the possibility of “the third” catalytic radical
reaction, we investigated
reaction, investigated the multiple introductions of chalcogen-centered functional
groups into various unsaturatedbonds
groups into various unsaturated bondsunder
underradical
radicalconditions
conditions and
and further
further examined
examined in
in detail
detail whether
whether the selenium
the selenium and tellurium
and tellurium functional
functional groupsgroups
of the of the thioselenation
thioselenation or thi-
or thiotelluration
otelluration products
products could
could be be replaced
replaced byfunctional
by sulfur sulfur functional groupsradical
groups under underreaction
radical
reaction conditions. We also discussed the possibility of constructing catalytic
conditions. We also discussed the possibility of constructing catalytic radical reactions radical
reactions based on
based on the results.the results.

2. Results and Discussion

2. Results and Discussion
In the case of organyl selenide, allylic selenides are known to be unstable under
In the case of organyl selenide, allylic selenides are known to be unstable under pho-
photoirradiated (or thermal) conditions because relatively stable allylic radicals can be
toirradiated (or thermal) conditions because relatively stable allylic radicals can be gener-
generated through the cleavage of the allylic C–Se bond. In general, the bond energy
ated through the cleavage of the allylic C–Se bond. In general, the bond energy of the C–
of the C–H bond at the allylic position (e.g., CH2 =CHCH2 –H, 87 kcal/mol) [36] can be
H bond at the allylic position (e.g., CH2=CHCH2–H, 87 kcal/mol) [36] can be estimated to
estimated to be about 15 kcal/mol less than that of the C–H bond at the primary alkyl group
be about 15 kcal/mol less than that of the C–H bond at the primary alkyl group (e.g.,
(e.g., CH3 CH2 –H, 101 kcal/mol) [37]. On the other hand, the bond energies of the C–S,
CH3CH2–H, 101 kcal/mol) [37]. On the other hand, the bond energies of the C–S, C–Se,
C–Se, and C–Te bonds are estimated to be 65.1, 56.0, and 47.8 kcal/mol, respectively [38].
and C–Te bonds are estimated to be 65.1, 56.0, and 47.8 kcal/mol, respectively [38]. Con-
Considering the replacement of C–Se bonds of the thioselenation adducts to C–S bonds
sidering the replacement of
under photoirradiation, theC–Se bonds of
following the steps
three thioselenation adductsthe
are considered to C–S
key bonds
factorsunder
for a
photoirradiation, the following
smooth transformation: three steps
(1) the cleavage are considered
of C–Se bonds under thelight,
key factors for a smooth
(2) the generation of
transformation:
the corresponding (1) relatively
the cleavage of C–Se
stable bonds under
carbon-centered light, (2)
radicals, andthe
(3)generation
the smooth oftrapping
the cor-
responding
of the carbon relatively
radicals stable
by (PhS)carbon-centered radicals, and (3) the smooth trapping of the
2 or PhS–SePh (generated in situ from (PhS)2 and (PhSe)2 ).
The formed C–S bond has a larger bond energy, and the formed dithiolation adduct might
be stable under photoirradiation. However, if the C–Se bond has a large bond energy, it
might be difficult to cleave. To achieve the efficient replacement of the C–Se bond with
the C–S bond, it is necessary to target not the usual C–Se bond but a C–Se bond activated
by some functional groups. On the other hand, the bond energy of the C–Te bond can be
 carbon
carbonradicals
radicalsby by(PhS)
(PhS)2 2ororPhS–SePh
PhS–SePh(generated
(generatedininsitu situfrom
from(PhS)
(PhS)2 2and and(PhSe)
(PhSe)2).2).The
The
formed
formed C–S bond has a larger bond energy, and the formed dithiolation adduct mightbe
C–S bond has a larger bond energy, and the formed dithiolation adduct might be
carbonunder
stable radicals by (PhS)2 or PhS–SePh (generated in situ from (PhS)2 and (PhSe)2). The
stable underphotoirradiation.
photoirradiation.However, However,ififthe theC–Se
C–Sebond bondhas hasaalarge
largebond bondenergy,
energy,itit
formed
might C–S bondto has a larger bond energy, and the replacement
formed dithiolationC–Se adduct might be
Molecules 2023, 28, 2450 mightbe bedifficult
difficult tocleave.cleave.To Toachieve
achievethe theefficient
efficient replacementofofthe the C–Sebond bond4with with
of 12
stable
the under photoirradiation. However, if the C–Se bond has a large bond energy, it
theC–S
C–Sbond,
bond,ititisisnecessary
necessarytototarget targetnot notthetheusual
usualC–SeC–Sebondbondbut butaaC–SeC–Sebondbondactivated
activated
might
by be difficult to cleave. Tothe achieve the efficient replacement of the C–Se bond with
bysome
somefunctional
functionalgroups. groups.On On theother otherhand,hand,the thebond
bondenergy
energyofofthe theC–Te
C–Tebondbondcan canbe be
the C–S
estimated bond,
to be it is
aboutnecessary
8 kcal/molto target
less not
than the
thatusual
of C–Se
the C–Se bond but
bond. a
It C–Se
may bond
be activated
possible to
estimatedtotobe
estimated beabout
about8 8kcal/mol
kcal/molless lessthan
thanthat thatofof theC–Se C–Sebond.
bond. Itmay maybe bepossible
possible to
by some
replace the functional
C–Te bond groups.
with aOnC–S the other
bond under thethe
hand,radical bond energy of It
conditions. the C–Te bond canto be
replace
replace the
the to C–Te
C–Te bond
bond with
with a C–S
a C–S bond bond under
underthat radical
radical conditions.
conditions.
estimated
Keeping be
the about 8
difference kcal/mol
in the less
bond than
energy of the
ofofC–S, C–Se
C–Se, bond.
and C–TeIt may be
bonds possible
ininmind, to
Keepingthe
Keeping thedifference
difference inainthethebondbond energy
energy of C–S, C–S,
C–Se,C–Se,
andand
C–Te C–Tebonds bonds
in mind, mind,
we
replace
we the C–Te bond with C–S bond under radical conditions.
weperformed
performed
performed
thioselenation
thioselenation
thioselenation of some
ofofsome
some
alkenes
alkenes
alkenes
by
bybyprolonging
prolonging
prolonging
photoirradiation
photoirradiation
photoirradiation and
and
andinves-
investigatedinves-
tigated Keeping
whether the thedifference in
thioselenation the bond
products energy of
changed C–S, C–Se,
totothe and C–Te
corresponding bonds in mind,
dithiolation
tigated
whether whether the
the thioselenation thioselenation
products products
changed changed
tobythe the
corresponding corresponding
dithiolation and dithiolation
products,
we performed
products, even ifthioselenation of some alkenes prolonging photoirradiation inves-
products,
even if only even ifonly
slightly. only slightly.
Theslightly.
results
The
The results
results
showed
showed
showed
that
that
thatthioselenation
thioselenation thioselenation
proceeded
proceeded
proceeded
well for
well
wellfor
alkenes for
tigated
alkenes whether
from 1a the
toto1h thioselenation
ininScheme 4,4,butproducts
no changed
dithiolation to
adduct the corresponding
was produced dithiolation
asasaabyprod-
alkenes
from from
1a to even 1a
1h inifScheme 1h Scheme
4, but no but no
dithiolation dithiolation
adduct adduct
was was produced
produced as a byproduct. byprod-In
products,
uct. only slightly. The results showed that thioselenation proceeded wellfor-
for
uct.InIncontrast,
contrast, contrast, thioselenation
thioselenationthioselenation
ofScheme
ofofbutyl
butyl vinyl butyl vinyl
ethervinyl ether
ether
1i and
1i1iand
styreneand1j styrene
styrene
resulted
1j1jresulted
inresulted
ininthe
the formation the for-
of
alkenes
mation from
ofofsmall 1a to 1h
amounts in ofofthe 4, but no dithiolation adduct was produced as a byprod-
mation
small amounts smallof amounts
the dithiolationthedithiolation
dithiolation
byproducts.
byproducts.
byproducts.
uct. In contrast, thioselenation of butyl vinyl ether 1i and styrene 1j resulted in the for-
mation of small amounts of the dithiolation byproducts.

Scheme
Scheme
Scheme4. 4.4.A
AAlist
listof
list ofofsome
somealkenes
some alkenesfor
alkenes forthe
for theattempted
the attempted dithiolation
dithiolationby
attempteddithiolation by prolonging
byprolonging the
prolongingthe photoirradiation
thephotoirradiation
photoirradiation
in the
ininthe thioselenation.
thethioselenation.
thioselenation.
Scheme 4. A list of some alkenes for the attempted dithiolation by prolonging the photoirradiation
in the thioselenation.
Based on
onthese
thesepreliminary
preliminary experiments,
experiments,we we
nextnext
focused on vinyl
focused ethersethers
on vinyl such assuch
2,3-
Based on these preliminary experiments, we next focused on vinyl ethers such as 2,3-
dihydrofuran
as 2,3-dihydrofuran
dihydrofuran totoexamine
examine bisthiolation
to examine assisted
bisthiolation
bisthiolation byby(PhSe)
assistedassisted 2, and
by
(PhSe) andthe
2,(PhSe) the2results
, results
and the were compared
results
were were
compared
with Based
those
compared ofon these
standard preliminary
terminal experiments,
alkenes such as we next
1-hexene.focused
When on
a vinyl
mixture ethers
of 1i such
(1.0 as
mmol)2,3-
with thosewith those ofterminal
of standard standard terminal
alkenes suchalkenes such When
as 1-hexene. as 1-hexene.
a mixture When
of 1ia(1.0
mixture
mmol)
dihydrofuran
and
of 1i(PhS) (1.0 to
(1.0 2mmol) examine
mmol) wasbisthiolation
and (PhS) irradiated
(1.0 mmol) assisted
for 20
wash in by
the(PhSe) 2, and the results were compared
presence
irradiated for 20of an
h in equimolar amount
the presence of anof
and (PhS) 2 (1.0 mmol) was 2irradiated for 20 h in the presence of an equimolar amount of
with
(PhSe) those
equimolar of standard
2, thioselenation
amount of terminal
product
(PhSe) , alkenes
2 and such
thioselenation as
dithiolation1-hexene.
product product
2 andWhen
3 werea mixture
obtained
dithiolation of 1i
in
product(1.0
50%3mmol)
and
were
(PhSe)2, thioselenation product 2 and dithiolation product 3 were obtained in 50% and
2
and yields,
(PhS)in
obtained 2 (1.0 mmol) was irradiated for 20 h in the presence of an equimolar amount of
50% and 10% yields, respectively (Equation (1)).
10%
10% yields, respectively
respectively (Equation
(Equation (1)).
(1)).Interestingly,
Interestingly, when
when theInterestingly,
the photoinduced
photoinduced when the
reaction
reaction
(PhSe) 2, thioselenation product 2 and dithiolation product 3 were obtained in 50% and
photoinduced
with 2,3-dihydrofuan 1k instead of 1i was conducted under the same conditions, thethe
with reaction
2,3-dihydrofuan 1k with 2,3-dihydrofuan
instead of 1i was 1k
conductedinstead of
under 1i was
the sameconducted
conditions,under
the di-
di-
10% yields,
same conditions,
thiolation respectively
product the
4 was (Equation
dithiolation
obtained as (1)).
product
the Interestingly,
4
mainwas obtained
product when
in aas41%theyield
the photoinduced
main product
along with inreaction
a
the 41%
thi-
thiolation product 4 was obtained as the main product in a 41% yield along with the thi-
with along
yield 2,3-dihydrofuan
oselenation with 1k instead
the5thioselenation of product
1i was conducted 3% under
5 in(Equation
a(Equation
yield, the same conditions,
respectively (Equation the(2)).
di-
oselenationproduct
product 5ininaa3%3%yield,
yield,respectively
respectively (2)).
(2)).
thiolation product 4 was obtained as the main product in a 41% yield along with the thi-
oselenation product 5 in a 3% yield, respectively (Equation (2)).
(1)
(1)(1)
(1)

(2)
(2)
(2)(2)

The
Theresults
resultsshown
shownininEquations
Equations(1)
(1)and
and(2)
(2)clearly
clearlyindicated
indicatedthat
thatthe
thephenylseleno
phenylseleno
group
group of the thioselenation products 2 or 5 could be replaced by a phenylthiogroup
of the thioselenation products 2 or 5 could be replaced by a phenylthio groupunder
under
The results conditions.
photoirradiation shown in Equations
The results(1) and (2) clearly
motivated us to indicated that
investigate the the phenylseleno
(PhSe) 2-catalyzed
photoirradiation conditions.
The results shown The results
in Equations motivated
(1) and us toindicated
(2) clearly investigate thethe
that (PhSe) 2-catalyzed
phenylseleno
group of the thioselenation products 2 or 5 could be replaced by a phenylthio group under
group of the thioselenation products 2 or 5 could be replaced by a phenylthio group under
photoirradiation conditions. The results motivated us to investigate the (PhSe)2-catalyzed
photoirradiation conditions. The results motivated us to investigate the (PhSe)2 -catalyzed
dithiolation of 1k, and the results are summarized in Table 1. Upon irradiation with a
tungsten lamp through Pyrex (hv > 300 nm), the reaction of 1k (1.0 mmol) with (PhS)2
(0.5 equiv.) was conducted in the presence of (PhSe)2 (30 mol%) for 20 h, yielding 29% of
the dithiolation product 4 along with the thioselenation product 5 in a 4% yield (entry 1).
Adding 0.1 mL of CDCl3 or prolonging the reaction time to 100 h did not improve the yield
 dithiolation of 1k, and the results are summarized in Table 1. Upon irradiation with a
tungsten lamp through Pyrex (hv >300 nm), the reaction of 1k (1.0 mmol) with (PhS)2 (0.5
Molecules 2023, 28, 2450 equiv.) was conducted in the presence of (PhSe) 2 (30 mol%) for 20 h, yielding 29% of 5 of 12
the
dithiolation product 4 along with the thioselenation product 5 in a 4% yield (entry 1).
Adding 0.1 mL of CDCl3 or prolonging the reaction time to 100 h did not improve the
of 4 (entries
yield 2 and2 3).
of 4 (entries andIn3).the
In latter reaction
the latter (entry
reaction 3), 3),
(entry thethe
yields of of
yields thethe
products
products 4 and
4 and 5
5decreased,
decreased, suggesting
suggestingthatthat
4 and 5 are5 unstable
4 and under
are unstable the photoirradiated
under conditions.
the photoirradiated Since
conditions.
the replacement
Since of the of
the replacement phenylseleno groupgroup
the phenylseleno of 5 with
of 5the
withphenylthio groupgroup
the phenylthio was relatively
was rel-
slow, the
atively photoinduced
slow, reactionreaction
the photoinduced of 1k with an with
of 1k equimolar mixture mixture
an equimolar of (PhS)2ofand (PhSe)
(PhS) 2 and 2
was conducted at 25 ◦ C upon irradiation with a 100 W xenon lamp for 50 h. As a result, the
(PhSe)2 was conducted at 25 °C upon irradiation with a 100 W xenon lamp for 50 h. As a
yield
result,ofthe
4 slightly
yield of improved (44% yield)
4 slightly improved (entry
(44% 5). (entry
yield) In the 5).
absence
In the of (PhSe)of
absence 2 , (PhSe)
the desired
2, the
dithiolation
desired product product
dithiolation 4 was obtained with only
4 was obtained a 6%
with onlyyield
a 6%(entry
yield6).(entry 6).

Table 1. (PhSe)
Table 1. (PhSe)22-assisted dithiolation of 2,3-dihydrofuran 1k under photoirradiation.
photoirradiation.

(PhS)2 (PhSe)2 Solvent Time Yield

Yield (%)
(%) a a
Entry (PhS)2 (PhSe) Solvent
Entry (equiv.) (mol%)3.3 (mL) (h)
Time (h) 4 [trans/cis] 5
(Equiv.) (mol%) (mL) 4
1 0.5 30 neat 20 [trans/cis]
29 [79:21] 5 4
2 1 0.50.5 30
30
CDCl
neat
3 (0.10)
20
20 20 [75:25]
29 [79:21] 4
2
3 0.5 30 CDCl3neat 100 8 N. D.
2 0.5 30 20 20 [75:25] 2
4 1.0 100 neat
(0.10) 20 41 [93:7] 3
5b3 1.00.5 30
100 neat
neat 100 50 8 [89:11] N. trace
44 D.
4 1.0 100 neat 20 41 [93:7] 3
Molecules 2023, 28, x FOR PEER REVIEW6 b
5
1.0
1.0 100
-
neat 50
neat
44 [89:11]
20 6 [83:17]
trace
N. D. 12
6 of
a Yields were determined by 1H NMR spectroscopy. b 100 W xenon lamp was used, and the reaction
6 1.0 - neat 20 6 [83:17] N. D.
was
a
conducted at 25 °C. 1 b
Yields were determined by H NMR spectroscopy. 100 W xenon lamp was used, and the reaction was conducted
at 25 ◦ C.
TableWe next investigated
2. Attempted the of
dithiolation photoinduced
styrene 1j assisteddithiolation
by (PhSe)of 2.
styrene 1j in the presence of
(PhSe) 2. To suppress the thermal polymerization of styrene 1j itself during the photoirra-
We next investigated the photoinduced dithiolation of styrene 1j in the presence of
diation,. the
(PhSe) reaction vessels (NMR tubes) were immersed in water during light exposure
2 To suppress the thermal polymerization of styrene 1j itself during the photoirradi-
to maintain the
ation, the reaction reaction temperature
vessels (NMR tubes) at 25
were °C immersed
by measuring the water
in water during temperature
light exposure withto a
thermometer. As shown in Table 2, the
◦ reaction of styrene 1j (0.5
maintain the reaction temperature at 25 C by measuring the water temperature with a ther- mmol) with (PhS) 2 (1

mmol)
mometer. in the
As presence
shown inof (PhSe)
Table 2 (30 mol%) in CDCl3 (0.5 mL) upon irradiation with a 100
2, the reaction of styrene 1j (0.5 mmol) with (PhS)2 (1 mmol)
W Xe lamp
in the presence for
(PhSe) 11 h led to the formation
of 2(PhSe)2 (30 mol%) in CDCl of 3dithiolation
CDCl (0.5
3 mL) upon product 6a and
Yield
irradiation (%) thioselenation
with
a aRecovery
100 W Xe
Entry 7a in 11% andLight
product 21% Sourcerespectively (entryTime
yields, 1). A (h)
high concentration of1jproduct
the sub-
lamp for 11(mol%)
h led to the formation of dithiolation (mL) product 6a and6a thioselenation
7a (%) a
strates under irradiation
7a in111% and3021% yields, with a 500 W Xe lamp improved the yield of 6a to 30% (entry 2).
100 Wrespectively
Xe lamp (entry
0.5 1). A high11concentration 11 of the substrates
21 33
When
under stoichiometric amounts of (PhSe) were used, the yield of 6a increased to 35% with-
2 irradiation
30 with a 500 Wlamp
Xe lamp improved the yield
10 of 6a30 to 30%N. (entry 2).
N.When
2
500 W Xe 0.1 D. D.
out the formation
stoichiometric of theofthioselenation
amounts (PhSe) were product
used, the 7a (entry
yield of 3). Using
increased up toto
35%200 mol%
without (1.0
3 100 500 W Xe lamp 2 0.1 6a
10 35 N. D. 4 the
mmol)
formationof (PhSe) produced 6a inproduct
of the2 thioselenation a similar7ayield and
(entry 3).the thioselenation
Using up to 200 mol%product 7ammol)
(1.0 in a 23% of
4 200 500 W Xe lamp 0.1 10 39 23 13
yield
(PhSe) (entry
2
a Yields
4).
produced 6a in a similar yield and the thioselenation product 7a in a 23% yield
were determined by 1H NMR spectroscopy.
(entry 4).
It was notable that (PhSe)2 -assisted dithiolation of 4-trifluoromethylstyrene 1l success-
It was notable that (PhSe)2-assisted dithiolation of 4-trifluoromethylstyrene 1l suc-
fully proceeded to form the corresponding dithiolation product 6b in 38% yield with good
cessfully proceeded to form the corresponding dithiolation product 6b in 38% yield with
product selectivity (Equation (3)).
good product selectivity (Equation (3)).

(3)(3)

For vinylic ethers and styrenes, when the photoinduced reaction was examined using
disulfides alone, a polymerization reaction occurred in preference to the desired dithiola-
tion reaction. In contrast, it was found that the dithiolation reaction proceeded when
diselenide was added to the system. These results strongly suggest that it is possible to
replace the seleno group with a thio group for alkenes having active groups such as alkoxy
and phenyl groups.
In sharp contrast to the activated alkenes such as vinylic ethers and styrenes, nonac-
tivated alkenes barely underwent photoinduced dithiolation using a (PhS) 2-(PhSe)2 binary
system. This is most probably due to the relatively strong bond energy of the C–Se bond.
es 2023, 28, x FOR PEER REVIEW 6 of 12
Molecules 2023, 28, 2450 (PhSe)2 CDCl3 Yield (%) a Recovery 6 of 12
Entry Light Source Time (h)
(mol%) (mL) 6a 7a 1j (%) a
1 30 100 W Xe lamp 0.5 11 11 21 33
2 30
Table
Table 2. Attempted 2. 500 of
dithiolation Wstyrene
Attempted Xe lamp1j assisted0.1
dithiolation of by (PhSe)2. 10
styrene 1j assisted by 302 N. D.
(PhSe) . N. D.
3 100 500 W Xe lamp 0.1 10 35 N. D. 4
4 200 500 W Xe lamp 0.1 10 39 23 13
a Yields were determined by 1H NMR spectroscopy.

It was notable that (PhSe)2-assisted dithiolation of 4-trifluoromethylstyrene 1l suc-

cessfully proceeded
(PhSe) 2 to form the corresponding
CDCl3 dithiolationYield
product
(%)6ba inRecovery
38% yield with
Entry
(PhSe)2 Light Source Time (h) Yield (%) a Recovery 1j
Entry good(mol%)
product
Lightselectivity
Source (Equation (3)).
CDCl3 (mL)
(mL) Time (h) 6a 7a 1j (%) a a
(mol%) 6a 7a (%)
1 30 100 W Xe lamp 0.5 11 11 21 33
1 30 100 W Xe lamp 0.5 11 11 21 33
2 30 500 W Xe lamp 0.1 10 30 N. D. N. D.
2 30 500 W Xe lamp 0.1 10 30 N. D. N. D.
3 3
100 100 500lamp
500 W Xe W Xe lamp 0.1 0.1 10 10 3535 N. D. 4
N. D. (3) 4
4 4
200 200 500lamp
500 W Xe W Xe lamp 0.1 0.1 10 10 3939 23 2313 13
a Yields were determined by determined
a Yields were
1H NMR spectroscopy.
by 1 H NMR spectroscopy.
For vinylic ethers and styrenes, when the photoinduced reaction was examined using
It was notable
disulfides that
alone,
For (PhSe)ethers
a vinylic 2-assisted dithiolation of 4-trifluoromethylstyrene 1l suc-
polymerization andreaction occurred
styrenes, in preference
when the photoinducedto the desired
reaction dithiola-
was examined using
cessfully proceeded to form
disulfides
tion reaction. the corresponding
alone, aitpolymerization
In contrast, was found that dithiolation
reaction product 6b in 38%
occurred in preference
the dithiolation yield
reaction proceededwith
to the desired
whendithiolation
good diselenide
product selectivity
reaction. In(Equation
was added contrast, (3)).
it was found
to the system. Thesethat the dithiolation
results reaction
strongly suggest proceeded
that whentodiselenide
it is possible
replace the wasselenoadded to with
group the system.
a thio groupThese forresults
alkenesstrongly suggest
having active that such
groups it is possible
as alkoxyto replace
and phenyl thegroups.
seleno group with a thio group for alkenes having active groups such as alkoxy and
phenyl
In sharp groups.
contrast to the activated alkenes such as vinylic ethers and styrenes,(3) nonac-
tivated alkenes barely underwent photoinduced dithiolation using a (PhS) 2-(PhSe)2 binary nonacti-
In sharp contrast to the activated alkenes such as vinylic ethers and styrenes,
system. Thisvated alkenes
is most barely due
probably underwent photoinduced
to the relatively strongdithiolation
bond energy using
of thea (PhS)
C–Se2bond.-(PhSe)2 binary
Thevinylic system.
next possibility This is most probably due to the relatively strong bond energy of theC–
C–Se bond.
For ethers andfor preferential
styrenes, whendithiolation
the photoinduced of suchreaction
simple alkenes is to utilize
was examined using the
Te bond, The next
which haspossibility
a bindingfor preferential
energy dithiolation
of 8 kcal/mol lower of than
such the
simple
C–Sealkenes
bond. isThus,
to utilize
we the C–Te
disulfides alone, a polymerization reaction occurred in preference to the desired dithiola-
bond, which has a binding energy of 8 kcal/mol lower than the C–Se bond. Thus, we next
tion reaction. In contrast, it was found that the dithiolation reaction proceeded when di-
next focused on the utilization of the thiotelluration reaction system for the catalytic
thiolation focused on the utilization of the thiotelluration reaction system for the catalytic dithiolation
diselenide was of the unsaturated
added to the system. compounds.
These resultsIn fact, we previously
strongly suggest reported
that it is two dithiolation
possible to
reactions of the unsaturated
using the compounds.
thiotelluration reaction Insystem.
fact, weOne previously
is the reported two dithiolation
regioselective dithiolation reactions
replace the seleno group with a thio group for alkenes having active groups such as alkoxy
of allenes using
in thethe thiotelluration
presence reaction system.
of stoichiometric or catalytic Oneamounts
is the regioselective
of ditelluride dithiolation
(Equation of allenes
and phenyl groups.
(4)) in the
[28].contrast presence
This dithiolation of stoichiometric
is considered or catalytic amounts of ditelluride (Equation
allenes (4)) [28].
In sharp This to the activated
dithiolation is alkenes to
considered such
to
have
have
proceeded
as vinylic
proceeded
successfully
ethers and styrenes,
successfully
because
nonac-
because allenes have an
have
tivated an accumulated
alkenes barely doublephotoinduced
underwent bond and aredithiolation
highly reactive using unsaturated
a (PhS) bonds. Another
2-(PhSe)2 binary
example accumulated doubledithiolation
bond and are highly reactive unsaturated bonds. Another
presenceexample is
system. This isisthe
the cycloadditive
most probably due
cycloadditive dithiolation of
of o-isocyanostyrene
to the relatively strong bond energy
o-isocyanostyrene
derivatives
of the in
derivatives
in the
C–Sethe bond.
presence of stoichio-
of stoichiometric
The next possibility for amounts
preferentialof ditelluride,
dithiolation inofwhich
suchthe the dithiolation
simple isreaction
alkenes reaction
to utilize was
the success-
C–
fullywhich metric
carriedhas out byamounts of
incorporatingditelluride, in which dithiolation was successfully
a rad- carried
Te bond, out bya incorporating
binding ofradical
energyradical cyclization
8 kcal/mol
cyclization lower (Equation
than the(5))
(Equation
(5)) [29].
C–Se bond.
[29].
However,
Thus, we
However, a radical dithiola-
ical dithiolation
next focused on reaction toofsimple
thereaction
utilization alkenes in thereaction
the thiotelluration presence of ditelluride
system for thehas has not yet
catalytic been
di-been
tion to simple alkenes in the presence of ditelluride not yet successful.
successful.
thiolation of the unsaturated compounds. In fact, we previously reported two dithiolation
reactions using the thiotelluration reaction system. One is the regioselective dithiolation
of allenes in the presence of stoichiometric or catalytic amounts of ditelluride (Equation
(4)) [28]. This dithiolation is considered to have proceeded successfully because allenes (4) (4)
Molecules 2023, 28, x FOR PEER
have REVIEW
an accumulated double bond and are highly reactive unsaturated bonds. Another 7 of 12
example is the cycloadditive dithiolation of o-isocyanostyrene derivatives in the presence
of stoichiometric amounts of ditelluride, in which the dithiolation reaction was success-
fully carried out by incorporating radical cyclization (Equation (5)) [29]. However, a rad-
ical dithiolation reaction to simple alkenes in the presence of ditelluride has not yet been
successful.
(5) (5)

(4)

In our previous work, photoinduced thiotelluration proceeds in alkynes and in spe-

cial alkenesInsuch
our as
previous work,1h
norbornene photoinduced
[34]. Thus, we thiotelluration
examined theproceeds in alkynes
photoinduced and in special
dithiolation
alkenes such as norbornene 1h [34]. Thus, we examined the photoinduced
of norbornene 1h using a (PhS)2-(PhTe)2 system. In the presence of (PhTe)2 (30 mol%), thedithiolation of
norbornene
thiolation 1h using
of norbornene 1haproceeded
(PhS)2 -(PhTe) 2 system.
to give In the presence
the corresponding of (PhTe)2product
bisthiolated (30 mol%),
8 the
thiolation of norbornene 1h proceeded to give the corresponding bisthiolated
and the thiotelluration product 9 in 2% and 30% yields, respectively (entry 1, Table 3). The product 8
photoinduced reaction of 1h and (PhS)2 with stoichiometric amounts of (PhTe)2 improved
the yield of the thiotelluration product 9 (entry 3). Prolonging the irradiation time with 30
mol% of (PhTe)2 improved the yield of 8 (10%) (entry 4). It was suggested that it is not
impossible to replace the C–Te bond in 9 with the C–S bond, although optimization of the
 (5)

In our previous work, photoinduced thiotelluration proceeds in alkynes and in spe-

Molecules 2023, 28, 2450 cial alkenes such as norbornene 1h [34]. Thus, we examined the photoinduced dithiolation 7 of 12
of norbornene 1h using a (PhS)2-(PhTe)2 system. In the presence of (PhTe)2 (30 mol%), the
thiolation of norbornene 1h proceeded to give the corresponding bisthiolated product 8
and the
and the thiotelluration
thiotelluration product
product 99 in
in 2%
2% and
and 30%
30% yields,
yields, respectively
respectively (entry
(entry 1,
1, Table
Table3).3). The
The
photoinducedreaction
photoinduced reactionof of1h
1hand
and(PhS)
(PhS)22 with stoichiometric
stoichiometric amounts
amounts of of (PhTe)
(PhTe)22 improved
improved
the yield of the thiotelluration
the thiotellurationproduct
product99(entry
(entry3).3).Prolonging
Prolonging the irradiation
the irradiation time
timewith
with30
30 mol%
mol% of of (PhTe)
(PhTe) improved
2 improved
2 the
the yield
yield ofof8 8 (10%)
(10%) (entry
(entry 4).
4). It
It was
was suggested
suggested that it is not
not
impossible
impossible to to replace
replace the
the C–Te
C–Tebond
bondin in99 with
with the
the C–S
C–S bond,
bond, although
although optimization
optimization of of the
the
reaction conditions is necessary.
reaction conditions is necessary.

Table3.3.Attempted
Table Attempteddithiolation
dithiolationof
ofnorbornene
norbornene1h
1hassisted
assistedby
by(PhTe)
(PhTe)2 2under
underphotoirradiation.
photoirradiation.

Yield (%) a
Yield (%) a
Entry (PhS)2 (equiv.)
(PhS)2 (PhTe) 2 (mol%)
(PhTe) 2 Time (h)
Entry Time (h) 8 9 [endo/exo]
(Equiv.) (mol%) 8 9 [endo/exo]
1 b 2.0 30 13 2 30 [23:77]
b 2.0 30 13 2 30 [23:77]
2 1 1.0 30 26 4 40 [20:80]
2 1.0 30 26 4 40 [20:80]
3 3 2.0 2.0 100
100 26 26 33 60
60 [25:75]
[25:75]
4 4 2.0 2.0 30
30 50 50 1010 39
39 [37:63]
[37:63]
5c 5c 2.0 2.0 30
30 26 26 77 40 [21:79]
40 [21:79]
aa Yields
Yieldswere
weredetermined
determined by 1by 1H NMR
H NMR spectroscopy. b Norbornene
spectroscopy. b Norbornene
1h (0.251h (0.25and
mmol) mmol)
CDCland CDCl (0.25
3 (0.25 mL)3 were
used. c Norbornenec 1h (1.0 mmol) was used.
mL) were used. Norbornene 1h (1.0 mmol) was used.

The
The experimental
experimentalresults
resultsshown
shownininTables
Tables1–3 suggest
1–3 suggest that notnot
that only the the
only weakness
weaknessof the
of
carbon–chalcogen
the carbon–chalcogen bondbond
but also
butthealsostability of the of
the stability carbon radicalsradicals
the carbon generated in the system
generated in the
by the homolytic
system cleavage
by the homolytic of the carbon–chalcogen
cleavage of the carbon–chalcogenbond are bondimportant in promoting
are important the
in promot-
replacement of the seleno
ing the replacement of theand telluro
seleno andgroups
telluro of the products
groups by the thio
of the products by group.
the thio group.
Considering
Considering the weakness
weakness of the the carbon–heteroatom
carbon–heteroatom bond and the the stability
stability of
of the
the
generated
generated radicals, we further investigated in detail the influence of
we further investigated in detail the influence of the substituents ad- the substituents
adjacent
jacent to to
thethe carbon
carbon radicals
radicals on on
thethe radical
radical substitution
substitution reaction.
reaction. In the
In the casecase of alkenes,
of alkenes, the
the reaction proceeds by 1,2-addition, whereas the reaction of isocyanides
reaction proceeds by 1,2-addition, whereas the reaction of isocyanides bearing a C–N bearing a C–N
un-
unsaturated
saturated bond bond proceeds
proceeds by by 1,1-addition.
1,1-addition. Therefore,
Therefore, the the heteroatom
heteroatom radical
radical attacks
attacks the
the isocyanide
isocyanide to form
to form a radical
a radical on theon carbon
the carbon
of theofC=N
the C=Nbond bond, , whichwhich is affected
is affected by
by the
the heteroatom group and the C–N double bond. Using isocyanide
heteroatom group and the C–N double bond. Using isocyanide as a substrate, we investi- as a substrate, we
investigated the photoinduced
gated the photoinduced addition
addition reaction
reaction and found
and found that,that, interestingly,
interestingly, the the catalytic
catalytic di-
dithiolation reaction with (PhS)
thiolation reaction with (PhS)2 occurs 2 occurs in the presence of (PhSe)
in the presence of (PhSe)2. 2 .
As
As shown
shownininTableTable4, the reaction
4, the of cyclohexyl
reaction isocyanide
of cyclohexyl isocyanide10a (0.25
10ammol) with (PhS)
(0.25 mmol) with 2
(2.0 equiv.) in the presence of (PhSe)
(PhS)2 (2.0 equiv.) in the presence of (PhSe) 2 (30 mol%) under light afforded the
2 (30 mol%) under light afforded the 1,1-addi-
1,1-addition
product 11a in11a
tion product good yield yield
in good (entry(entry
1). High1). concentration
High concentration of the of starting materials
the starting led to the
materials led
corresponding dithiolation product 11a in up to 81% yield (entry 3).
to the corresponding dithiolation product 11a in up to 81% yield (entry 3). It is noteworthyIt is noteworthy that
the
thatthioselenation adduct
the thioselenation 12a was
adduct 12aobtained in traceinyields
was obtained trace under
yields the conditions
under of entries
the conditions of
1–3; therefore, the transformation of the in situ-generated 12a to the dithiolation adduct
entries 1–3; therefore, the transformation of the in situ-generated 12a to the dithiolation
11a might proceed very smoothly under these conditions. In the absence of (PhSe)2 , the
yield of 11a dramatically decreased, indicating that the presence of catalytic amounts of
(PhSe)2 was essential for the efficient transformation of 10a to 11a (entry 4).
Molecules Molecules
2023, 28, x2023,
FOR28,
PEER REVIEW
x FOR PEER REVIEW 8 of 12 8 of 12

adduct 11a might

adduct 11aproceed very smoothly
might proceed under these
very smoothly underconditions. In the absence
these conditions. of (PhSe)
In the absence of2,(PhSe)2,
Molecules 2023, 28, 2450 8 of 12
the yield of 11a dramatically decreased, indicating that the presence of catalytic amounts
the yield of 11a dramatically decreased, indicating that the presence of catalytic amounts
of (PhSe) was essential
of2 (PhSe) for the efficient
2 was essential transformation
for the efficient of 10a toof11a
transformation 10a(entry
to 11a4).
(entry 4).

Table 4. Table
Optimization
Table of the reaction
Optimization
4. Optimization ofofthe conditions
thereaction for (PhSe)
reactionconditions
conditions
for2-catalyzed
for (PhSe)
(PhSe) 2dithiolation
-catalyzed
2-catalyzed of cyclohexyl
dithiolation
dithiolation ofiso-
cyclohexyl
of cyclohexyl iso-
cyanide cyanide
10a.
isocyanide
10a.10a.

CDCl3 CDCl3 Yield (%) a

Yield (%) (%)
a
a Recovery of
Recovery of
Entry Entry Time (h)
Time (h) Yield
Entry(mL) CDCl Time11a 12a 10a (%) aRecovery of
(mL)3 (mL) (h) 11a 12a 10a (%) a
10a (%) a
11a 12a
1 1 0.50 0.50 50 50 45 45 trace trace 50 50
2 1 0.50 50 61 45trace trace 31 50
2 0.10 0.10 24 24 61 trace 31
2 0.10 24 61 trace 31
3 33 0.10 0.1050
0.10 50 5081 (70) 81 (70) trace tracetrace 13
81 (70) 1313
4b 44bb 0.10 0.1050
0.10 50 50 11 11 11N. D. N. D. N. D. 85 8585
a Yields were determined
aa Yields
Yields by 1Hby
weredetermined
were determinedNMR
1by spectroscopy
1H
H NMRNMR (isolated
spectroscopy
spectroscopy yield).
yield). bIn
(isolated
(isolated
b
Inthe
theabsence
yield). b In the of
absence (PhSe)of
absence
of (PhSe) . 2. (PhSe)2.
2

SchemeScheme
5 shows the scope
theand limitations of the (PhSe) -catalyzed dithiolation of
Scheme 55 shows
shows the scope
scope and limitations
and limitations of the
of the2(PhSe)
(PhSe) 2-catalyzed
2
-catalyzed dithiolation
dithiolation of
of
isocyanides. Various
isocyanides. isocyanide derivatives
Variousisocyanide could
isocyanidederivatives be tolerated
derivativescould
couldbebe by the
tolerated catalytic dithiola-
isocyanides. Various tolerated byby thethe catalytic
catalytic dithiola-
dithiolation,
tion, and theand
tion, corresponding adductsadducts
the corresponding 11a–11e11a–11e
were obtained in moderate to goodtoyields
and the corresponding adducts 11a–11e were were obtained
obtained in moderate
in moderate to good good
yieldsyields
with
with excellent
with productproduct
excellent selectivity.
selectivity.
excellent product selectivity.

Scope and limitations

limitations of a a
Scheme
Scheme Scheme 5.
5. Scope 5.
and limitations
Scope and of the
of the (PhSe) (PhSe)
2-catalyzed
the -catalyzed dithiolation
dithiolation
(PhSe)22-catalyzed of
of isocyanides
of isocyanides
dithiolation a.. were
a. a Yields
isocyanides Yields were
a Yields were
determined by 1 H NMR spectroscopy (isolated yields). b Reactionctime: 23c h. c The reaction was
determined by 1H NMR spectroscopy (isolated yields). b Reaction time: 23 h. The reaction
determined by H NMR spectroscopy (isolated yields). Reaction time: 23 h. The reaction was con-
1 b was con-
ducted without
conducted
ducted the without
solvent.
without the the solvent.
solvent.

As described
As described
As described
above, in above, ininthe
the addition
above, theaddition
addition
to to to
isocyanides, isocyanides,
the C–Se
isocyanides, the
bond
the C–SeC–Se bond
generated
bond generated
by by
thi- by thi-
generated
thioselenation
oselenation could be could
converted be converted
to a C–S to
bond a C–S
more bond more
efficiently efficiently
than in the
oselenation could be converted to a C–S bond more efficiently than in the addition of al-than in
addition the addition
of al- of
alkenes.
kenes. In In other
otherInwords,
kenes. words, in the
in the thioselenation
other words, thioselenation
of isocyanides,
in the thioselenation of isocyanides,
an addition
of isocyanides, an addition
productproduct
an addition product with
with anwith an
an imino
imino group
imino group (PhS–C(=N–R)–SePh)
(PhS–C(=N–R)–SePh)
group (PhS–C(=N–R)–SePh) is formed, isand
formed,
is formed, theand and
additiontheaddition
the addition
of a thiylofofradical
aathiyl
thiylradical
radical
to this toto this
this
C=N bondC=N
C=N bond
and and
theand
bond the
subsequentsubsequent
elimination
the subsequent elimination of
of the seleno
elimination the seleno
of theradical
seleno canradical can
efficiently
radical efficiently replace
replace replace
can efficiently the the
the
selenoof
seleno group
seleno group of
of the
the thioselenation
the thioselenation
group product
thioselenation product
with a with
product thio aathio
withgroup; thiogroup;
thus,
group; thus,
thus,catalytic
catalytic dithiolation
dithiolation
catalytic dithiolation is
considered
is considered to to
proceed proceed
well. well.
is considered to proceed well.
3. Materials and Methods
3.1. General Information
Unless otherwise stated, all starting materials were purchased from commercial
sources and used without further purification. Isocyanide derivatives 10b–10e were pre-
pared according to the previously reported procedures [39]. All solvents were distilled and
Molecules 2023, 28, 2450 9 of 12

degassed with argon before use. 1 H and 13 C{1 H} NMR spectra were recorded in CDCl3
using a Bruker BioSpin Ascend 400 spectrometer (Tokyo, Japan) at 400 and 100 MHz, respec-
tively, with Me4 Si as the internal standard. High-resolution mass spectra were obtained
on the JEOL JMS-700 Mstation (Tokyo, Japan) in the analytical section of the Nanotech-
nology Platform Program of the Nara Institute of Science and Technology (NAIST). The
characterization data of compounds are shown as follows (1 H and 13 C{1 H} NMR spectra
are included in the Supplementary Materials).

3.2. (PhSe)2 -Assisted Dithiolation of 2,3-Dihydrofuran 1k under Photoirradiation

In a sealed Pyrex NMR tube under an argon atmosphere, 2,3-Dihydrofuran 1k
(1.0 mmol), (PhS)2 (1.0 mmol), and (PhSe)2 (1.0 mmol) were placed, and the mixture
was irradiated with a tungsten lamp (500 W) at a distance of 5 cm for 50 h at 40 ◦ C. After the
reaction, the resulting mixture was transferred to a flask, the solvent was removed under
reduced pressure, and the residue was analyzed by NMR spectroscopy using 1,3,5-trioxane
as the internal standard. The production of 4 was determined and characterized from the
reported 1 H and 13 C{1 H} NMR data (Table 1) [40].

3.3. (PhSe)2 -Assisted Dithiolation of Styrene 1j under Photoirradiation

Styrene 1j (0.5 mmol), (PhS)2 (1.0 mmol), and (PhSe)2 (30 mol%) in degassed CDCl3
(0.1 mL) were placed in a sealed Pyrex NMR tube under an argon atmosphere, and the
mixture was irradiated with a xenon lamp (500 W) at a distance of 5 cm for 50 h at 25 ◦ C.
To suppress the thermal polymerization of styrene 1j itself during the photoirradiation, the
reaction vessels (NMR tubes) were immersed in water during light exposure to maintain
the reaction temperature at 25 ◦ C by measuring the water temperature with a thermometer.
After the reaction, the resulting mixture was transferred to a flask, the solvent was removed
under reduced pressure, and the residue was analyzed by NMR spectroscopy using 1,3,5-
trioxane as the internal standard. The production of 6a was determined and characterized
from the reported 1 H and 13 C{1 H} NMR data (Table 2) [41].

3.4. (PhTe)2 -Assisted Dithiolation of Norbornene 1h under Photoirradiation

Norbornene 1h 1j (0.5 mmol), (PhS)2 (2.0 mmol), and (PhTe)2 (30 mol%) in degassed
CDCl3 (0.05 mL) were placed in a sealed Pyrex NMR tube under an argon atmosphere,
and the mixture was irradiated with a tungsten lamp (500 W) at a distance of 5 cm for
50 h. After the reaction, the resulting mixture was transferred to a flask, the solvent was
removed under reduced pressure, and the residue was analyzed by NMR spectroscopy
using 1,3,5-trioxane as the internal standard. The production of 8 and 9 was determined
and characterized from the reported 1 H and 13 C{1 H} NMR data (Table 3) [34].

3.5. General Procedure for the (PhSe)2 -Catalyzed Dithiolation of Isocyanides

Isocyanide 10 (0.25 mmol), (PhS)2 (2.0 mmol), and (PhSe)2 (30 mol%) in degassed
CDCl3 (0.1 mL) were placed in a sealed Pyrex NMR tube under an argon atmosphere, and
the mixture was irradiated with a tungsten lamp (500 W) at a distance of 5 cm for 50 h at
40 ◦ C. After the reaction, the resulting mixture was transferred to a flask, and the solvent
was removed under reduced pressure. Finally, the residue was purified by preparative thin-
layer chromatography (eluent: iso-hexane/Et2 O) to obtain the corresponding dithiolation
product 11 (Scheme 5).
Diphenyl cyclohexylcarbonimidodithioate (11a) [CAS no. 924622-07-1] [31]. White
solid, 57.5 mg, 70%; 1 H NMR (400 MHz, CDCl3 ) δ 7.51 (d, J = 6.8 Hz, 2H), 7.35-7.26 (m,
8H), 3.81-3.75 (m, 1H), 1.68-1.65 (m, 4H), 1.56-1.54 (m, 2H), 1.43-1.18 (m, 4H); 13 C{1 H} NMR
(100 MHz, CDCl3 ): δ 151.9, 135.1, 134.0, 131.6, 130.5, 129.0 (two carbons were overlapped),
128.4, 128.2, 62.6, 33.0, 25.8, 24.2.
Diphenyl (2-(cyclohex-1-en-1-yl)ethyl)carbonimidodithioate (11b) [CAS no. 924622-08-
2] [31]. Yellow oil, 63.3 mg, 66%; 1 H NMR (400 MHz, CDCl3 ) δ 7.56-7.54 (m, 2H), 7.39-7.34
(m, 5H), 7.28-7.26 (m, 3H), 5.37-5.37 (m, 1H), 3.60 (t, J = 7.0 Hz, 2H), 2.18 (t, J = 7.1 Hz, 2H),
Molecules 2023, 28, 2450 10 of 12

1.98-1.97 (m, 2H), 1.88-1.88 (m, 2H), 1.62-1.51 (m, 4H); 13 C{1 H} NMR (100 MHz, CDCl3 ): δ
154.6, 135.8, 135.1, 134.5, 131.0, 130.1, 129.2, 129.1, 128.6, 128.5, 122.6, 53.3, 38.6, 28.5, 25.4,
23.1, 22.5.
Diphenyl (3-phenylpropyl)carbonimidodithioate (11c). Yellow oil, 38.4 mg, 44%; 1 H
NMR (400 MHz, CDCl3 ) δ 7.58-7.56 (m, 2H), 7.43-7.35 (m, 5H), 7.31-7.30 (m, 3H), 7.27-7.24
(m, 2H), 7.18-7.14 (m, 1H), 7.10-7.08 (m, 2H), 3.48 (t, J = 6.6 Hz, 2H), 2.56 (t, J = 7.8 Hz, 2H),
1.87-1.80 (m, 2H); 13 C{1 H} NMR (100 MHz, CDCl3 ): δ 155.0, 142.3, 135.4, 134.8, 131.0, 129.8,
129.3, 129.1, 128.7, 128.6 (two carbons were overlapped), 128.3, 125.7, 53.2, 33.5, 32.3; HRMS
(CI) calcd for C22 H22 NS2 [M+H]+ : 364.1194, found: 363.1194.
Diphenyl octylcarbonimidodithioate (11d). Colorless oil, 57.2 mg, 59%; 1 H NMR
(400 MHz, CDCl3 ) δ 7.55-7.54 (m, 2H), 7.39-7.34 (m, 5H), 7.30-7.27 (m, 3H), 3.49 (t, J = 6.9 Hz,
2H), 1.56-1.51 (m, 2H), 1.34-1.25 (m, 10H), 0.90-0.87 (m, 3H); 13 C{1 H} NMR (100 MHz,
CDCl3 ): δ 154.3, 135.2, 134.4, 131.1, 130.1, 129.2, 129.1, 128.6, 128.5, 54.3, 31.9, 30.4, 29.3
(two carbons were overlapped), 27.3, 22.7, 14.2; HRMS (CI) calcd for C21 H28 NS2 [M+H]+ :
358.1663, found: 358.1670.
Diphenyl benzylcarbonimidodithioate (11e) [CAS no. 924622-05-9] [31]. White solid,
25.4 mg, 28%; 1 H NMR (400 MHz, CDCl3 ) δ 7.61 (dd, J = 7.8, 1.5 Hz, 2H), 7.43-7.37 (m,
5H), 7.33-7.30 (m, 3H), 7.27-7.23 (m, 2H), 7.20-7.15 (m, 3H), 4.72 (s, 2H); 13 C{1 H} NMR
(100 MHz, CDCl3 ): δ 157.0, 139.6, 135.6, 135.1, 130.7, 129.6, 129.4, 129.2, 128.8, 128.7, 128.2,
127.2, 126.5, 57.0.

4. Conclusions
In this study, we investigated the multiple introductions of chalcogen functional
groups into various unsaturated bonds under radical conditions and examined in detail
whether the selenium and tellurium functional groups of the thioselenation or thiotellura-
tion products can be replaced by a sulfur functional group under radical reaction conditions.
For simple alkenes without an active substituent, it was difficult to replace the C–Se or C–Te
bond of the thioselenation or thiotelluration products with a C–S bond, but for the activated
alkenes such as vinylic ethers and styrenes, it was found that it was possible to replace the
seleno group with a thio group. In addition, isocyanides were successfully bisthiolated by
photoirradiation in the presence of catalytic (PhSe)2 to afford the corresponding adducts in
moderate to high yields with excellent product selectivity. Although the establishment of a
“third” catalytic radical reaction, in which a typical element radical catalyzes the radical re-
actions of a homologous heteroatom compound, is still a challenge, the relative reactivities
of unsaturated compounds demonstrated in this study are a new milestone in considering
the substitution of the carbon–chalcogen bond by sulfur functional groups under radical
conditions. We believe that this research on the development of a “third” catalytic radical
reaction will lead to a new approach for the precise introduction of heteroatom-centered
functional groups.

Supplementary Materials: The following supporting information can be downloaded at: https:
//www.mdpi.com/article/10.3390/molecules28062450/s1. Copies of 1 H and 13 C{1 H} NMR spectra.
Author Contributions: Investigation, Y.Y., Q.C. and A.O.; formal analysis, Y.Y. and Q.C.; resources,
Y.Y., Q.C. and A.O.; writing—original draft preparation, Y.Y. and A.O.; writing—review and editing,
Y.Y., Q.C. and A.O.; funding acquisition, Y.Y. and A.O. All authors have read and agreed to the
published version of the manuscript.
Funding: This work was supported by JSPS KAKENHI Grant Numbers 22J14638 and 22H02124, the
Ministry of Education, Culture, Sports, Science, and Technology, Japan, and also the Nanotechnology
Platform Program of the Nara Institute of Science and Technology (NAIST).
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: The data presented in this study are available in the article and in its
Supplementary Materials.
Molecules 2023, 28, 2450 11 of 12

Acknowledgments: Y.Y. thanks the Japan Society for the Promotion of Science for the Research
Fellowship for Young Scientists.
Conflicts of Interest: The authors declare no conflict of interest.
Sample Availability: Samples of the compounds are not available from the authors.

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