Photoinduced syntheses and reactivities of phosphorus-containing interelement compounds

Article abstract of DOI:10.1021/acs.joc.0c02014

The photoinduced reactions of tetraphenyldiphosphine disulfide with a range of organic dichalcogenides successfully afforded a series of phosphorus(V)-chalcogen interelement compounds via a radical process. The relative reactivities of the organic dichalcogenides (i.e., (PhS)₂, (PhSe)₂, and (PhTe)₂) toward the P^III or P^V groups in the diphosphine analogues under light were investigated in detail, and a convenient method was developed to form P-S or P-Se interelement compounds from tetraphenyldiphosphine disulfide and (PhS)₂ or (PhSe)₂ upon photoirradiation. Furthermore, the relative photochemical properties and reactivities of tetraphenyldiphophine (P- P interelement compound) and its analogues toward photoinduced radical addition reactions were also discussed. The formed P-E (E = S, Se) interelement compounds could be utilized for ionic reactions, and they could be transformed into various phosphine reagents via one-pot processes.

Full text of DOI:10.1021/acs.joc.0c02014

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Article
Photoinduced Syntheses and Reactivities of Phosphorus-Containing
Interelement Compounds
Yuki Yamamoto, Ryo Tanaka, Miyuto Ota, Misaki Nishimura, Cong Chi Tran, Shin-ichi Kawaguchi,
Shintaro Kodama, Akihiro Nomoto, and Akiya Ogawa*
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ABSTRACT: The photoinduced reactions of tetraphenyl-
diphosphine disulfide with a range of organic dichalcogenides
successfully afforded a series of phosphorus(V)−chalcogen
interelement compounds via a radical process. The relative
reactivities of the organic dichalcogenides (i.e., (PhS)2, (PhSe)2,
and (PhTe)2) toward the PIII or PV groups in the diphosphine
analogues under light were investigated in detail, and a convenient
method was developed to form P−S or P−Se interelement
compounds from tetraphenyldiphosphine disulfide and (PhS)2 or
(PhSe)2 upon photoirradiation. Furthermore, the relative photo-
chemical properties and reactivities of tetraphenyldiphophine (P−
P interelement compound) and its analogues toward photoinduced radical addition reactions were also discussed. The formed P−E
(E = S, Se) interelement compounds could be utilized for ionic reactions, and they could be transformed into various phosphine
reagents via one-pot processes.
regioselectively after treatment with elemental sulfur (Scheme
1-(2)).7 In addition, we found that tetraphenyldiphosphine
monosulfide 1c is more reactive than 1b (Scheme 1-(3)).8 In
particular, the radical addition of 1c to cyclic alkenes was
efficient, whereas this was not the case for 1b. Tetraphenyl-
diphosphine disulfide 1d, which bears a PV−PV linkage, is
usually the most reactive species for the radical addition to
alkenes, which reaches completion upon photoirradiation for
over 6 h (Scheme 1-(4)).9 The obtained vicinal diphosphine
derivatives are useful bidentate ligands for transition-metal-
catalyzed reactions and are promising eco-friendly flame
retardants.
In addition to bisphosphination reactions, phosphination
accompanied by the simultaneous introduction of other
heteroatom groups is a fascinating pathway in synthetic
organic chemistry, since it allows the direct syntheses of
multifunctionalized molecules as promising synthetic inter-
mediates for functional materials and bioactive compounds.
Hence, we previously studied a series of photoinduced
addition reactions of diphosphine 1a to alkynes in the presence
of organic dichalcogenides such as (PhS)2 9a, (PhSe)2 12a,
INTRODUCTION
■
Interelement compounds, which contain a heteroatom−
heteroatom linkage, are versatile synthetic intermediates for
the introduction of heteroatom-based functional groups into
organic molecules.1 For this purpose, Lewis acids and bases or
transition metal catalysts have generally been employed to
activate heteroatom−heteroatom linkages.2 Furthermore, the
homolytic cleavage of heteroatom−heteroatom linkages upon
heating or photoirradiation can also be employed. Notably, the
photoinduced radical addition of interelement compounds to
carbon−carbon unsaturated bonds is of great importance in
the context of green chemistry, since this reaction can achieve a
high atom economy under metal-free conditions using sunlight
or related light sources.3
Recently, we developed a series of photoinduced radical
addition reactions using P−P linkage compounds composed of
trivalent and/or pentavalent phosphorus groups, as outlined in
Scheme 1.4
More specifically, we initially focused on tetraphenyl-
diphosphine 1a, which contains a PIII−PIII interelement
linkage. Upon irradiation with a Xe lamp through Pyrex, a
radical addition of 1a to terminal alkynes successfully occurred
to afford the corresponding 1,2-adduct 2, where the (Z)-
isomers were formed as the major product (Scheme 1-(1)).5,6
Although the radical addition of 1a to alkenes did not occur,
tetraphenyldiphosphine monoxide 1b bearing a PIII−PV linkage
successfully added to terminal alkenes to afford the
corresponding bis(phosphino)alkanes 1-P-oxide 2-P-sulfide 5
Special Issue: The New Golden Age of Organo-
phosphorus Chemistry
Received: August 20, 2020
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Scheme 1. Photoinduced Addition of Diphosphine and its Analogues to Alkenes/Alkynes
Scheme 2. Reactive Intermediates Generated from the Interelement Compounds
and (PhTe)2 15a (Scheme 2). The combination of
diphosphine 1a and dichalcogenides resulted in the highly
regioselective phosphinochalcogenation of alkynes under light.
In the case of (PhS)2 9a10,11 or (PhSe)2 12a,12 the PhS or
PhSe group and the Ph2P group were regioselectively
introduced into the terminal and inner positions, respectively
(Schemes 2-(1) and 2-(2)). In the case of (PhTe)2 15a, a
different regioselectivity was observed, where the Ph2P and
PhTe groups were introduced into the terminal and inner
positions, respectively (Scheme 2-(3)).13 These results may
indicate the relative reactivities of the heteroatom radicals
toward C−C unsaturated bonds (i.e., PhS· > PhSe· > Ph2P· >
PhTe·); however, this had not been examined on a mixed
system of dichalcogenides and diphosphine analogues, such as
diphosphine disulfide 1d. Hence, we herein report the
photoinduced reactions of diphosphine disulfide 1d with
organic dichalcogenides to afford phosphorus−chalcogen
interelement compounds. These phosphorus−chalcogen inter-
element compounds have been synthesized mainly by ionic
reactions. The present photoinduced method proceeds via a
novel radical process, which makes it possible to synthesize a
new series of P−S and P−Se interelement compounds
successfully.
RESULTS AND DISCUSSION
■
Prior to describing the photoinduced reaction of diphosphine
disulfide 1d with organic dichalcogenides 9a, 12a, and 15a, we
wish to clarify photochemical properties and relative
reactivities of the diphosphine analogues in the radical addition
to alkenes.
Diphosphine disulfide 1d, bearing no trivalent phosphine
group, is both air- and moisture-stable and can be stored at
room temperature in the dark for a few months.9 In contrast,
diphosphines 1a−1c, which contain trivalent phosphine
groups, are air- and moisture-sensitive and require handling
in a glovebox or using the Schlenk technique; diphosphine 1a
is particularly air-sensitive. Considering the relative stabilities
of 1a−1d, diphosphine disulfide 1d can be assumed to possess
a high generality as a synthetic reagent.
The UV−visible spectra of 1a−1d are shown in Figure 1. As
indicated, diphosphine 1a presents an absorption maximum in
the UV and near-UV regions, although the absorption cutoff
reaches 360 nm. Compared to 1a, diphosphine monoxide 1b
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phenyl diphenylphosphinoselenodithioate 20a (43% yield),
respectively, as the sole products (eqs 2 and 3). Under these
conditions, however, no addition products based on the
phosphorus and/or chalcogen functional groups were formed.
It is expected that the obtained PV−S and PV−Se
interelement compounds 19a and 20a will be promising
synthetic reagents and intermediates for the syntheses of
multifunctionalized organic molecules,14−21 use in living
polymerization processes,22 and trapping of radical spe-
cies.23−25 Although a number of synthetic methods for 19a,
20a, and their related derivatives have been reported, the
majority involve ionic pathways, such as nucleophilic
substitution using air- and moisture-sensitive phosphorus
sources (e.g., Ph2P(S)−SH, Ph2P(S)−Cl).26−34 Recently, a
transition-metal-catalyzed route to synthesis of 19a and its
related derivatives has also been reported.35
However, no examples of radical methods for the
preparation of PV−S and PV−Se interelement compounds
have been reported, despite the fact that radical methods are
generally advantageous in terms of their excellent tolerances to
a wide variety of functional groups and solvents. The results
obtained for the reactions outlined in eqs 2 and 3 strongly
suggest that the photoinduced reaction between the air- and
moisture-stable tetraphenyldiphosphine disulfide 1d and either
diphenyl disulfide 9a or diselenide 12a may be a powerful tool
to obtain PV−S and PV−Se interelement compounds.
Figure 1. UV−visible spectra of diphosphine analogues 1a−1d in
CH2Cl2 (7.0 × 10−5 M).
and monosulfide 1c exhibit weaker absorptions, and their
cutoffs reach 318 and 345 nm, respectively.
To avoid the π−π* transition of the alkene and alkyne
carbon−carbon unsaturated bonds, it is convenient to use light
from the near-UV (300−400 nm) and/or visible (400−800
nm) regions for the photoinduced addition of heteroatom−
heteroatom interelement compounds to alkenes and alkynes.
As can be seen from Figure 1, the photoinduced addition of
diphosphine monoxide 1b is less efficient compared to those
the other diphosphine analogous; therefore, prolonged photo-
irradiation was necessary for the addition of 1b to alkenes.
In terms of the relative reactivities of tetraphenyl-
diphosphine monoxide 1b and monosulfide 1c, our previous
results8 indicate that, compared with 1b, tetraphenyl-
diphosphine monosulfide 1c is more reactive toward the
photoinduced radical addition to alkenes. For example, upon
irradiation with a Xe lamp through Pyrex for 6 h, the reaction
of 1c with 1-dodecene afforded adduct 6a in 87% yield, while
adduct 4a was obtained from 1b in only 6% yield under the
same reaction conditions.
Hence, we subsequently investigated the photoinduced
synthesis of phosphorus−chalcogen interelement compounds
using 1d and organic dichalcogenides 9a, 12a, and 15a (eq 4).
Thus, we initially investigated the photoinduced formation
of the P−S linkage from Ph2P(S)−P(S)Ph2 1d and PhS−SPh
9a (Table 1). When equimolar amounts of 1d and 9a in
Table 1. Reaction of Tetraphenyldiphosphine Disulfide 1d
with Diphenyl Disulfide 9a under Light Irradiation
Tetraphenyldiphosphine derivatives bearing trivalent phos-
phorus unit(s), such as in the cases of 1a−1c, undergo
photoinduced homolysis to generate the corresponding
phosphino radicals, and in the absence of alkenes or alkynes,
the generated phosphino radicals recombine to reform the
starting diphosphine derivatives without the formation of any
other phosphorus compounds. In contrast, tetraphenyl-
diphosphine disulfide 1d forms an equilibrium mixture of 1e,
1c, 1f, and 1d upon photoirradiation, as shown in eq 1.9
Among the various components of the equilibrium mixture, 1e
may be a key species for trapping radical intermediates. When
a radical species attacks the −PIIIPh2 group, the reaction with
1e is favorable in comparison with those with 1c, 1d, and 1f,
since the presence of a −S− bond between the PIII and PV
groups leads to reduction of steric hindrance at the PIII site.
Keeping the above-mentioned features in the radical
addition of diphosphine derivatives 1a−1d to alkenes or
alkynes in mind, we investigated the photoinduced reactions of
diphenylphosphine disulfide 1d with diphenyl disulfide 9a and
diselenide 12a in the presence of alkynes to selectively afford S-
phenyl diphenylphosphinodithioate 19a (25% yield) and Se-
a
a
Entry
Time (h)
Yield 19a (%)
Recovery 1d (%)
1
2
3
1
3
5
9
12
14
7
76
52
46
33
4
33
42
57
76
b
4
5
6
78
trace
a
b
Determined by 31P NMR spectroscopy. In entry 4, the yield (57%)
of 19a was higher than that (25%) in a similar reaction in the
presence of phenylacetylene (eq 2). This might be because the
absorption of phenylacetylene (or its oligomers formed during the
reaction) retarded the formation of 19a.
dichloromethane were irradiated through Pyrex with an Xe
lamp (λ > 300 nm), the desired P−S interelement compound
19a was gradually formed over time, giving a 78% yield after 14
h (entry 6).
Figure 2 shows the UV−visible spectra of diphosphine
disulfide 1d, diphenyl disulfide 9a, diselenide 12a, and
C
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equilibrium mixture of 1e, 1c, 1f, and 1d (see eq 1) formed by
the photoirradiation of 1d being observed by 31P NMR
measurements. Since the radical-capturing ability of (PhS)2 is
known to be particularly low (k(PhSe) /k(PhS) = ca. 160),36 the
2
2
highly reactive PhS• could be efficiently trapped by the
equilibrium mixture, especially by Ph2P(S)−S−PPh2 1e, to
afford the P−S interelement compound 19a (vide post; see
Scheme 3).
We then examined the photoinduced reaction of
tetraphenyldiphosphine disulfide 1d and diphenyl diselenide
12a (Table 2). Upon increasing the reaction time, the P−Se
ditelluride 15a, which suggest that the photoinduced
homolysis of diphosphine disulfide 1d and dichalcogenide
9a, 12a, or 15a may occur competitively. However, in general,
only the starting materials 1d and 9a and the product 19a were
observed during the reaction, with only a trace amount of the
Figure 2. UV−visible spectra of diphosphine disulfide 1d and dichalcogenides 9a, 12a, and 15a in EtOH (2.0 × 10−4 M).
D
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Scheme 3. Possible Reaction Pathways for the Formation of P−S or P−Se Interelement Compounds
the photoirradiation conditions, owing to their poor solubilities
in CH2Cl2, and could not be isolated owing to contamination
from the equilibrium mixture of 1e, 1c, 1f, and 1d.
Furthermore, aliphatic disulfides, such as 9d and 9e, were
converted to the corresponding PV(S)−S interelement
compounds 19d and 19e in excellent yields. This reaction
could also be conducted using 1d and 9d in gram scale, and
the corresponding PV−S interelement compound 19d was
successfully obtained in 91% isolated yield (1.45 g).
Table 2. Reaction of Tetraphenyldiphosphine Disulfide 1d
with Diphenyl Diselenide 12a under Light Irradiation
a
a
Entry
Time (h)
Yield 20a (%)
Recovery 1d (%)
1
2
3
4
5
1
4
12
18
24
7
22
55
66
78
76
62
28
15
4
For the synthesis of Se-phenyl diphenylphosphinoseleno-
dithioate derivatives 20a−e, diaryl diselenides bearing
electron-withdrawing groups, such as p-chloro, p-fluoro, p-
trifluoromethyl, and m-trifluoromethyl groups, smoothly
afforded the corresponding PV(S)−Se interelement com-
pounds in good yields (20b−20e). Unfortunately, bis(p-
methoxyphenyl) diselenide and bis(o,p-dimethylphenyl) dis-
elenide, which were among the electron-rich diselenides,
reacted only slightly with 1d to afford the corresponding
PV(S)−Se compounds in poor yields (21% and 12% yields,
a
Determined by 31P NMR spectroscopy.
interelement compound 20a was gradually formed, and after
irradiation for 24 h, the yield of 20a reached 78% (entry 5).
Compared to the photoinduced reaction with (PhS)2 9a, a
longer reaction time was required using (PhSe)2 12a, likely
owing to the stronger absorption of 12a retarding the
homolysis of 1d to produce Ph2P(S)•. Compared with that
of PhS•, the lower reactivity of PhSe• (kPhS•/kPhSe• = ca. 10−
50) may also contribute to the increased reaction time.37
In contrast to (PhS)2 9a and (PhSe)2 12a, (PhTe)2 15a did
not react with diphosphine disulfide 1d under light irradiation
(eq 5). Indeed, the starting 15a was recovered almost
n
respectively). The use of a dialkyl diselenide, i.e., Bu2Se2 12f,
successfully afforded the corresponding PV(S)−SeBun interele-
ment compound 20f in 98% yield under the same conditions.
The majority of synthesized PV−S interelement compounds
and all synthesized PV−Se interelement compounds are new
compounds, and in particular, no previous reports exist on the
synthesis of Se-aryl diphenylphosphinoselenodithioate deriva-
tives 20a−f. Therefore, the present photoinduced radical
method provides a new approach to the use of PV−S and PV−
Se interelement compounds for organic synthesis.
To gain an insight into the reaction pathways, we conducted
a control experiment using excess amounts of TEMPO as a
radical scavenger. To shorten the reaction time, a superhigh
pressure Hg lamp (250 W) was used in this control experiment
in place of a xenon lamp. Upon irradiation with a superhigh
pressure Hg lamp for 9 h in the presence of TEMPO (5.0
equiv), 19a was produced in 15% yield, whereas in the absence
of TEMPO, 19a was formed in 78% yield under the same
conditions (eq 6). This result supports the assumption that the
formation of PV−S interelement compounds occurs via a
radical pathway.
We then conducted a Hammett linear free energy relation-
ship study of the photoinduced formation of PV(S)−S
interelement compounds. However, the 31P NMR chemical
shifts (δP) of products 19a−e were too similar to determine
the yields of each PV−S interelement compound precisely. We
therefore attempted the construction of a Hammett plot using
PV−Se interelement compounds 20a−e. As a result, a ρ value
quantitatively. As to 1d, about 80−90% of 1d was recovered
unchanged and about 10−20% of 1d converted to 1e, 1c, and
1f. As can be seen from Figure 2, large absorption of 15a
retarded the photoinduced rearrangement of 1d to 1e, 1c, and
1f. In addition, PhTe• is less reactive compared with PhS• and
PhSe•.13 Furthermore, the instability of the desired P−Te
interelement compound 21a under light also contributes to
inefficiency of the formation of 21a.
Table 3 summarizes the scope and limitations of the
syntheses of P−S/P−Se interelement compounds 19 and 20.
In terms of the synthesis of S-phenyl diphenylphosphino-
dithioate derivatives 19a−e, both electron-donating groups
(e.g., p-MeO) and electron-withdrawing groups (e.g., m-F) are
tolerated by the photoinduced reaction, affording 19b and 19c,
respectively, in moderate to good yields. In contrast, diaryl
disulfides bearing p-cyano (7% yield of 19) and o,o-dichloro
(21% yield of 19) groups did not smoothly react with 1d under
E
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Table 3. Photoinduced Syntheses of P−S/P-Se Interelement Compounds from Diphosphine Disulfide 1d and Dichalcogenides
a b
,
9 and 12
a
Reaction conditions: 1d (0.3 mmol), 9 (0.3 mmol), CH2Cl2 (0.3 mL), 14 h, hv (λ>300 nm). 1d (0.3 mmol), 12 (0.3 mmol), CH2Cl2 (0.3 mL),
b
c
d
36 h, hv (λ>300 nm). Determined by 31P NMR spectroscopy (isolated yield). Reaction time: 36 h. 1d (3.0 mmol), 9d (3.0 mmol), CH2Cl2 (3.0
mL), 36 h, hv (λ>300 nm).
of 0.084 was obtained, thereby supporting the assumption that
the photoinduced reaction of 1d and 12 includes a radical
pathway (see Supporting Information).
During our studies on the radical addition of tetraaryldi-
phosphine and its analogous to alkenes and alkynes, we noticed
that the PV radical species is more reactive to carbon−carbon
unsaturated bonds than the PIII radical species, whereas the PIII
group possesses a higher radical capturing ability compared
with the PV group. Therefore, the radical-trapping ability of 1e
F
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could potentially be higher than that of 1d. From these
insights, a possible pathway for the formation of P−S or P−Se
interelement compounds is outlined in Scheme 3. More
specifically, tetraphenyldiphosphine disulfide 1d undergoes a
photoinduced rearrangement to give an equilibrium of 1e, 1c,
1f, and 1d. Upon photoirradiation, diphenyl disulfide 9a or
diphenyl diselenide 12a undergoes homolysis to produce the
corresponding chalcogen-centered radical (PhE•), which
preferentially attacks the PIII group of 1e rather than the PV
group of 1d. Subsequent PV(S)−S bond cleavage then results
in formation of the desired PV−E interelement compounds. In
the case of organic diselenides 12, which possess excellent
carbon radical-capturing abilities, the photogenerated Ph2P-
(S)• may alternatively be trapped with the diselenides to afford
the desired PV−Se interelement compounds 20a−e.
the syntheses of unsymmetrical selenides and sulfides;
therefore, the method may also be applicable in the selective
syntheses of unsymmetrical chalcogenides.
CONCLUSIONS
■
We herein reported our investigation of the photoinduced
reactions of tetraphenyldiphosphine disulfide with a range of
organic dichalcogenides to afford a series of phosphorus(V)−
chalcogen interelement compounds via a radical process,
whereby the reactivities of the P−P interelement compound
and its analogues under photoinduced radical conditions are
discussed in detail. By focusing on the reactivities of PIII• and
PV• toward carbon−carbon unsaturated bonds, a facile method
was developed for the formation of PV(S)−S and PV(S)−Se
linkages from tetraphenyldiphosphine disulfide and (PhS)2 or
(PhSe)2. To date, the majority of methods reported for the
syntheses of PV(S)−E (E = S, Se) compounds involve ionic
pathways or transition-metal-catalyzed reactions using air- and
moisture sensitive reagents. In contrast, our method provides
PV(S)−E compounds via photoinduced radical reactions,
whereby all reagents were air- and moisture-stable. The
formed PV−E interelement compounds were suitable for
application in ionic reactions, and their transformation into
various phosphine reagents and chalcogenides was possible via
one-pot processes. We therefore believe that our studies on the
reactivities of the diphosphines and chalcogenides could lead
to new synthetic approaches toward organophosphorus
reagents.
However, owing to the high stabilities of P−S and P−Se
interelement compounds 19a−e and 20a−e under photo-
irradiation conditions, they were unable to add to the alkenes
or alkynes. Even in the presence of radical initiators, such as
AIBN and V-40, the reaction remained unsuccessful (eqs
7−10). This was attributed to the PV(S)−E (E = S, Se) bonds
potentially being strongly stabilized by conjugation between
the PVS bond and the lone pair on E.38As homolytic
cleavage of the PV−S and PV−Se bonds was challenging,24 we
examined the heterolytic cleavage of these bonds by
nucleophilic substitution using a range of nucleophiles.
Interestingly, compounds 19 and 20 were reactive under the
ionic reaction conditions. More specifically, 19a smoothly
reacted with decanethiolate, produced from decanethiol and an
equimolar amount of DMAP, to result in cleavage of the
PV(S)−SPh bond, giving S-decyl diphenylphosphinodithioate
19f in a moderate yield in a one-pot process (eq 11).39 This
process is therefore advantageous for the following reasons:
(1) starting materials 1d and 9a are stable to handle under
atmospheric conditions; (2) the use of the method outlined in
Table 3 allows the introduction of an arylthiol group (a good
leaving group) into key intermediate 19; and (3) using the
present one-pot method, a variety of PV(S)−heteroatom
interelement compounds can be synthesized. As a pioneering
work concerning PV(S)−S interelement compounds, Inamoto
EXPERIMENTAL SECTION
■
General Remarks. Unless otherwise stated, all starting materials
and catalysts were purchased from commercial sources and used
without further purification. All solvents were distilled and degassed
with nitrogen before use. Disulfide 9b, diselenide (12b−12f), and
tetraphenyldiphosphine disulfide 1d were prepared according to
previously reported procedures.9,40−42 As the light source of the Xe
lamp, USHIO optical ModuleX (SX-UI500XQ) was used. As the light
source of the superhigh pressure Hg lamp, USHIO optical ModuleX
(SX-UI251H) was used. The distance from the light source to the
irradiation vessel was ca. 40 cm. 1H NMR spectra were recorded on a
JEOL JNM-ECS400 (400 MHz) FT NMR system or a JEOL JNM-
ECX400 (400 MHz) FT NMR system in CDCl3 with Me4Si as an
internal standard. 13C NMR spectra were recorded on a JEOL JNM-
ECX400 (100 MHz) FT NMR or JEOL JNM-ECS400 (100 MHz)
n
et al. reported the reaction of 19a with BuLi, which afforded
unsymmetrical sulfides PhSBun and Ph2P(S)Li.39 Hence, we
applied this reaction with butyllithium as a convenient one-pot
reaction based on the air- and moisture-stable 1d and 9a, as
shown in eq 12. More specifically, the photoinduced reaction
n
of 1d and 9a, followed by reaction with BuLi, successfully
afforded the corresponding unsymmetrical sulfide 22 in a good
yield. This one-pot, unsymmetrical sulfide synthesis was then
applied to the synthesis of unsymmetrical selenide 23 (eq 12).
The present method is therefore of importance since it can be
performed using organophosphorus compounds synthesized
from air- and moisture-stable reagents and can be extended to
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FT NMR system in CDCl3. 31P NMR spectra were recorded on a
JEOL JNM-ECX400 (162 MHz) FT NMR or JNM-ECS400 (162
MHz) FT NMR system in CDCl3 with an 85% H3PO4 solution as an
external standard. 77Se NMR spectra were recorded on a JEOL JNM-
ECX400 (75 MHz) FT NMR or JNM-ECS400 (75 MHz) FT NMR
system in CDCl3 with Me2Se as an external standard. High resolution
mass spectroscopy (HRMS) was conducted on a Bruker micrOTOF
II ESI/TOF analyzer. In this work, we selected AcOMe and iso-
hexane for the purification using silica-gel chromatography; however,
these procedures can also be carried out with AcOEt and n-hexane
instead of these solvents, respectively.
disulfide 1d (0.3 mmol) and diselenide 12 (0.3 mmol) were dissolved
in degassed dry CH2Cl2 (0.3 mL) and placed in a 10 mL Schlenk tube
(Pyrex grass) with a stirrer bar under an Ar atmosphere. The resulting
mixture was irradiated with a xenon lamp (500 W) for 36 h.
Subsequently, the resulting mixture was transferred to a round-bottom
flask with CH2Cl2 (5 mL), and the solvent was removed under
reduced pressure. Finally, the residue was purified by silica-gel
chromatography (AcOMe/iso-hexane) and gel permeation chroma-
tography (eluent: CH2Cl2) to give product 20.
Se-Phenyl Diphenylphosphinoselenothioate (20a). Purified by
silica-gel chromatography (AcOMe/iso-hexane = 1:10) and gel
permeation chromatography (eluent: CH2Cl2), yellow oil, 147.3 mg,
66%; 1H NMR (400 MHz, CDCl3): δ 7.92−7.87 (m, 4H), 7.46−7.37
(m, 8H), 7.30−7.26 (m, 1H), 7.18−7.14 (m, 2H); 13C{1H} NMR
(100 MHz, CDCl3): δ 137.1 (d, J = 2.9 Hz), 134.0 (d, J = 76.7 Hz),
132.0 (d, J = 2.9 Hz), 131.8 (d, J = 10.5 Hz), 129.6 (d, J = 2.9 Hz),
128.6 (d, J = 12.5 Hz), 125.5 (d, J = 6.7 Hz); 31P NMR (162 MHz,
CDCl3): δ 55.2 (with 2 satellite, JP−Se = 360. One Hz); 77Se NMR (75
MHz, CDCl3): δ 459.9 (d, J = 358.0 Hz); HRMS (ESI) m/z calcd for
C18H15NaPSSe [M + Na]+: 396.9695, found: 396.9696.
Se-(4-Chlorophenyl) Diphenylphosphinoselenothioate (20b).
Purified by silica-gel chromatography (AcOMe/iso-hexane = 1:20)
and gel permeation chromatography (eluent: CH2Cl2), light yellow
oil, 87.0 mg, 36%, mp 49.1−50.0 °C; 1H NMR (400 MHz, CDCl3): δ
7.90 (dd, J = 14.2, 8.2 Hz, 4H), 7.52−7.42 (m, 6H), 7.33 (d, J = 7.8
Hz, 2H), 7.17 (d, J = 8.2 Hz, 2H); 13C{1H} NMR (100 MHz,
CDCl3): δ 138.3 (d, J = 2.9 Hz), 136.3, 133.8 (d, J = 63.3 Hz), 133.4
(d, J = 8.6 Hz), 132.1 (d, J = 2.9 Hz), 131.8 (d, J = 11.5 Hz), 129.4
(d, J = 1.9 Hz), 128.7 (d, J = 13.4 Hz); 31P NMR (162 MHz, CDCl3):
55.7 (with 2 satellites, JP−Se = 351.5 Hz); 77Se NMR (75 MHz,
CDCl3): δ 457.6 (d, J = 352.1 Hz); HRMS (ESI) m/z calcd for
C18H14ClNaPSSe [M + Na]+: 430.9305, found: 430.9300.
Se-(4-Fluorophenyl) Diphenylphosphinoselenothioate (20c).
Purified by silica-gel chromatography (AcOMe/iso-hexane = 1:10)
and gel permeation chromatography (eluent: CH2Cl2), light yellow
solid, 196.3 mg, 84%, mp 80.0−81.0 °C; 1H NMR (400 MHz, CDCl3,
ppm): δ 7.91 (q, J = 7.2 Hz, 4H), 7.54 (d, J = 7.8 Hz, 2H), 7.47−7.39
(m, 8H); 13C{1H} NMR (100 MHz, CDCl3): δ 137.2 (d, J = 2.9 Hz),
133.6 (d, J = 77.6 Hz), 132.3 (d, J = 2.9 Hz), 131.8 (d, J = 10.5 Hz),
130.2 (d, J = 4.8 Hz), 128.8 (d, J = 13.4 Hz), 125.8, 122.6; 31P NMR
(162 MHz, CDCl3): δ 56.5 (with 2 satellites, JP−Se = 347.2 Hz); 77Se
NMR (75 MHz, CDCl3): δ 466.0 (d, J = 346.3 Hz); HRMS (ESI) m/
z calcd for C18H14FNaPSSe [M + Na]+: 414.9601, found: 414.9600.
Se-(4-(Trifluoromethyl)phenyl) Diphenylphosphinoselenothioate
(20d). Purified by gel permeation chromatography (eluent: CH2Cl2),
yellow oil, 164.7 mg, 62%; 1H NMR (400 MHz, CDCl3): δ 7.91 (q, J
= 7.2 Hz, 4H), 7.54 (d, J = 7.8 Hz, 2H), 7.47−7.39 (m, 8H); 13C{1H}
NMR (100 MHz, CDCl3): δ 166.1 (d, J = 2.9 Hz), 162.7 (d, J = 2.9
Hz), 139. One (dd, J = 7.7, 2.9 Hz), 133.8 (d, J = 76.7 Hz), 132.1 (d,
J = 2.9 Hz), 131.8 (d, J = 10.5 Hz), 128.7 (d, J = 13.4 Hz), 120.2 (m),
116.5 (dd, J = 21.1, 1.9 Hz); 31P NMR (162 MHz, CDCl3): δ 56.4
(with 2 satellites, JP−Se = 347.2 Hz); 77Se NMR (75 MHz, CDCl3): δ
466.1 (d, J = 346.3 Hz); HRMS (ESI) m/z calcd for C19H14F3NaPSSe
[M + Na]+: 464.9569, found: 464.9566.
Synthesis of PV(S)−S Interelement Compounds Using Diphos-
phine 1d and Disulfides (19a−e). Tetraphenyldiphosphine disulfide
1d (0.3 mmol) and disulfide 9 (0.3 mmol) were dissolved in degassed
dry CH2Cl2 (0.3 mL) and placed in a 10 mL Schlenk tube (Pyrex
grass) with a stirrer bar. The resulting mixture was irradiated with a
xenon lamp (500 W) for 14 h. Subsequently, the resulting mixture
was transferred to a round-bottom flask with CH2Cl2 (5 mL), and the
solvent was removed under reduced pressure. Finally, the residue was
purified by silica-gel chromatography (AcOMe/iso-hexane) and gel
permeation chromatography (eluent: CH2Cl2) to give product 19.
S-Phenyl Diphenylphosphinodithioate (19a). [CAS no. 57664-
86-7];39 Purified by silica-gel chromatography (AcOMe/iso-hexane =
1:10) and gel permeation chromatography (eluent: CH2Cl2),
colorless oil, 145.5 mg, 74%; 1H NMR (400 MHz, CDCl3): δ
7.99−7.92 (m, 4H), 7.52−7.47 (m, 2H), 7.46−7.41 (m, 4H), 7.35−
7.30 (m, 3H), 7.22 (t, J = 7.6 Hz, 2H); 13C{1H} NMR (100 MHz,
CDCl3): δ 136.5 (d, J = 3.8 Hz), 133.7 (d, J = 84.4 Hz), 132.0 (d, J =
2.9 Hz), 131.9 (d, J = 11.5 Hz), 129.7 (d, J = 2.9 Hz), 129.0 (d, J =
2.9 Hz), 128.7, 128.5; 31P NMR (162 MHz, CDCl3): δ 66.2.
S-(4-Methoxyphenyl) Diphenylphosphinodithioate (19b). Puri-
fied by gel permeation chromatography (eluent: CH2Cl2), white solid,
112.7 mg, 53%, mp 112.0−113.0 °C; 1H NMR (400 MHz, CDCl3): δ
7.98−7.92 (m, 4H), 7.53−7.43 (m, 6H), 7.25−7.23 (m, 2H), 6.76 (d,
J = 8.2 Hz, 2H), 3.76 (s, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ
161.0 (d, J = 3.1 Hz), 138.0 (d, J = 3.6 Hz), 134.1 (d, J = 82.4 Hz),
131.9 (d, J = 3.3 Hz), 131.8 (d, J = 10.7 Hz), 128.5 (d, J = 13.0 Hz),
116.9 (d, J = 5.3 Hz), 114.7 (d, J = 2.3 Hz), 55.3; 31P NMR (162
MHz, CDCl3): δ 65.5; HRMS (ESI) m/z calcd for C19H17NaOPS2
[M + Na]+: 379.0356, found: 379.0356.
S-(3-Fluorophenyl) Diphenylphosphinodithioate (19c). Purified
by gel permeation chromatography (eluent: CH2Cl2), yellow oil,
145.1 mg, 70%; 1H NMR (400 MHz, CDCl3): δ 7.97−7.92 (m, 4H),
7.51−7.40 (m, 6H), 7.19−7.12 (m, 2H), 7.08−7.05 (m, 1H), 7.02−
6.97 (m, 1H); 13C{1H} NMR (100 MHz, CDCl3): δ 162.2 (d, J =
250.2 Hz), 133.4 (d, J = 84.4 Hz), 132.3, 132.2, 131.9 (d. J = 11.5
Hz), 130.1 (dd, J = 8.2, 2.9 Hz), 128.7 (d, J = 13.4 Hz), 123.2 (dd, J =
22.5, 2.9 Hz), 117.0 (dd, J = 21.1, 2.9 Hz); 31P NMR (162 MHz,
CDCl3): δ 66.7; HRMS (ESI) m/z calcd for C18H14FNaPS2 [M +
Na]+: 367.0156, found: 367.0157.
S-Methyl Diphenylphosphinodithioate (19d). [CAS no. 15288-
70-7];43 Purified by silica-gel chromatography (AcOMe/iso-hexane =
1
1:5), white solid, 153.3 mg, 97%, mp 77.5−78.3 °C; H NMR (400
MHz, CDCl3): δ 7.99−7.93 (m, 4H), 7.53−7.44 (m, 6H), 2.30 (d, J =
14.7 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ 133.8 (d, J =
84.4 Hz), 132.0 (d, J = 2.9 Hz), 131.5 (d, J = 10.5 Hz), 128.7 (d, J =
13.4 Hz), 12.9 (d, J = 1.9 Hz); 31P NMR (162 MHz, CDCl3): δ 66.6.
S-Cyclohexyl Diphenylphosphinodithioate (19e). Purified by
silica-gel chromatography (AcOMe/iso-hexane = 1:5) and gel
permeation chromatography (eluent: CH2Cl2), colorless oil, 138.9
mg, 70%; 1H NMR (400 MHz, CDCl3): δ 7.98−7.92 (m, 4H), 7.49−
7.40 (m, 6H), 3.53−3.43 (m, 1H), 1.93−1.87 (m, 2H), 1.79−1.76
(m, 1H), 1.69−1.63 (m, 2H), 1.53−1.44 (m, 2H), 1.39−1.22 (m,
3H); 13C{1H} NMR (100 MHz, CDCl3): δ 135.4 (d, J = 85.3 Hz),
131.7 (d, J = 2.9 Hz), 131.5 (d, J = 11.5 Hz), 128.5 (d, J = 12.5 Hz),
47.0, 35.0 (d, J = 3.8 Hz), 25.9, 25.4; 31P NMR (162 MHz, CDCl3): δ
62.3; HRMS (ESI) m/z calcd for C18H21NaPS2 [M + Na]+: 355.0720,
found: 355.0721.
Se-(3-(Trifluoromethyl)phenyl) Diphenylphosphinoselenothioate
(20e). Purified by silica-gel chromatography (AcOMe/iso-hexane =
1:15) and gel permeation chromatography (eluent: CH2Cl2),
colorless oil, 171.4 mg, 65%; 1H NMR (400 MHz, CDCl3): δ
7.92−7.86 (m, 4H), 7.68 (d, J = 7.3 Hz, 1H), 7.57 (d, J = 7.8 Hz,
1H), 7.53−7.49 (m, 3H), 7.47−7.43 (m, 4H), 7.36 (t, J = 7.8 Hz,
1H); 13C{1H} NMR (100 MHz, CDCl3): δ 140.5, 133.8 (m), 132.2
(d, J = 2.9 Hz), 131.7 (d, J = 11.5 Hz), 130.0, 129.4 (d, J = 1.9 Hz),
128.7 (d, J = 13.4 Hz), 126.3 (d, J = 4.8 Hz), 124.8, 122.1; 31P NMR
(162 MHz, CDCl3): δ 56.5 (with 2 satellites, JP−Se = 347.2 Hz); 77Se
NMR (75 MHz, CDCl3): δ 476.9 (d, J = 346.3 Hz); HRMS (ESI) m/
z calcd for C19H14F3NaPSSe [M + Na]+: 464.9569, found: 464.9558.
Se-n-Butyl Diphenylphosphinoselenothioate (20f). Purified by
silica-gel chromatography (AcOMe/iso-hexane = 1:5) and gel
permeation chromatography (eluent: CH2Cl2), yellow oil, 208.5 mg,
98%; 1H NMR (400 MHz, CDCl3): δ 7.97−7.91 (m, 4H), 7.50−7.41
Synthesis of PV(S)−Se Interelement Compounds Using Diphos-
phine 1d and Diselenides (20a−f). Tetraphenyldiphosphine
H
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Article
(m, 6H), 3.03−2.96 (m, 2H), 1.66−1.59 (m, 2H), 1.39−1.30 (m,
2H), 0.83 (t, J = 7.3 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ
135.2 (d, J = 76.7 Hz), 131.7 (d, J = 2.9 Hz), 131.5 (d, J = 11.5 Hz),
128.6 (d, J = 13.4 Hz), 32.4 (d, J = 3.8 Hz), 29.3 (d, J = 1.9 Hz), 23.0,
Butyl(phenyl)sulfane (22). [CAS No. 1126-80-3];45 Purified by
silica-gel chromatography (iso-hexane), light yellow oil, 69.5 mg, 70%;
1H NMR (400 MHz, CDCl3): δ 7.33−7.25 (m, 4H), 7.18−7.13 (m,
1H), 2.92 (t, J = 7.5 Hz, 2H), 1.67−1.60 (m, 2H), 1.50−1.40 (m,
2H), 0.92 (t, J = 7.2 Hz, 3H); 13C{1H} NMR (100 MHz, CDCl3): δ
137.1, 131.3, 128.9, 125.7, 33.3, 31.3, 22.1, 13.7.
13.5; 31P NMR (162 MHz, CDCl3): δ 52.5 (with 2 satellites, JP−Se
=
368.7 Hz); 77Se NMR (75 MHz, CDCl3): δ 283.3 (d, J = 369.7 Hz);
HRMS (ESI) m/z calcd for C16H19NaPSSe [M + Na]+: 377.0008,
found: 377.0006.
Butyl(phenyl)selane (23). [CAS No. 28622-61-9];46 Purified by
gel permeation chromatography (eluent: CH2Cl2), yellow oil, 103.4
Gram-Scale Synthesis of PV-Chalcogen Compounds (Table 3,
19d). Tetraphenyldiphosphine disulfide 1d (3.0 mmol) and dimethyl
disulfide 9d (3.0 mmol) were dissolved in degassed dry CH2Cl2 (3.0
mL) and placed in a 30 mL Schlenk tube (Pyrex grass) with a stirrer
bar under an Ar atmosphere. The resulting mixture was irradiated
with a superhigh pressure Hg lamp (250 W) for 36 h. Subsequently,
the resulting mixture was transferred to a round-bottom flask with
CH2Cl2 (10 mL), and the solvent was removed under reduced
pressure. Finally, the residue was purified by silica-gel chromatog-
raphy (AcOMe/iso-hexane = 1:5) to give product 19d in 91% isolated
yield (1.45 g) as a white solid.
1
mg, 81%; H NMR (400 MHz, CDCl3): δ 7.48 (dd, J = 7.8, 1.4 Hz,
2H), 7.26−7.19 (m, 3H), 2.90 (t, J = 7.6 Hz, 2H), 1.72−1.64 (m,
2H), 1.47−1.37 (m, 2H), 0.90 (t, J = 7.3 Hz, 3H); 13C{1H} NMR
(100 MHz, CDCl3): δ 132.4, 130.8, 129.1, 126.7, 32.4, 27.7, 23.1,
13.7; 77Se NMR (75 MHz, CDCl3): δ 291.5.
ASSOCIATED CONTENT
■
sı
* Supporting Information
Radical Trapping Experiment Using Diphosphine Disulfide 1d,
Disulfide 9a, and TEMPO (eq 6, entry 2). Tetraphenyldiphosphine
disulfide 1d (0.3 mmol), disulfide 9a (0.3 mmol), and TEMPO (5
equiv) were dissolved in degassed dry CH2Cl2 (0.3 mL) and placed in
a sealed NMR tube (Pyrex grass). The resulting mixture was
irradiated with a super high-pressure lamp (250 W) for 9 h. The yield
of 19a was determined by 31P NMR spectroscopy.
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.joc.0c02014.
1H NMR, 13C NMR, 31P NMR, and 77Se NMR spectra
(PDF)
One-Pot Reaction between 20a Generated in Situ and an
Alkanethiol in the Presence of Base (eq 11). Tetraphenyl-
diphosphine disulfide 1d (0.3 mmol) and disulfide 9 (0.3 mmol)
were dissolved in degassed dry CH2Cl2 (0.3 mL) and placed in a 10
mL Schlenk tube (Pyrex grass) with a stirrer bar. The resulting
mixture was irradiated with a super high-pressure lamp (250 W) for
14 h. Afterward, the solvent was removed under reduced pressure. 1-
Decanethiol (1.2 mmol), DMAP (1.2 mmol), and CH3CN (0.3 mL)
were added to the reaction mixture and heated under reflux for 4 h in
an oil bath. Subsequently, the resulting mixture was transferred to a
round-bottom flask with CH2Cl2 (5 mL), and the solvent was
removed under reduced pressure. Finally, the residue was purified by
gel permeation chromatography (eluent: CH2Cl2) to give product
19f.
AUTHOR INFORMATION
■
Corresponding Author
Akiya Ogawa − Department of Applied Chemistry, Graduate
School of Engineering, Osaka Prefecture University, Sakai,
Osaka 599-8531, Japan; orcid.org/0000-0002-8543-2560;
Email: ogawa@chem.osakafu-u.ac.jp
Authors
Yuki Yamamoto − Department of Applied Chemistry, Graduate
School of Engineering, Osaka Prefecture University, Sakai,
Osaka 599-8531, Japan
Ryo Tanaka − Department of Applied Chemistry, Graduate
School of Engineering, Osaka Prefecture University, Sakai,
Osaka 599-8531, Japan
Miyuto Ota − Department of Applied Chemistry, Graduate
School of Engineering, Osaka Prefecture University, Sakai,
Osaka 599-8531, Japan
Misaki Nishimura − Department of Applied Chemistry,
Graduate School of Engineering, Osaka Prefecture University,
Sakai, Osaka 599-8531, Japan
Cong Chi Tran − Department of Applied Chemistry, Graduate
School of Engineering, Osaka Prefecture University, Sakai,
Osaka 599-8531, Japan
Shin-ichi Kawaguchi − Center for Education and Research in
Agricultural Innovation, Faculty of Agriculture, Saga University,
Saga 847-0021, Japan; orcid.org/0000-0002-4140-9959
Shintaro Kodama − Department of Applied Chemistry,
Graduate School of Engineering, Osaka Prefecture University,
Sakai, Osaka 599-8531, Japan; orcid.org/0000-0003-
4190-9539
S-Decyl Diphenylphosphinodithioate (19f). [CAS no. 102545-40-
4];43 Purified by gel permeation chromatography (eluent: CH2Cl2),
1
colorless oil, 104.8 mg, 45%; H NMR (400 MHz, CDCl3): δ 7.99−
7.92 (m, 4H), 7.50−7.40 (m, 6H), 2.94−2.87 (m, 2H), 1.61−1.53
(m, 2H), 1.35−1.19 (m, 14H), 0.87 (t, J = 7.1 Hz, 3H); 13C{1H}
NMR (100 MHz, CDCl3): δ 134.8 (d, J = 85.3 Hz), 131.8 (d, J = 3.8
Hz), 131.5 (d, J = 10.5 Hz), 128.6 (d, J = 13.4 Hz), 32.0, 31.9 (d, J =
1.9 Hz), 30.1 (d, J = 5.8 Hz), 29.6, 29.5, 29.4, 29.1, 28.8, 27.8, 14.2;
31P NMR (162 MHz, CDCl3): δ 64.4.
Syntheses of Unsymmetrical Chalcogenides from the P−E (E =
S, Se) Compound and nBuLi (eq 12). Tetraphenyldiphosphine
disulfide 1d (0.3 mmol) and disulfide 9a or diselenide 12a (0.3
mmol) were dissolved in degassed dry CH2Cl2 (0.3 mL) and placed
in a 10 mL Schlenk tube (Pyrex grass) with a stirrer bar. The resulting
mixture was irradiated with a super high-pressure lamp (250 W) for
14 h (in the case of using 1d and 9a) or 36 h (in the case of using 1d
n
and 12a). Subsequently, BuLi (1.6 M in hexane, see eq 12) was
slowly added to the reaction vessel in a dry ice−acetone bath at −78
°C. After removal of the dry ice−acetone bath and returning to room
temperature, the reaction mixture was stirred overnight at 25 °C.
After the reaction was complete, H2O (1 mL) was added slowly to the
reaction vessel in an ice−water bath at 0 °C. The resulting mixture
was extracted with CH2Cl2 (3 × 5 mL), and the organic layer was
washed with H2O (10 mL) and brine (10 mL). The solution was
dried over anhydrous Na2SO4 and then filtered, and the filtrate was
distilled under reduced pressure. Finally, the residue was purified by
silica-gel chromatography (eluent: iso-hexane) or gel permeation
chromatography (eluent: CH2Cl2), to give product 22 or 23, as
appropriate. The generation of diphenylphosphine sulfide was
confirmed by 31P NMR spectroscopy (CDCl3, δP = 23.3 ppm).44
Akihiro Nomoto − Department of Applied Chemistry, Graduate
School of Engineering, Osaka Prefecture University, Sakai,
Osaka 599-8531, Japan
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.joc.0c02014
Notes
The authors declare no competing financial interest.
I
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J. Org. Chem. XXXX, XXX, XXX−XXX

The Journal of Organic Chemistry
pubs.acs.org/joc
Article
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ACKNOWLEDGMENTS
■
This work is supported by Grant-in-Aid for Scientific Research
on Scientific Research (19K17746; B, 19H02756) from The
Japan Society for the Promotion of Science (JSPS).
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