Rh(I)-Catalyzed Intramolecular Decarbonylation of Thioesters

Article abstract of DOI:10.1021/acs.joc.1c01117

Decarbonylative synthesis of thioethers from thioesters proceeds in the presence of a catalytic amount of [Rh(cod)Cl]2 (2 mol %). The protocol represents the first Rh-catalyzed decarbonylative thioetherification of thioesters to yield valuable thioethers. Notable features include the absence of phosphine ligands, inorganic bases, and other additives and excellent group tolerance to aryl chlorides and bromides that are problematic using other metals to promote decarbonylation. Gram scale synthesis, late-stage pharmaceutical derivatization, and orthogonal site-selective cross-couplings by C-S/C-Br cleavage are reported.

Full text of DOI:10.1021/acs.joc.1c01117

pubs.acs.org/joc
Note
Rh(I)-Catalyzed Intramolecular Decarbonylation of Thioesters
Han Cao, Xuejing Liu,* Fusheng Bie, Yijun Shi, Ying Han, Peng Yan, Michal Szostak,*
and Chengwei Liu*
Cite This: J. Org. Chem. 2021, 86, 10829−10837
Read Online
sı
*
Metrics & More
Article Recommendations
Supporting Information
ACCESS
ABSTRACT: Decarbonylative synthesis of thioethers from
thioesters proceeds in the presence of a catalytic amount of
[Rh(cod)Cl]2 (2 mol %). The protocol represents the first Rh-
catalyzed decarbonylative thioetherification of thioesters to yield
valuable thioethers. Notable features include the absence of
phosphine ligands, inorganic bases, and other additives and
excellent group tolerance to aryl chlorides and bromides that are
problematic using other metals to promote decarbonylation. Gram scale synthesis, late-stage pharmaceutical derivatization, and
orthogonal site-selective cross-couplings by C−S/C−Br cleavage are reported.
fundamental methods for C−S bond formation.4a,b Recently,
hioethers are fundamental sulfur-containing motifs that
decarbonylative couplings have attracted significant attention
Thave found wide application in organic synthesis and are
because carboxylic acids and their derivatives can be converted
into C−C, C−B, C−Si, C−N, C−O, and C−S bonds under
redox-neutral conditions with a concomitant loss of CO.5−9
In this context, our laboratory has been focused on the
development of decarbonylative cross-coupling reactions as an
orthogonal strategy for conventional cross-couplings of aryl
halides and pseudohalides.5b,6,7 Decarbonylative synthesis of
sulfides represents an attractive strategy for harnessing
thioesters as electrophilic substrates for homogeneous
catalysis10 by CO extrusion as an orthogonal method to
oxidative methods for decarboxylative C−S coupling (Figure
1B).11 Decarbonylative thioetherification of thioesters has been
reported via Ni and Pd catalysis by the groups of Wenkert,12
Sanford,13 Yamaguchi,14 and our group.15,16 Studies of the
mechanism by Kambe17 and early precedents by Yamamoto18
are noteworthy. Considering significant advantages of Rh as a
catalysis platform for organic synthesis19 and decarbonylative
coupling,5 we recently questioned whether Rh(I) can be
catalytically employed to promote decarbonylative thioether-
ification of thioesters.
a central component of bioactive compounds, including
pharmaceuticals, natural products, and agrochemicals (Figure
1A).1,2 Methods for the synthesis of thioethers have gained a
great deal of attention due to the privileged role of sulfur and
diverse applications of thioesters.3,4 In this regard, transition-
metal-catalyzed cross-couplings are one of the most
Herein, we report the first Rh-catalyzed decarbonylative
thioetherification of thioesters (Figure 1C). Notable features
include (1) a practical catalyst system using [Rh(cod)Cl]2 in
the absence of phosphine ligands, inorganic bases, and other
additives and (2) excellent functional group tolerance to aryl
halides, such as chlorides and bromides that are problematic,
Received: May 12, 2021
Published: July 9, 2021
Figure 1. Context of this study: intramolecular decarbonylation of
thioesters.
https://doi.org/10.1021/acs.joc.1c01117
J. Org. Chem. 2021, 86, 10829−10837
© 2021 American Chemical Society
10829

The Journal of Organic Chemistry
pubs.acs.org/joc
Note
using other metals to promote decarbonylation. Furthermore,
we present gram scale synthesis, late-stage pharmaceutical
derivatization, and orthogonal site-selective cross-couplings by
C−S/C−Br cleavage. The protocol should facilitate the
synthesis of valuable thioethers under decarbonylative
conditions.
furnishing the desired thioether product in excellent 87% yield
(Table 1, entry 4). Various rhodium catalysts were tested,
including [Rh(PPh3)3Cl], [Rh(cod)Cl]2, [Rh(cod)2]BF4, and
[RhCp*Cl2]2, and the catalytic system in the presence of
[Rh(cod)Cl]2 as a catalyst shows the optimal condition (Table
1, entries 4−7). Control experiments indicated that lower
catalyst loading resulted in a lower but promising reactivity
(Table 1, entries 8 and 9). Interestingly, toluene was found as
the preferred solvent over the more typically used dioxane in
this cross-coupling manifold5−8 (Table 1, entry 10). Finally, we
found that the reaction proceeds at temperatures as low as 120
°C (Table 1, entries 11 and 12), consistent with a high
efficiency of decarbonylation under these conditions.
The novelty of this work should be compared and contrasted
with (1) the use of aryl halides and pseudohalides for the
synthesis of thioethers3,4 and (2) the use of Ni- and Pd-
catalyzed protocols for intramolecular decarbonylation of
thioesters.12−16 Thus, in terms of using thioesters versus aryl
halides for the synthesis of thioethers, the ultimate pool of
precursors is different; in the latter case, thioesters are formed
from carboxylic acids, which represent a ubiquitous class of
substrates in organic synthesis and are inherently present in
many pharmaceuticals and natural products.9 With respect to
other protocols for decarbonylation of thioesters,12−16 this
method provides the first example of using Rh for catalytic
decarbonylative thioetherification. The development of new
metal catalysts for functional group interconversions is one of
the most fundamental aspects of catalysis. The advantages can
be identified as follows. (1) There is functional group tolerance
to aryl bromides. This chemoselectivity cannot be easily
achieved using low-valent Ni or Pd systems, while the bromide
handle is extremely useful for sequential transformations. (2)
The Rh system is very practical in that phosphine or NHC
ligands are not required, while phosphines and/or NHCs are
required for Ni or Pd systems. (3) Additionally, the Rh system
shows better chemoselectivity for carbonyl-containing sub-
strates and vinyl substrates. (4) Furthermore, Rh(I) is well-
known to promote other decarbonylative processes,5 which
might open the door for sequential catalysis using Rh systems.
The optimization was conducted using PhCOSPh 1a as a
modular, unbiased substrate. Selected results are summarized
in Table 1. First, we screened various combinations of
[Rh(PPh3)3Cl] with inorganic bases, which furnished the
desired product in 70−88% yields (Table 1, entries 1−3).
Next, we found that the base is not needed for the reaction,
With the optimal conditions in hand, the scope of the
reaction was next investigated. As shown, this protocol shows
very broad substrate scope to afford aryl−aryl, aryl−heteroaryl,
vinyl−aryl, and aryl−alkyl thioether products (Figure 2). Thus,
a
Table 1. Summary of Optimization Studies
b
entry
catalyst
base
yield (%)
1
2
3
4
5
6
7
Rh(PPh3)3Cl
Rh(PPh3)3Cl
Rh(PPh3)3Cl
Rh(PPh3)3Cl
[Rh(cod)Cl]2
[Rh(cod)2]BF4
[RhCp*Cl2]2
[Rh(cod)Cl]2
[Rh(cod)Cl]2
[Rh(cod)Cl]2
[Rh(cod)Cl]2
[Rh(cod)Cl]2
Na2CO3
K2CO3
K3PO4
−
−
−
−
−
−
88
72
70
87
97
65
75
51
39
56
77
43
Figure 2. Scope of rhodium-catalyzed intramolecular decarbonylation
of thioesters. Conditions: thioester (1.0 equiv), [Rh(cod)Cl]2 (2 mol
%), toluene, 160 °C, 15 h. Isolated yields.
a range of electronically diverse thioesters can be utilized,
including electron-neutral (2a−c), electron-donating (2d), and
electron-withdrawing substrates (2e). Furthermore, halide-
containing substrates, such as fluoro (2f) and chloro (2g)
thioesters, are well accommodated. Moreover, electrophilic
substrates that would be problematic under traditional
organometallic conditions, such as cyano (2h), ester (2i),
and ketone (2j), are perfectly compatible with this method.
These findings are consistent with the high chemoselectivity
exhibited by Rh19 and attest to the high practicality of this
c
8
9
d
e
10
11
12
−
−
−
f
g
a
Conditions: thioester (1.0 equiv), catalyst (2 mol %), base (1.5
b
c
equiv), toluene, 160 °C, 15 h. GC/1H NMR yields. Catalyst (1 mol
d
e
f
g
%). Catalyst (0.5 mol %). Dioxane as the solvent. At 140 °C. At
120 °C.
10830
https://doi.org/10.1021/acs.joc.1c01117
J. Org. Chem. 2021, 86, 10829−10837

The Journal of Organic Chemistry
pubs.acs.org/joc
Note
method. Furthermore, sterically hindered substrates (2k and
2l) are well tolerated in this protocol. As expected, meta
substitution (2m) is also quite compatible. Moreover, this
protocol can be employed to incorporate heterocyclic
thioesters, such as furyl and thienyl in excellent yields (2n
and 2o). Finally, vinyl thioesters are also well accommodated,
delivering vinyl-aryl thioesters by this protocol (2p).
development, preliminary mechanistic studies have been
performed (not shown). As such, intermolecular competition
using PhCOS-4-Tol with external 4-F-C6H4-SH showed that
the electron-deficient product is favored (56:44 Ph-S-4-F-
C6H4:Ph-S-4-Tol), while the use of external 4-MeO-C6H4-SH
showed that the electron-donating product is less favored
(41:59 Ph-S-4-MeO-C6H4:Ph-S-4-Tol). These results are
consistent with the ease of oxidative addition. Importantly,
this protocol can be easily scaled as demonstrated by gram
scale coupling conducted under the standard condition, which
resulted in a 90% yield (0.81 g) of the desired product,
demonstrating the scalability of the method (Figure 4B).
To further demonstrate the utility of this Rh(I)-catalyzed
intramolecular decarbonylative thioester synthesis, we con-
ducted additional selectivity studies (Figure 5). First, we
We were pleased to find that the scope of the thiophenol
group is also broad (Figure 3). As shown herein, high yields are
Figure 3. Scope of rhodium-catalyzed intramolecular decarbonylation
of thioesters. Conditions: thioester (1.0 equiv), [Rh(cod)Cl]2 (2 mol
%), toluene, 160 °C, 15 h. Isolated yields.
achieved using electron-neutral (2c′), electron-rich (2d′), and
electron-deficient (2e′ and 2f′) substrates. Moreover, sterically
hindered (2k′) and heterocyclic thioester substrates (2o′) can
be readily employed to afford the desired products in high
yields. Finally, we demonstrated that this Rh(I)-catalyzed
strategy is also amenable for the synthesis of challenging aryl-
alkyl thioesters (2q) in the absence of β-hydride elimination.
To illustrate the utility of this Rh(I)-catalyzed intramolecular
decarbonylation of thioesters, we conducted intramolecular
selectivity studies and gram scale synthesis (Figure 4). Thus,
Figure 5. (A) Facile synthesis of probenecid thioether. (B)
Chemoselective C−N/C−Br sequential cleavage.
employed this method for late-stage derivatization of
pharmaceuticals as demonstrated by probenecid (antihyperur-
icemic), which could be readily converted to the correspond-
ing thioether in 87% yield (Figure 5A). One of the most
important advantages of this robust Rh(I) is highlighted by the
fact that this method readily tolerates aryl halides, such as Ar−
Br, which are not compatible with other decarbonylative
protocols for thioether synthesis (Figure 5B).12−18 Thus,
sequential C−S/C−Br cross-coupling is readily feasible by our
standard catalytic system, leaving the bromide bond in
thioether 2s fully intact. This sets up the C−Br bond for
Buchwald−Hartwig amination by the standard Pd2(dba)3/P-t-
Bu3 catalytic system, which highlights the orthogonal nature of
this process.
Figure 4. (A) Selectivity study: C−S vs C−O coupling. (B) Gram
scale reaction.
CONCLUSIONS
intramolecular decarbonylation of thioesters by C−S cleavage
is possible with full chemoselectivity in the presence of an
activated phenolic ester (Figure 4A).20 This result is consistent
with the fact that even activated ester carbonyl groups are well
accommodated under these Rh(I) conditions, while the
carbonyl group in the ester moiety remains fully intact and
C−O cleavage is not observed. At this stage of reaction
■
In conclusion, we have reported the first rhodium-catalyzed
method for decarbonylative thioetherification of thioesters.
The catalytic system employs commercially available [Rh-
(cod)Cl]2 in the absence of phosphine ligands, inorganic bases,
or other additives. The method proceeds with excellent
functional group tolerance to furnish aryl−aryl, aryl−alkyl,
10831
https://doi.org/10.1021/acs.joc.1c01117
J. Org. Chem. 2021, 86, 10829−10837

The Journal of Organic Chemistry
pubs.acs.org/joc
Note
S-Phenyl 4-Methylbenzothioate (1c).15 Yield: 81% (0.925 g).
White solid. H NMR (400 MHz, CDCl3): δ 7.94−7.92 (d, J = 8.2
and vinyl−aryl thioether products. Gram scale synthesis, late-
stage pharmaceutical derivatization, and orthogonal sequential
cross-couplings by C−S/C−Br cleavage have been demon-
strated, highlighting the practicality of the method. We
anticipate that this Rh(I)-catalyzed strategy will provide a
facile means for decarbonylative thioether synthesis. Further
studies of decarbonylative cross-couplings are underway in our
laboratory and will be reported in due course.
1
Hz, 2H), 7.53−7.51 (dd, J = 6.6, 3.1 Hz, 2H), 7.46−7.45 (m, 3H),
7.29 (d, J = 8.0 Hz, 2H), 2.44 (s, 3H). 13C{1H} NMR (100 MHz,
CDCl3): δ 189.9, 144.7, 135.3, 134.2, 129.6, 129.6, 129.4, 127.7,
127.7, 21.9.
S-Phenyl 4-Methoxybenzothioate (1d).15 Yield: 95% (1.158 g).
1
White solid. H NMR (400 MHz, CDCl3): δ 8.03−7.99 (m, 2H),
7.53−7.50 (m, 2H), 7.47−7.44 (m, 3H), 6.98−6.95 (m, 2H), 3.89 (s,
3H). 13C{1H} NMR (100 MHz, CDCl3): δ 188.8, 164.1, 135.4, 129.9,
129.5, 129.3, 127.8, 114.1, 55.7.
EXPERIMENTAL SECTION
■
S-Phenyl 4-(Trifluoromethyl)benzothioate (1e).15 Yield: 89%
General Methods. All starting materials reported in this work
have been prepared according to the method reported previously.14
All compounds reported in this work have been previously reported
or are commercially available. Spectroscopic data matched literature
values. General methods have been published.14
1
(1.253 g). White solid. H NMR (400 MHz, CDCl3): δ 8.15−8.13
(d, J = 7.9 Hz, 2H), 7.78−7.75 (d, J = 8.2 Hz, 2H), 7.55−7.48 (m,
5H). 13C{1H} NMR (100 MHz, CDCl3): δ 189.6, 139.6, 135.1, 135.1
(d, J2 = 33.0 Hz), 130.0, 129.6, 128.0, 126.7, 126.0 (q, J3 = 3.8 Hz),
123.6 (d, J1 = 272.6 Hz). 19F (376 MHz, CDCl3): δ −63.10.
S-Phenyl 4-Fluorobenzothioate (1f).15 Yield: 96% (1.113 g).
White solid. 1H NMR (400 MHz, CDCl3): δ 8.09−8.04 (ddd, J = 8.9,
5.2, 2.5 Hz, 2H), 7.53−7.46 (m, 5H), 7.20−7.14 (m, 2H). 13C{1H}
NMR (100 MHz, CDCl3): δ 188.6, 166.2 (d, J1 = 255.7 Hz), 135.2,
133.1 (d, J4 = 2.9 Hz), 130.2 (d, J3 = 9.4 Hz), 129.8, 129.5, 127.2,
116.1 (d, J2 = 21.9 Hz). 19F (376 MHz, CDCl3): δ −104.11.
S-Phenyl 4-Chlorobenzothioate (1g).15 Yield: 80% (0.990 g).
General Procedure for Thioester Synthesis. An oven-dried
flask (25 mL) equipped with a stir bar was charged with thiophenol
(typically, 5.0 mmol, 1.0 equiv), acyl chloride (typically, 1.0 equiv),
and dichloromethane (typically, 0.50 M), placed under a positive
pressure of argon, and subjected to three evacuation/backfilling cycles
under high vacuum. Triethylamine (typically, 2.0 equiv) was added
dropwise to the reaction mixture with vigorous stirring at 0 °C, and
the reaction mixture was stirred for 12 h at room temperature. After
the indicated time, the reaction mixture was diluted with ethyl acetate
(30 mL). The reaction mixture was washed with HCl (1 × 10 mL),
brine (1 × 10 mL), and H2O (1 × 10 mL), dried, and concentrated.
The crude product was washed with hexane to give the analytically
pure product.
1
White solid. H NMR (400 MHz, CDCl3): δ 7.99−7.95 (m, 2H),
7.53−7.49 (m, 2H), 7.48−7.46 (m, 5H). 13C{1H} NMR (100 MHz,
CDCl3): δ 189.3, 140.2, 135.2, 135.1, 129.9, 129.5, 129.2, 129.0,
127.1.
S-Phenyl 4-Cyanobenzothioate (1h).15 Yield: 83% (0.988 g).
1
White solid. H NMR (400 MHz, CDCl3): δ 8.13−8.10 (d, J = 8.6
General Procedure for Decarbonylation of Thioester. An
oven-dried vial equipped with a stir bar was charged with thioester
substrate (neat, 1.0 equiv) and [Rh(cod)Cl]2 (typically, 2 mol %)
placed under a positive pressure of argon, and subjected to three
evacuation/backfilling cycles under high vacuum. Toluene (typically,
0.20 M) was added with vigorous stirring at room temperature, and
the reaction mixture was placed in a preheated oil bath at 160 °C and
stirred for the indicated time at 160 °C. After the indicated time, the
reaction mixture was diluted with CH2Cl2 (10 mL), filtered, and
Hz, 2H), 7.81−7.79 (d, J = 8.6 Hz, 2H), 7.52−7.48 (m, 5H). 13C{1H}
NMR (100 MHz, CDCl3): δ 189.3, 139.9, 135.1, 132.8, 130.2, 129.6,
128.1, 126.3, 117.9, 117.0.
Methyl 4-[(Phenylthio)carbonyl]benzoate (1i).15 Yield: 81%
1
(1.105 g). White solid. H NMR (400 MHz, CDCl3): δ 8.16−8.14
(m, 2H), 8.09−8.07 (m, 2H), 7.54−7.47 (m, 5H), 3.96 (s, 3H).
13C{1H} NMR (100 MHz, CDCl3): δ 189.9, 166.2, 140.1, 135.2,
134.6, 130.1, 129.9, 129.5, 127.6, 126.9, 52.7.
S-Phenyl 4-Acetylbenzothioate (1j).15 Yield: 66% (0.850 g).
1
concentrated. The sample was analyzed by H NMR (CDCl3, 400
1
Orange solid. H NMR (400 MHz, CDCl3): δ 8.12−8.10 (m, 2H),
MHz) and GC-MS to obtain the conversion, yield, and selectivity
using an internal standard and comparison with authentic samples.
Purification by chromatography on silica gel (hexanes/ethyl acetate)
afforded the title product.
8.06−8.04 (m, 2H), 7.54−7.47 (m, 5H), 2.66 (s, 3H). 13C{1H} NMR
(100 MHz, CDCl3): δ 197.4, 189.9, 140.8, 140.0, 135.1, 130.0, 129.5,
128.8, 127.8, 126.9, 27.1.
S-Phenyl 2-Methylbenzothioate (1k).15 Yield: 88% (1.009 g).
Representative Procedure for Decarbonylation of Thio-
ester. An oven-dried vial equipped with a stir bar was charged with S-
phenyl benzothioate (neat, 42.9 mg, 0.20 mmol, 1.0 equiv) and
[Rh(cod)Cl]2 (1.0 mg, 0.004 mmol, 0.02 equiv), placed under a
positive pressure of argon, and subjected to three evacuation/
backfilling cycles under high vacuum. Toluene (1.0 mL, 0.20 M) was
added with vigorous stirring at room temperature, and the reaction
mixture was placed in a preheated oil bath at 160 °C and stirred for 15
h at 160 °C. After the indicated time, the reaction mixture was cooled
to room temperature, diluted with CH2Cl2 (10 mL), filtered, and
concentrated. A sample was analyzed by 1H NMR (CDCl3, 400
MHz) and GC-MS to obtain the conversion, yield, and selectivity
using an internal standard and comparison with authentic samples.
Purification by chromatography on silica gel (hexanes/ethyl acetate)
afforded the title product. Yield: 97% (36.1 mg, 0.194 mmol). White
solid. Characterization data are included below.
1
White solid. H NMR (400 MHz, CDCl3): δ 7.97−7.95 (d, J = 7.6
Hz, 1H), 7.55−7.52 (m, 2H), 7.50−7.42 (m, 4H), 7.33−7.27 (m,
2H), 2.50 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3): δ 192.3,
137.6, 136.9, 135.1, 132.2, 131.9, 129.6, 129.4, 128.8, 128.3, 126.0,
20.9.
S-Phenyl 2-Fluorobenzothioate (1l).15 Yield: 94% (1.091 g).
White solid. 1H NMR (400 MHz, CDCl3): δ 7.95−7.91 (t, J = 7.5 Hz,
1H), 7.58−7.53 (m, 3H), 7.48−7.47 (m, 3H), 7.28−7.17 (m, 2H).
13C{1H} NMR (100 MHz, CDCl3): δ 187.3 (d, J5 = 5.2 Hz), 160.6
(d, J1 = 258.3 Hz), 135.1, 134.8 (d, J4 = 8.9 Hz), 130.0, 129.8, 129.4,
127.3 (d, J6 = 4.3 Hz), 125.2 (d, J3 = 11.6 Hz), 124.5 (d, J7 = 3.6 Hz),
117.1 (d, J2 = 22.4 Hz). 19F (376 MHz, CDCl3): δ −109.75.
S-Phenyl 3-Chlorobenzothioate (1m).16 Yield: 90% (1.119 g).
White solid. 1H NMR (400 MHz, CDCl3): δ 8.00 (s, 1H), 7.93−7.91
(d, J = 7.9 Hz, 1H), 7.60−7.57 (ddd, J = 8.0, 2.1, 1.1 Hz, 1H), 7.54−
7.47 (m, 5H), 7.46−7.42 (t, J = 7.9 Hz, 1H). 13C{1H} NMR (100
MHz, CDCl3): δ 189.2, 138.3, 135.1, 133.7, 130.2, 129.9, 129.5,
127.6, 126.9, 125.7.
S-Phenyl Benzothioate (1a).15 Yield: 96% (1.029 g). White solid.
1H NMR (400 MHz, CDCl3): δ 8.05−8.03 (d, J = 7.2 Hz, 2H), 7.64−
7.60 (t, J = 7.4 Hz, 1H), 7.54−7.46 (m, 7H). 13C{1H} NMR (100
MHz, CDCl3): δ 190.3, 136.8, 135.3, 133.8, 129.7, 129.4, 128.9,
127.6, 127.5.
S-Phenyl Furan-2-carbothioate (1n).16 Yield: 87% (0.887 g). Pale
yellow solid. 1H NMR (400 MHz, CDCl3): δ 7.62 (s, 1H), 7.53−7.49
(m, 2H), 7.47−7.44 (m, 3H), 7.27−7.26 (d, J = 4.3 Hz, 1H), 6.58−
6.57 (dd, J = 3.7, 1.8 Hz, 1H). 13C{1H} NMR (100 MHz, CDCl3): δ
178.8, 150.5, 146.6, 135.3, 129.8, 129.4, 126.3, 116.4, 112.6.
S-Phenyl Thiophene-2-carbothioate (1o).16 Yield: 76% (0.835 g).
Pale yellow solid. 1H NMR (400 MHz, CDCl3): δ 7.92−7.91 (dd, J =
3.8, 1.2 Hz, 1H), 7.67−7.66 (d, J = 5.0 Hz, 1H), 7.55−7.52 (m, 2H),
S-Phenyl Naphthalene-2-carbothioate (1b).15 Yield: 70% (0.919
g). White solid. 1H NMR (400 MHz, CDCl3): δ 8.63 (s, 1H), 8.05−
8.00 (m, 2H), 7.94−7.89 (m, 2H), 7.65−7.56 (m, 4H), 7.51−7.47
(m, 3H). 13C{1H} NMR (100 MHz, CDCl3): δ 190.3, 136.0, 135.3,
134.1, 132.6, 129.8, 129.7, 129.4, 129.2, 128.8, 128.0, 127.6, 127.2,
123.4.
10832
https://doi.org/10.1021/acs.joc.1c01117
J. Org. Chem. 2021, 86, 10829−10837

The Journal of Organic Chemistry
pubs.acs.org/joc
Note
7.46−7.45 (m, 3H), 7.17−7.15 (m, 1H). 13C{1H} NMR (100 MHz,
CDCl3): δ 182.2, 141.5, 135.2, 133.4, 131.7, 129.8, 129.4, 128.2,
127.0.
MHz, CDCl3): δ 189.4, 144.9, 139.5, 135.1, 130.1, 129.6, 128.2,
127.5, 126.6, 50.1, 22.1, 11.3.
Diphenylsulfane (2a, Figure 2).15 According to the general
procedure, the reaction of S-phenyl benzothioate (0.20 mmol) and
[Rh(cod)Cl]2 (2 mol %) in toluene (0.20 M) for 15 h at 160 °C
afforded after workup and chromatography (hexane) the title
compound in 97% yield (36.1 mg). Yellow solid. 1H NMR (400
MHz, CDCl3): δ 7.36−7.33 (m, 4H), 7.32−7.28 (m, 4H), 7.26−7.22
(m, 2H). 13C{1H} NMR (100 MHz, CDCl3): δ 135.9, 131.2, 129.3,
127.2.
S-Phenyl (E)-3-Phenylprop-2-enethioate (1p).15 Yield: 84%
1
(1.012 g). Pale yellow solid. H NMR (400 MHz, CDCl3): δ 7.70−
7.66 (d, J = 15.8 Hz, 1H), 7.58−7.56 (dd, J = 6.6, 3.1 Hz, 2H), 7.51−
7.48 (m, 2H), 7.46−7.40 (m, 6H), 6.82−6.78 (d, J = 15.8 Hz, 1H).
13C{1H} NMR (100 MHz, CDCl3): δ 188.2, 141.7, 134.8, 134.2,
130.9, 129.6, 129.4, 129.2, 128.7, 127.7, 124.3.
S-(p-Tolyl) Benzothioate (1q).15 Yield: 77% (0.881 g). White solid.
1H NMR (400 MHz, CDCl3): δ 8.05−8.03 (d, J = 7.0 Hz, 2H), 7.63−
7.59 (t, J = 7.4 Hz, 1H), 7.51−7.47 (t, J = 7.7 Hz, 2H), 7.42−7.40 (d,
J = 7.9 Hz, 2H), 7.29−7.27 (d, J = 7.6 Hz, 2H), 2.42 (s, 3H). 13C{1H}
NMR (100 MHz, CDCl3): δ 190.7, 139.9, 136.8, 135.2, 133.7, 130.2,
128.8, 127.6, 123.9, 21.5.
Naphthalen-2-yl(phenyl)sulfane (2b, Figure 2).15 According to
the general procedure, the reaction of S-phenyl naphthalene-2-
carbothioate (0.20 mmol) and [Rh(cod)Cl]2 (2 mol %) in toluene
(0.20 M) for 15 h at 160 °C afforded after workup and
chromatography (hexane) the title compound in 97% yield (45.8
1
S-(4-Methoxyphenyl) Benzothioate (1r).15 Yield: 87% (1.062 g).
mg). White solid. H NMR (400 MHz, CDCl3): δ 7.85 (s, 1H),
1
7.82−7.73 (m, 3H), 7.50−7.45 (m, 2H), 7.43−7.37 (m, 3H), 7.34−
7.24 (m, 3H). 13C{1H} NMR (100 MHz, CDCl3): δ 136.0, 133.9,
133.1, 132.4, 131.1, 130.0, 129.4, 129.0, 128.9, 127.9, 127.6, 127.2,
126.7, 126.4.
White solid. H NMR (400 MHz, CDCl3): δ 8.04−8.02 (d, J = 7.3
Hz, 2H), 7.62−7.59 (t, J = 7.4 Hz, 1H), 7.50−7.47 (t, J = 7.7 Hz,
2H), 7.44−7.40 (m, 2H), 7.01−6.97 (m, 2H), 3.85 (s, 3H). 13C{1H}
NMR (100 MHz, CDCl3): δ 191.2, 160.9, 136.8, 133.7, 128.9, 127.6,
118.0, 115.1, 55.5.
Phenyl(p-tolyl)sulfane (2c, Figure 2).15 According to the general
procedure, the reaction of S-phenyl 4-methylbenzothioate (0.20
mmol) and [Rh(cod)Cl]2 (2 mol %) in toluene (0.20 M) for 15 h at
160 °C afforded after workup and chromatography (hexane) the title
compound in 94% yield (37.7 mg). White solid. 1H NMR (400 MHz,
CDCl3): δ 7.32−7.30 (d, J = 8.1 Hz, 2H), 7.28−7.27 (d, J = 4.4 Hz,
4H), 7.23−7.17 (m, 1H), 7.16−7.14 (d, J = 7.9 Hz, 2H), 2.35 (s,
3H). 13C{1H} NMR (100 MHz, CDCl3): δ 137.8, 137.3, 132.4, 131.4,
130.2, 129.9, 129.2, 126.5, 21.3.
S-[4-(Trifluoromethyl)phenyl] Benzothioate (1s).15 Yield: 83%
1
(1.177 g). White solid. H NMR (400 MHz, CDCl3): δ 8.04−8.02
(dd, J = 8.4, 1.2 Hz, 2H), 7.73−7.62 (m, 5H), 7.53−7.50 (t, J = 7.7
Hz, 2H). 13C{1H} NMR (100 MHz, CDCl3): δ 189.1, 136.4, 135.4,
134.2, 132.3, 131.6 (q, J2 = 33.0 Hz), 129.0, 127.7, 126.1 (q, J3 = 3.8
Hz), 124.0 (d, J1 = 272.4 Hz). 19F (376 MHz, CDCl3): δ −62.82.
S-(4-Fluorophenyl) Benzothioate (1t).15 Yield: 96% (1.115 g).
1
White solid. H NMR (400 MHz, CDCl3): δ 8.03−8.01 (d, J = 7.2
(4-Methoxyphenyl)(phenyl)sulfane (2d, Figure 2).15 According to
the general procedure, the reaction of S-phenyl 4-methoxybenzo-
thioate (0.20 mmol) and [Rh(cod)Cl]2 (2 mol %) in toluene (0.20
M) for 15 h at 160 °C afforded after workup and chromatography
(hexane) the title compound in 96% yield (41.5 mg). White solid. 1H
NMR (400 MHz, CDCl3): δ 7.44−7.40 (m, 2H), 7.25−7.22 (m, 2H),
7.18−7.12 (m, 3H), 6.92−6.88 (m, 2H), 3.82 (s, 3H). 13C{1H} NMR
(100 MHz, CDCl3): δ 160.0, 138.8, 135.5, 129.1, 128.3, 125.9, 124.4,
115.1, 55.5.
Hz, 2H), 7.62−7.60 (t, J = 7.4 Hz, 1H), 7.52−7.47 (m, 4H), 7.19−
7.13 (m, 2H). 13C{1H} NMR (100 MHz, CDCl3): δ 190.3, 163.8 (d,
J1 = 250.0 Hz), 137.3 (d, J3 = 8.6 Hz), 136.5, 134.0, 129.0, 127.6,
122.7 (d, J4 = 3.6 Hz), 116.7 (d, J2 = 22.3 Hz). 19F (376 MHz,
CDCl3): δ −111.02.
S-(o-Tolyl) Benzothioate (1u).15 Yield: 93% (1.065 g). Colorless
1
oil. H NMR (400 MHz, CDCl3): δ 8.08−8.06 (d, J = 7.5 Hz, 2H),
7.64−7.60 (t, J = 7.4 Hz, 1H), 7.52−7.48 (m, 3H), 7.41−7.36 (m,
2H), 7.30−7.27 (m, 1H), 2.41 (s, 3H). 13C{1H} NMR (100 MHz,
CDCl3): δ 189.8, 142.8, 136.9, 136.5, 133.7, 131.0, 130.4, 128.9,
127.7, 126.9, 126.8, 21.0.
Phenyl[4-(trifluoromethyl)phenyl]sulfane (2e, Figure 2).15 Ac-
cording to the general procedure, the reaction of S-phenyl 4-
(trifluoromethyl)benzothioate (0.20 mmol) and [Rh(cod)Cl]2 (2 mol
%) in toluene (0.20 M) for 15 h at 160 °C afforded after workup and
chromatography (hexane) the title compound in 87% yield (44.2 mg).
S-(Thiophen-2-yl) Benzothioate (1v).16 Yield: 73% (0.804 g).
Brown solid. 1H NMR (400 MHz, CDCl3): δ 8.03−8.01 (dd, J = 8.4,
1.0 Hz, 2H), 7.65−7.61 (m, 2H), 7.52−7.48 (t, J = 7.8 Hz, 2H),
7.27−7.26 (dd, J = 3.6, 1.2 Hz, 1H), 7.18−7.16 (dd, J = 5.3, 3.6 Hz,
1H). 13C{1H} NMR (100 MHz, CDCl3): δ 190.0, 136.5, 136.1, 134.1,
132.3, 129.0, 128.1, 127.7, 124.3.
1
White solid. H NMR (400 MHz, CDCl3): δ 7.50−7.47 (m, 5H),
7.41−7.38 (m, 3H), 7.28 (s, 1H). 13C{1H} NMR (100 MHz, CDCl3):
δ 143.0, 133.7, 132.6, 129.8, 128.8, 128.4, 128.2 (d, J2 = 32.7 Hz),
126.0 (q, J3 = 3.8 Hz), 124.2 (d, J1 = 271.8 Hz). 19F (376 MHz,
CDCl3): δ −62.46.
S-Decyl Benzothioate (1w).15 Yield: 90% (1.259 g). Yellow oil. 1H
NMR (400 MHz, CDCl3): δ 7.98−7.96 (dd, J = 8.4, 1.3 Hz, 2H),
7.58−7.54 (t, J = 7.4 Hz, 1H), 7.46−7.42 (t, J = 7.7 Hz, 2H), 3.09−
3.05 (t, J = 8.0 Hz, 2H), 1.71−1.63 (p, J = 7.3 Hz, 2H), 1.46−1.39 (p,
J = 6.7 Hz, 2H), 1.32−1.26 (m, 12H), 0.90−0.86 (t, J = 6.9 Hz, 3H).
13C{1H} NMR (100 MHz, CDCl3): δ 192.3, 137.4, 133.3, 128.7,
127.3, 32.0, 29.7, 29.7, 29.6, 29.4, 29.3, 29.2, 29.1, 22.8, 14.3.
4-[(Phenylthio)carbonyl]phenyl Benzoate (1x).15 Yield: 94%
(4-Fluorophenyl)(phenyl)sulfane (2f, Figure 2).15 According to
the general procedure, the reaction of S-phenyl 4-fluorobenzothioate
(0.20 mmol) and [Rh(cod)Cl]2 (2 mol %) in toluene (0.20 M) for 15
h at 160 °C afforded after workup and chromatography (hexane) the
1
title compound in 93% yield (38.0 mg). White solid. H NMR (400
MHz, CDCl3): δ 7.39−7.35 (m, 2H), 7.30−7.21 (m, 5H), 7.04−7.00
(m, 2H). 13C{1H} NMR (100 MHz, CDCl3): δ 162.6 (d, J1 = 247.8
Hz), 136.8, 134.3 (d, J3 = 8.0 Hz), 130.3 (d, J4 = 3.4 Hz), 130.1,
129.3, 126.9, 116.6 (d, J2 = 21.8 Hz). 19F (376 MHz, CDCl3): δ
−114.02.
1
(1.571 g). White solid. H NMR (400 MHz, CDCl3): δ 8.23−8.21
(d, J = 9.5 Hz, 2H), 8.14−8.12 (d, J = 8.8 Hz, 2H), 7.69−7.65 (t, J =
6.8 Hz, 1H), 7.56−7.52 (m, 4H), 7.48−7.46 (m, 3H), 7.38−7.36 (d, J
= 8.8 Hz, 2H). 13C{1H} NMR (100 MHz, CDCl3): δ 189.2, 164.7,
155.3, 135.3, 134.3, 134.1, 130.4, 129.8, 129.5, 129.3, 129.1, 128.9,
127.3, 122.3.
(4-Chlorophenyl)(phenyl)sulfane (2g, Figure 2).15 According to
the general procedure, the reaction of S-phenyl 4-chlorobenzothioate
(0.20 mmol) and [Rh(cod)Cl]2 (2 mol %) in toluene (0.20 M) for 15
h at 160 °C afforded after workup and chromatography (hexane) the
S-Phenyl 4-Bromobenzothioate (1y).21 Yield: 78% (1.143 g).
1
White solid. H NMR (400 MHz, CDCl3): δ 7.91−7.88 (m, 2H),
1
7.65−7.62 (m, 2H), 7.53−7.46 (m, 5H). 13C{1H} NMR (100 MHz,
CDCl3): δ 189.5, 135.5, 135.2, 132.2, 129.9, 129.5, 129.1, 128.9,
127.0.
title compound in 92% yield (40.6 mg). White solid. H NMR (400
MHz, CDCl3): δ 7.36−7.30 (m, 4H), 7.29−7.23 (m, 5H). 13C{1H}
NMR (100 MHz, CDCl3): δ 135.3, 134.8, 133.1, 132.2, 131.5, 129.5,
129.5, 127.6.
S-Phenyl 4-(N,N-Dipropylsulfamoyl)benzothioate (1z).15 Yield:
80% (1.510 g). Pale yellow solid. H NMR (400 MHz, CDCl3): δ
4-(Phenylthio)benzonitrile (2h, Figure 2).15 According to the
general procedure, the reaction of S-phenyl 4-cyanobenzothioate
(0.20 mmol) and [Rh(cod)Cl]2 (2 mol %) in toluene (0.20 M) for 15
h at 160 °C afforded after workup and chromatography (hexane) the
1
8.14−8.12 (d, J = 8.6 Hz, 2H), 7.93−7.91 (d, J = 8.6 Hz, 2H), 7.53−
7.47 (m, 5H), 3.13−3.09 (t, J = 7.6 Hz, 4H), 1.61−1.52 (dq, J = 14.9,
7.6 Hz, 4H), 0.90−0.86 (t, J = 7.4 Hz, 6H). 13C{1H} NMR (100
10833
https://doi.org/10.1021/acs.joc.1c01117
J. Org. Chem. 2021, 86, 10829−10837

The Journal of Organic Chemistry
pubs.acs.org/joc
Note
1
title compound in 90% yield (38.0 mg). White solid. H NMR (400
MHz, CDCl3): δ 7.53−7.50 (m, 2H), 7.49−7.47 (d, J = 8.7 Hz, 2H),
7.44−7.43 (m, 3H), 7.18−7.15 (m, 2H). 13C{1H} NMR (100 MHz,
CDCl3): δ 145.9, 134.7, 132.5, 130.97, 130.1, 129.6, 127.5, 119.0,
108.8.
(0.20 M) for 15 h at 160 °C afforded after workup and
chromatography (1/15 ethyl acetate/hexane) the title compound in
1
98% yield (41.6 mg). White solid. H NMR (400 MHz, CDCl3): δ
7.43−7.41 (m, 2H), 7.36−7.22 (m, 8H), 6.91−6.87 (d, J = 15.5 Hz,
1H), 6.75−6.72 (d, J = 15.5 Hz, 1H). 13C{1H} NMR (100 MHz,
CDCl3): δ 136.7, 135.4, 132.0, 130.0, 129.3, 128.8, 127.7, 127.1,
126.2, 123.5.
Methyl 4-(Phenylthio)benzoate (2i, Figure 2).15 According to the
general procedure, the reaction of methyl 4-[(phenylthio)carbonyl]-
benzoate (0.20 mmol) and [Rh(cod)Cl]2 (2 mol %) in toluene (0.20
M) for 15 h at 160 °C afforded after workup and chromatography
(hexane) the title compound in 83% yield (40.6 mg). White solid. 1H
NMR (400 MHz, CDCl3): δ 7.91−7.88 (m, 2H), 7.50−7.48 (m, 2H),
7.42−7.38 (m, 3H), 7.22−7.19 (m, 2H), 3.89 (s, 3H). 13C{1H} NMR
(100 MHz, CDCl3): δ 166.7, 144.5, 133.9, 132.50, 130.2, 129.8,
128.8, 127.7, 127.6, 52.2.
Phenyl(p-tolyl)sulfane (2c′, Figure 3).15 According to the general
procedure, the reaction of S-(p-tolyl) benzothioate (0.20 mmol) and
[Rh(cod)Cl]2 (2 mol %) in toluene (0.20 M) for 15 h at 160 °C
afforded after workup and chromatography (hexane) the title
compound in 98% yield (39.3 mg). White solid. 1H NMR (400
MHz, CDCl3): δ 7.32−7.30 (d, J = 8.1 Hz, 2H), 7.28−7.27 (d, J = 4.4
Hz, 4H), 7.23−7.17 (m, 1H), 7.16−7.14 (d, J = 7.9 Hz, 2H), 2.35 (s,
3H). 13C{1H} NMR (100 MHz, CDCl3): δ 137.8, 137.3, 132.4, 131.4,
130.2, 129.9, 129.2, 126.5, 21.3.
1-[4-(Phenylthio)phenyl]ethan-1-one (2j, Figure 2).15 According
to the general procedure, the reaction of S-phenyl 4-acetylbenzo-
thioate (0.20 mmol) and [Rh(cod)Cl]2 (2 mol %) in toluene (0.20
M) for 15 h at 160 °C afforded after workup and chromatography (1/
15 ethyl acetate/hexane) the title compound in 72% yield (32.9 mg).
(4-Methoxyphenyl)(phenyl)sulfane (2d′, Figure 3).15 According
to the general procedure, the reaction of S-(4-methoxyphenyl)
benzothioate (0.20 mmol) and [Rh(cod)Cl]2 (2 mol %) in toluene
(0.20 M) for 15 h at 160 °C afforded after workup and
chromatography (hexane) the title compound in 98% yield (42.4
1
White solid. H NMR (400 MHz, CDCl3): δ 7.83−7.80 (m, 2H),
7.51−7.49 (m, 2H), 7.42−7.39 (m, 3H), 7.23−7.19 (m, 2H), 2.55 (s,
3H). 13C{1H} NMR (100 MHz, CDCl3): δ 197.3, 145.1, 134.6, 134.0,
132.2, 129.8, 129.1, 129.0, 127.6, 26.6.
1
mg). White solid. H NMR (400 MHz, CDCl3): δ 7.44−7.40 (m,
2H), 7.25−7.22 (m, 2H), 7.18−7.12 (m, 3H), 6.92−6.88 (m, 2H),
3.82 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3): δ 160.0, 138.8,
135.5, 129.1, 128.3, 125.9, 124.4, 115.1, 55.5.
Phenyl(o-tolyl)sulfane (2k, Figure 2).15 According to the general
procedure, the reaction of S-phenyl 2-methylbenzothioate (0.20
mmol) and [Rh(cod)Cl]2 (2 mol %) in toluene (0.20 M) for 15 h at
160 °C afforded after workup and chromatography (hexane) the title
compound in 70% yield (28.0 mg). White solid. 1H NMR (400 MHz,
CDCl3): δ 7.35−7.13 (m, 9H), 2.38 (s, 3H). 13C{1H} NMR (100
MHz, CDCl3): δ 140.1, 136.3, 133.9, 133.1, 131.2, 130.7, 129.8,
129.3, 128.1, 126.9, 126.5, 20.7.
Phenyl[4-(trifluoromethyl)phenyl]sulfane (2e′, Figure 3).15 Ac-
cording to the general procedure, the reaction of S-[4-
(trifluoromethyl)phenyl] benzothioate (0.20 mmol) and [Rh(cod)-
Cl]2 (2 mol %) in toluene (0.20 M) for 15 h at 160 °C afforded after
workup and chromatography (hexane) the title compound in 97%
1
yield (49.3 mg). White solid. H NMR (400 MHz, CDCl3): δ 7.50−
(2-Fluorophenyl)(phenyl)sulfane (2l, Figure 2).15 According to
the general procedure, the reaction of S-phenyl 2-fluorobenzothioate
(0.20 mmol) and [Rh(cod)Cl]2 (2 mol %) in toluene (0.20 M) for 15
h at 160 °C afforded after workup and chromatography (1/15 ethyl
acetate/hexane) the title compound in 91% yield (37.2 mg). White
solid. 1H NMR (400 MHz, CDCl3): δ 7.36−7.23 (m, 7H), 7.13−7.05
(m, 2H). 13C{1H} NMR (100 MHz, CDCl3): δ 161.3 (d, J1 = 247.1
Hz), 134.3, 133.6, 131.1, 129.5 (d, J4 = 7.9 Hz), 129.4, 127.4, 124.9
7.47 (m, 5H), 7.41−7.38 (m, 3H), 7.28 (s, 1H). 13C{1H} NMR (100
MHz, CDCl3): δ 143.0, 133.7, 132.6, 129.8, 128.8, 128.4, 128.2 (d, J2
= 32.7 Hz), 126.0 (q, J3 = 3.8 Hz), 124.2 (d, J1 = 271.8 Hz). 19F (376
MHz, CDCl3): δ −62.46.
(4-Fluorophenyl)(phenyl)sulfane (2f′, Figure 3).15 According to
the general procedure, the reaction of S-(4-fluorophenyl) benzo-
thioate (0.20 mmol) and [Rh(cod)Cl]2 (2 mol %) in toluene (0.20
M) for 15 h at 160 °C afforded after workup and chromatography
(hexane) the title compound in 98% yield (40.0 mg). White solid. 1H
NMR (400 MHz, CDCl3): δ 7.40−7.35 (m, 2H), 7.29−7.21 (m, 5H),
7.05−7.01 (m, 2H). 13C{1H} NMR (100 MHz, CDCl3): δ 162.6 (d,
J1 = 247.8 Hz), 136.8, 134.3 (d, J3 = 8.0 Hz), 130.3 (d, J4 = 3.4 Hz),
130.1, 129.3, 126.9, 116.6 (d, J2 = 21.8 Hz). 19F (376 MHz, CDCl3):
δ −114.02.
(d, J5 = 3.7 Hz), 122.9 (d, J3 = 17.5 Hz), 116.1 (d, J2 = 22.4 Hz). 19
(376 MHz, CDCl3): δ −108.75.
F
(3-Chlorophenyl)(phenyl)sulfane (2m, Figure 2).16 According to
the general procedure, the reaction of S-phenyl 3-chlorobenzothioate
(0.20 mmol) and [Rh(cod)Cl]2 (2 mol %) in toluene (0.20 M) for 15
h at 160 °C afforded after workup and chromatography (hexane) the
title compound in 86% yield (38.0 mg). Colorless oil. 1H NMR (400
MHz, CDCl3): δ 7.42−7.39 (m, 2H), 7.38−7.31 (m, 3H), 7.25−7.22
(m, 1H), 7.21−7.14 (m, 3H). 13C{1H} NMR (100 MHz, CDCl3): δ
139.0, 135.0, 134.0, 132.5, 130.2, 129.6, 129.6, 128.1, 128.0, 126.9.
2-(Phenylthio)furan (2n, Figure 2).16 According to the general
procedure, the reaction of S-phenyl furan-2-carbothioate (0.20 mmol)
and [Rh(cod)Cl]2 (2 mol %) in toluene (0.20 M) for 15 h at 160 °C
afforded after workup and chromatography (hexane) the title
Phenyl(o-tolyl)sulfane (2k′, Figure 3).15 According to the general
procedure, the reaction of S-(o-tolyl) benzothioate (0.20 mmol) and
[Rh(cod)Cl]2 (2 mol %) in toluene (0.20 M) for 15 h at 160 °C
afforded after workup and chromatography (hexane) the title
compound in 93% yield (37.3 mg). White solid. 1H NMR (400
MHz, CDCl3): δ 7.35−7.13 (m, 9H), 2.38 (s, 3H). 13C{1H} NMR
(100 MHz, CDCl3): δ 140.1, 136.3, 133.9, 133.1, 131.2, 130.7, 129.8,
129.3, 128.1, 126.9, 126.5, 20.7.
compound in 88% yield (31.0 mg). H NMR (400 MHz, CDCl3):
2-(Phenylthio)thiophene (2o′, Figure 3).15 According to the
general procedure, the reaction of S-(thiophen-2-yl) benzothioate
(0.20 mmol) and [Rh(cod)Cl]2 (2 mol %) in toluene (0.20 M) for 15
h at 160 °C afforded after workup and chromatography (hexane) the
1
δ 7.59−7.58 (dd, J = 1.9, 0.8 Hz, 1H), 7.36−7.27 (m, 1H), 7.24 (s,
1H), 7.18−7.15 (m, 3H), 6.76−6.75 (dd, J = 3.2, 0.9 Hz, 1H), 6.49−
6.47 (dd, J = 3.3, 2.0 Hz, 1H). 13C{1H} NMR (100 MHz, CDCl3): δ
146.7, 143.2, 136.5, 131.2, 129.2, 127.7, 127.2, 126.5, 119.7, 112.0.
2-(Phenylthio)thiophene (2o, Figure 2).15 According to the
general procedure, the reaction of S-phenyl thiophene-2-carbothioate
(0.20 mmol) and [Rh(cod)Cl]2 (2 mol %) in toluene (0.20 M) for 15
h at 160 °C afforded after workup and chromatography (hexane) the
1
title compound in 80% yield (30.8 mg). White solid. H NMR (400
MHz, CDCl3): δ 7.49−7.47 (dd, J = 5.4, 1.2 Hz, 1H), 7.37−7.28 (m,
2H), 7.24 (s, 1H), 7.21−7.14 (m, 3H), 7.09−7.07 (dd, J = 5.4, 3.6
Hz, 1H). 13C{1H} NMR (100 MHz, CDCl3): δ 138.8, 136.2, 131.4,
131.2, 129.3, 129.1, 128.1, 127.3, 126.2.
title compound in 98% yield (37.7 mg). White solid. H NMR (400
Decyl(phenyl)sulfane (2q, Figure 3).15 According to the general
procedure, the reaction of S-decyl benzothioate (0.20 mmol) and
[Rh(cod)Cl]2 (2 mol %) in toluene (0.20 M) for 15 h at 160 °C
afforded after workup and chromatography (hexane) the title
compound in 97% yield (48.6 mg). Colorless oil. 1H NMR (400
MHz, CDCl3): δ 7.33−7.25 (m, 4H), 7.18−7.14 (m, 1H), 2.93−2.90
(m, 2H), 1.68−1.61 (p, J = 7.3 Hz, 2H), 1.45−1.38 (p, J = 6.8 Hz,
2H), 1.26 (s, 12H), 0.90−0.86 (t, J = 6.8 Hz, 3H). 13C{1H} NMR
1
MHz, CDCl3): δ 7.49−7.47 (dd, J = 5.4, 1.2 Hz, 1H), 7.37−7.28 (m,
2H), 7.24 (s, 1H), 7.21−7.14 (m, 3H), 7.09−7.07 (dd, J = 5.4, 3.6
Hz, 1H). 13C{1H} NMR (100 MHz, CDCl3): δ 138.8, 136.2, 131.4,
131.2, 129.3, 129.1, 128.1, 127.3, 126.2.
(E)-Phenyl(styryl)sulfane (2p, Figure 2).15 According to the
general procedure, the reaction of S-phenyl (E)-3-phenylprop-2-
enethioate (0.20 mmol) and [Rh(cod)Cl]2 (2 mol %) in toluene
10834
https://doi.org/10.1021/acs.joc.1c01117
J. Org. Chem. 2021, 86, 10829−10837

The Journal of Organic Chemistry
pubs.acs.org/joc
Note
(100 MHz, CDCl3): δ 137.2, 129.0, 125.8, 33.7, 32.0, 29.7, 29.7, 29.5,
29.3, 29.3, 29.0, 22.8, 14.3.
orcid.org/0000-0002-9650-9690;
Email: michal.szostak@rutgers.edu
Chengwei Liu − Chemistry Research Laboratory, University of
Oxford, Oxford OX1 3TA, United Kingdom; orcid.org/
0000-0003-1297-7188; Email: chengwei.liu@
chem.ox.ac.uk
4-(Phenylthio)phenyl Benzoate (2r, Figure 4A).15 According to
the general procedure, the reaction of 4-[(phenylthio)carbonyl]-
phenyl benzoate (0.20 mmol) and [Rh(cod)Cl]2 (2 mol %) in
toluene (0.20 M) for 15 h at 160 °C afforded after workup and
chromatography (1/15 ethyl acetate/hexane) the title compound in
1
91% yield (55.8 mg). Colorless oil. H NMR (400 MHz, CDCl3): δ
Authors
8.21−8.18 (dd, J = 8.2, 1.0 Hz, 2H), 7.67−7.63 (t, J = 7.4 Hz, 1H),
7.54−7.50 (t, J = 7.7 Hz, 2H), 7.43−7.40 (m, 2H), 7.37−7.30 (m,
4H), 7.27−7.25 (m, 1H), 7.20−7.16 (m, 2H). 13C{1H} NMR (100
MHz, CDCl3): δ 165.2, 150.3, 136.0, 133.9, 133.1, 132.6, 131.0,
130.4, 129.5, 129.4, 128.8, 127.3, 122.7.
Han Cao − Lunan Coal Chemical Research Institute of
Engineering and Technology, Zaozhuang University,
Zaozhuang, Shandong 277160, China; orcid.org/0000-
0001-7470-9213
Fusheng Bie − Lunan Coal Chemical Research Institute of
Engineering and Technology, Zaozhuang University,
Zaozhuang, Shandong 277160, China; orcid.org/0000-
0002-4711-5185
Yijun Shi − Lunan Coal Chemical Research Institute of
Engineering and Technology, Zaozhuang University,
Zaozhuang, Shandong 277160, China
Ying Han − Lunan Coal Chemical Research Institute of
Engineering and Technology, Zaozhuang University,
Zaozhuang, Shandong 277160, China
(4-Bromophenyl)(phenyl)sulfane (2s, Figure 4B).22 According to
the general procedure, the reaction of S-phenyl 4-bromobenzothioate
(1.0 g, 3.41 mmol) and [Rh(cod)Cl]2 (2 mol %) in toluene (0.20 M)
for 15 h at 160 °C afforded after workup and chromatography
1
(hexane) the title compound in 90% yield (0.81 g). Yellow solid. H
NMR (400 MHz, CDCl3): δ 7.42−7.39 (m, 2H), 7.37−7.22 (m, 5H),
7.19−7.16 (m, 2H). 13C{1H} NMR (100 MHz, CDCl3): δ 135.6,
135.0, 132.4, 132.2, 131.7, 131.6, 131.3, 129.5, 127.7, 121.0.
4-(Phenylthio)-N,N-dipropylbenzenesulfonamide (2t, Figure
5A).16 According to the general procedure, the reaction of S-phenyl
4-(N,N-dipropylsulfamoyl)benzothioate (0.20 mmol) and [Rh(cod)-
Cl]2 (2 mol %) in toluene (0.20 M) for 15 h at 160 °C afforded after
workup and chromatography (1/15 ethyl acetate/hexane) the title
compound in 87% yield (60.8 mg). White solid. 1H NMR (400 MHz,
CDCl3): δ 7.66−7.62 (m, 2H), 7.51−7.48 (m, 2H), 7.42−7.40 (m,
3H), 7.23−7.20 (m, 2H), 3.06−3.02 (m, 4H), 1.57−1.50 (m, 4H),
0.88−0.84 (t, J = 7.4 Hz, 6H). 13C{1H} NMR (100 MHz, CDCl3): δ
144.2, 137.3, 134.2, 131.8, 129.9, 129.2, 127.8, 127.7, 50.2, 22.2, 11.3.
(4-Bromophenyl)(phenyl)sulfane (2s, Figure 5B).16 According to
the general procedure, the reaction of S-phenyl 4-bromobenzothioate
(0.2 mmol) and [Rh(cod)Cl]2 (2 mol %) in toluene (0.20 M) for 15
h at 160 °C afforded after workup and chromatography (hexane) the
Peng Yan − Lunan Coal Chemical Research Institute of
Engineering and Technology, Zaozhuang University,
Zaozhuang, Shandong 277160, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.joc.1c01117
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
1
■
title compound in 91% yield (48.3 mg). Yellow solid. H NMR (400
The authors thank Zaozhuang University, the Shandong Lunan
Coal Chemical Research Institute of Engineering and
Technology, the Zaozhuang Science and Technology Develop-
ment Program (2018GH19), the National Science Foundation
(CAREER CHE-1650766), and Rutgers University for
financial support. The Bruker 400 MHz spectrometer used in
this study was supported by the College of Chemistry,
Chemical Engineering and Materials Science at Zaozhuang
University.
MHz, CDCl3): δ 7.42−7.39 (m, 2H), 7.37−7.22 (m, 5H), 7.19−7.16
(m, 2H). 13C{1H} NMR (100 MHz, CDCl3): δ 135.6, 135.0, 132.4,
132.2, 131.7, 131.6, 131.3, 129.5, 127.7, 121.0.
N-Methyl-N-phenyl-4-(phenylthio)aniline (2u, Figure 5B). The
reaction of (4-bromophenyl)(phenyl)sulfane (0.20 mmol), N-
methylaniline (0.40 mmol), Pd2(dba)3 (1 mol %), tri-tert-
butylphosphonium tetrafluoroborate (4 mol %), and sodium tert-
butoxide (0.4 mmol) in toluene (0.20 M) for 15 h at 110 °C afforded
after workup and chromatography (1/15 ethyl acetate/hexane) the
1
title compound in 98% yield (57.1 mg). Pale solid. H NMR (400
MHz, CDCl3): δ 7.36−7.32 (m, 4H), 7.27−7.19 (m, 4H), 7.16−7.14
(d, J = 7.6 Hz, 3H), 7.11−7.07 (t, J = 7.3 Hz, 1H), 6.92−6.87 (m,
2H), 3.34 (s, 3H). 13C{1H} NMR (100 MHz, CDCl3): δ 149.2,
148.4, 139.0, 135.0, 129.7, 129.0, 128.2, 125.8, 123.6, 123.5, 122.5,
118.3, 40.4. ESI-MS (m/z): calcd for C19H18NS (M+ + H), 292.1160;
found, 292.1157.
REFERENCES
■
(1) For general reviews of sulfur-containing drugs, see: (a) Ilardi, E.
A.; Vitaku, E.; Njardarson, J. T. Data-Mining for Sulfur and Fluorine:
An Evaluation of Pharmaceuticals To Reveal Opportunities for Drug
Design and Discovery. J. Med. Chem. 2014, 57, 2832−2842. (b) Beno,
B. R.; Yeung, K. S.; Bartberger, M. D.; Pennington, L. D.; Meanwell,
N. A. A Survey of the Role of Noncovalent Sulfur Interactions in Drug
Design. J. Med. Chem. 2015, 58, 4383−4438. (c) Scott, K. A.;
Njardarson, J. T. Analysis of US FDA-Approved Drugs Containing
Sulfur Atoms. Top Curr. Chem. 2019, 376 (5), 1−34. For recent
studies of the synthesis of sulfur heterocycles, see: (d) Lamers, P.;
Buglioni, L.; Koschmieder, S.; Chatain, N.; Bolm, C. Benzo[c]-
isothiazole 2-Oxides: Three-Dimensional Heterocycles with Cross-
Coupling and Functionalization Potential. Adv. Synth. Catal. 2016,
358, 3649−3653. (e) Lamers, P.; Bolm, C. Tetrahydrobenzo[c]-
thieno[2,1-e]isothiazole 4-Oxides: Three-Dimensional Heterocycles
as Cross-Coupling Building Blocks. Org. Lett. 2018, 20, 116−118.
(f) Yu, H.; Li, Z.; Bolm, C. Three-Dimensional Heterocycles by Iron-
Catalyzed Ring-Closing Sulfoxide Imidation. Angew. Chem., Int. Ed.
2018, 57, 12053−12056.
ASSOCIATED CONTENT
* Supporting Information
■
sı
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.joc.1c01117.
1H, 13C, and 19F NMR spectra (PDF)
AUTHOR INFORMATION
Corresponding Authors
■
Xuejing Liu − Lunan Coal Chemical Research Institute of
Engineering and Technology, Zaozhuang University,
Zaozhuang, Shandong 277160, China; Email: lxj3786749@
126.com
(2) Brunton, L.; Chabner, B.; Knollman, B. Goodman and Gilman’s
The Pharmacological Basis of Therapeutics; McGraw-Hill: New York,
2010.
Michal Szostak − Department of Chemistry, Rutgers
University, Newark, New Jersey 07102, United States;
10835
https://doi.org/10.1021/acs.joc.1c01117
J. Org. Chem. 2021, 86, 10829−10837

The Journal of Organic Chemistry
pubs.acs.org/joc
Note
(3) For selected examples of the synthesis of thioethers, see:
(a) Jouffroy, M.; Kelly, C. B.; Molander, G. A. Thioetherification via
Photoredox/Nickel Dual Catalysis. Org. Lett. 2016, 18, 876−879.
(b) Oderinde, M. S.; Frenette, M.; Robbins, D. W.; Aquila, B.;
Johannes, J. W. Photoredox Mediated Nickel Catalyzed Cross-
Coupling of Thiols With Aryl and Heteroaryl Iodides via Thiyl
Radicals. J. Am. Chem. Soc. 2016, 138, 1760−1763. (c) Liu, B.; Lim,
C. H.; Miyake, G. M. Visible-Light-Promoted C−S Cross-Coupling
via Intermolecular Charge Transfer. J. Am. Chem. Soc. 2017, 139,
13616−13619. (d) Uyeda, C.; Tan, Y.; Fu, G. C.; Peters, J. C. A New
Family of Nucleophiles for Photoinduced, Copper-Catalyzed Cross-
Couplings via Single-Electron Transfer: Reactions of Thiols with Aryl
Halides Under Mild Conditions (0 °C). J. Am. Chem. Soc. 2013, 135,
9548−9552. (e) Fernandez-Rodriguez, M. A.; Shen, Q.; Hartwig, J. F.
A General and Long-Lived Catalyst for the Palladium-Catalyzed
Coupling of Aryl Halides with Thiols. J. Am. Chem. Soc. 2006, 128,
2180−2181. (f) Saravanan, P.; Anbarasan, P. Palladium Catalyzed
Aryl(alkyl)thiolation of Unactivated Arenes. Org. Lett. 2014, 16, 848−
851.
(4) For reviews of C−S bond formation, see: (a) Stambuli, J. P. in
New Trends in Cross-Coupling; Colacot, T. J., Ed.; The Royal Society
of Chemistry, 2015; pp 254−275. (b) Eichman, C. C.; Stambuli, J. P.
Transition Metal Catalyzed Synthesis of Aryl Sulfides. Molecules 2011,
16, 590−608. (c) Beletskaya, I. P.; Ananikov, V. P. Transition-Metal-
Catalyzed C−S, C−Se, and C−Te Bond Formation via Cross-
Coupling and Atom-Economic Addition Reactions. Chem. Rev. 2011,
111, 1596−1636.
(5) For reviews of decarbonylative cross-coupling, see: (a) Lu, H.;
Yu, T. Y.; Xu, P. F.; Wei, H. Selective Decarbonylation via Transition-
Metal-Catalyzed Carbon−Carbon Bond Cleavage. Chem. Rev. 2021,
121, 365−411. (b) Liu, C.; Szostak, M. Decarbonylative Cross-
Coupling of Amides. Org. Biomol. Chem. 2018, 16, 7998−8010.
(6) For representative decarbonylative coupling of carboxylic acids,
see: (a) Liu, C.; Ji, C. L.; Hong, X.; Szostak, M. Palladium-Catalyzed
Decarbonylative Borylation of Carboxylic Acids: Tuning Reaction
Selectivity by Computation. Angew. Chem., Int. Ed. 2018, 57, 16721−
16726. (b) Liu, C.; Ji, C. L.; Zhou, T.; Hong, X.; Szostak, M.
Bimetallic Cooperative Catalysis for Decarbonylative Heteroarylation
of Carboxylic Acids via C-O/C-H Coupling. Angew. Chem., Int. Ed.
2021, 60, 10690−10699.
Catalyzed Reactions by N−C Amide Bond Activation. Chem. - Eur.
J. 2017, 23, 7157−7173. (b) Takise, R.; Muto, K.; Yamaguchi, J.
Cross-Coupling of Aromatic Esters and Amides. Chem. Soc. Rev. 2017,
46, 5864−5888. (c) Dzik, W.; Lange, P.; Gooßen, L. Carboxylates as
sources of carbon nucleophiles and electrophiles: comparison of
decarboxylative and decarbonylative pathways. Chem. Sci. 2012, 3,
2671−2678. (d) Gooßen, L. J.; Rodriguez, N.; Gooßen, K. Carboxylic
acids as substrates in homogeneous catalysis. Angew. Chem., Int. Ed.
2008, 47, 3100−3120.
(10) (a) Hirschbeck, V.; Gehrtz, P. H.; Fleischer, I. Metal-Catalyzed
Synthesis and Use of Thioesters: Recent Developments. Chem. - Eur.
J. 2018, 24, 7092−7107. (b) Liu, W.; Xu, W.; Wang, J.; Lu, H.; Xu, P.-
F.; Wei, H. Synthesis of Spirocycles via Ni-Catalyzed Intramolecular
Coupling of Thioesters and Olefins. Chem. - Eur. J. 2021, 27, 7651−
7656. (c) Arisawa, M.; Tanii, S.; Yamada, T.; Yamaguchi, M.
Palladium-Catalyzed Addition Reaction of Thioesters to Norbor-
nenes. Tetrahedron 2015, 71, 6449−6458.
(11) For representative decarboxylative C−S coupling of carboxylic
acids, see: (a) Li, M.; Hoover, J. M. Aerobic Copper-Catalyzed
Decarboxylative Thiolation. Chem. Commun. 2016, 52, 8733−8736.
(b) Duan, Z.; Ranjit, S.; Zhang, P.; Liu, X. Synthesis of Aryl Sulfides
by Decarboxylative C−S Cross-Couplings. Chem. - Eur. J. 2009, 15,
3666−3669. (c) Ranjit, S.; Duan, Z.; Zhang, P.; Liu, X. Synthesis of
Vinyl Sulfides by Copper-Catalyzed Decarboxylative C−S Cross-
Coupling. Org. Lett. 2010, 12, 4134−4136. For excellent controlled
C−S decarbonylations of α-ketothioesters, see: (d) Zheng, Z.-J.;
Jiang, C.; Shao, P.-C.; Liu, W.-F.; Zhao, T.-T.; Xu, P.-F.; Wei, H.
Controlled Ni-Catalyzed Mono- and Double-Decarbonylations of α-
Ketothioesters. Chem. Commun. 2019, 55, 1907−1910.
(12) Wenkert, E.; Chianelli, D. Nickel-catalysed Decarbonylation of
Thioesters. J. Chem. Soc., Chem. Commun. 1991, 627−628.
(13) (a) Ichiishi, N.; Malapit, C. A.; Wozniak, L.; Sanford, M. S.
Palladium- and Nickel-Catalyzed Decarbonylative C−S Coupling to
Convert Thioesters to Thioethers. Org. Lett. 2018, 20, 44−47.
(b) Brigham, C. E.; Malapit, C. A.; Lalloo, N.; Sanford, M. S. Nickel-
Catalyzed Decarbonylative Synthesis of Fluoroalkyl Thioethers. ACS
Catal. 2020, 10, 8315−8320.
(14) Ishitobi, K.; Isshiki, R.; Asahara, K. K.; Lim, C.; Muto, K.;
Yamaguchi, J. Decarbonylative Aryl Thioether Synthesis by Ni
Catalysis. Chem. Lett. 2018, 47, 756−759.
(15) Liu, C.; Szostak, M. Decarbonylative Thioetherification by
Nickel Catalysis Using Air- and Moisture-Stable Nickel Precatalysts.
Chem. Commun. 2018, 54, 2130−2133.
(16) Cao, H.; Liu, X.; Bie, F.; Shi, Y.; Han, Y.; Yan, P.; Szostak, M.;
Liu, C. General and Practical Intramolecular Decarbonylative
Coupling of Thioesters via Palladium Catalysis. Org. Chem. Front.
2021, 8, 1587−1592.
(17) (a) Kato, T.; Kuniyasu, H.; Kajiura, T.; Minami, Y.; Ohtaka, A.;
Kinomoto, M.; Terao, J.; Kurosawa, H.; Kambe, N. β-cis-SAr Effect
on Decarbonylation from α,β-Unsaturated Acyl and Aroyl Complexes.
Chem. Commun. 2006, 868−870. (b) Minami, Y.; Kuniyasu, H.;
Miyafuji, K.; Kambe, N. Transition-metal-catalyzed Regioselective
Aroyl- and Trifluoro-Acetylthiolation of Alkynes using Thioesters.
Chem. Commun. 2009, 3080−3082.
(18) Osakada, K.; Yamamoto, T.; Yamamoto, A. Decarbonylation of
Thiol Esters to Give Sulfides Promoted by Transition Metal
Complexes. Tetrahedron Lett. 1987, 28, 6321−6324.
(19) For representative examples of Rh catalysis, see: (a) Fagnou,
K.; Lautens, M. Rhodium-Catalyzed Carbon-Carbon Bond Forming
Reactions of Organometallic Compounds. Chem. Rev. 2003, 103,
169−196. (b) Varni, A. J.; Bautista, M. V.; Noonan, K. J. T.
Chemoselective Rhodium-Catalyzed Borylation of Bromoiodoarenes
Under Mild Conditions. J. Org. Chem. 2020, 85, 6770−6777. (c) Lu,
H.; Zhao, T.-T.; Bai, J.-H.; Ye, D.; Xu, P.-F.; Wei, H. Divergent
Coupling of Benzocyclobutenones with Indoles via C−H and C−C
Activations. Angew. Chem., Int. Ed. 2020, 59, 23537−23543. (d) Jiang,
C.; Wu, W.-Q.; Lu, H.; Yu, T.-Y.; Xu, W.-H.; Wei, H. Rhodium-
Catalyzed Hiyama Coupling Reaction of Unstrained Ketones via C−
C Bond Cleavage. Asian J. Org. Chem. 2019, 8, 1358−1362. (e) Lei,
(7) For representative decarbonylative coupling of amides, see:
(a) Meng, G.; Szostak, M. General Olefin Synthesis by the Palladium-
Catalyzed Heck Reaction of Amides: Sterically Controlled Chemo-
selective N−C Activation. Angew. Chem., Int. Ed. 2015, 54, 14518−
14522. (b) Shi, S.; Meng, G.; Szostak, M. Synthesis of Biaryls through
Nickel−Catalyzed Suzuki-Miyaura Coupling of Amides by Carbon-
Nitrogen Bond Cleavage. Angew. Chem., Int. Ed. 2016, 55, 6959−
6963. (c) Liu, C.; Szostak, M. Decarbonylative Phosphorylation of
Amides by Palladium and Nickel Catalysis: The Hirao Cross-
Coupling of Amide Derivatives. Angew. Chem., Int. Ed. 2017, 56,
12718−12722. (d) Bie, F.; Liu, X.; Shi, Y.; Cao, H.; Han, Y.; Szostak,
M.; Liu, C. Rh-Catalyzed Base-Free Decarbonylative Borylation of
Twisted Amides. J. Org. Chem. 2020, 85, 15676−15685. (e) Lee, S.
C.; Liao, H.-H.; Chatupheeraphat, A.; Rueping, M. Nickel-Catalyzed
C−S Bond Formation via Decarbonylative Thioetherification of
Esters, Amides and Intramolecular Recombination Fragment
Coupling of Thioesters. Chem. - Eur. J. 2018, 24, 3608−3612.
(8) For leading examples of decarbonylative coupling of esters, see:
(a) Amaike, K.; Muto, K.; Yamaguchi, J.; Itami, K. Decarbonylative
C−H Coupling of Azoles and Aryl Esters: Unprecedented Nickel
Catalysis and Application to the Synthesis of Muscoride A. J. Am.
Chem. Soc. 2012, 134, 13573−13576. (b) Muto, K.; Yamaguchi, J.;
Musaev, D. G.; Itami, K. Decarbonylative Organoboron Cross-
Coupling of Esters by Nickel Catalysis. Nat. Commun. 2015, 6, 7508.
(c) Okita, T.; Kumazawa, K.; Takise, R.; Muto, K.; Itami, K.;
Yamaguchi, J. Palladium-catalyzed Decarbonylative Alkynylation of
Aromatic Esters. Chem. Lett. 2017, 46, 218−220.
(9) For further reviews, see: (a) Liu, C.; Szostak, M. Twisted
Amides: From Obscurity to Broadly Useful Transition-Metal-
10836
https://doi.org/10.1021/acs.joc.1c01117
J. Org. Chem. 2021, 86, 10829−10837

The Journal of Organic Chemistry
pubs.acs.org/joc
Note
Z.-Q.; Pan, F.; Li, H.; Li, Y.; Zhang, X.-S.; Chen, K.; Wang, X.; Li, Y.-
X.; Sun, J.; Shi, Z.-J. Group Exchange between Ketones and
Carboxylic Acids through Directing Group Assisted Rh-Catalyzed
Reorganization of Carbon Skeletons. J. Am. Chem. Soc. 2015, 137,
5012−5020. (f) Wang, G.-W.; Boyd, O.; Young, T. A.; Bertrand, S.
M.; Bower, J. F. Rhodacyclopentanones as Linchpins for the Atom
Economical Assembly of Diverse Polyheterocycles. J. Am. Chem. Soc.
2020, 142, 1740−1745. (g) Neuhaus, J. D.; Willis, M. C.
Homogeneous Rhodium(I)-Catalysis in de novo Heterocycle Syn-
theses. Org. Biomol. Chem. 2016, 14, 4986−5000. (h) Wang, Q.;
Zhang, W.-W.; Zheng, C.; Gu, Q.; You, S.-L. Enantioselective
Synthesis of Azoniahelicenes by Rh-Catalyzed C−H Annulation with
Alkynes. J. Am. Chem. Soc. 2021, 143, 114−120. (i) Wang, Q.; Zhang,
W.-W.; Song, H.; Wang, J.; Zheng, C.; Gu, Q.; You, S.-L. Rhodium-
Catalyzed Atroposelective Oxidative C−H/C−H Cross-Coupling
Reaction of 1-Aryl Isoquinoline Derivatives with Electron-Rich
Heteroarenes. J. Am. Chem. Soc. 2020, 142, 15678−15685.
(20) For intramolecular decarbonylation of esters, see: Takise, R.;
Isshiki, R.; Muto, K.; Itami, K.; Yamaguchi, J. Decarbonylative Diaryl
Ether Synthesis by Pd and Ni Catalysis. J. Am. Chem. Soc. 2017, 139,
3340−3343.
(21) Cao, H.; McNamee, L.; Alper, H. Palladium-Catalyzed
Thiocarbonylation of Iodoarenes with Thiols in Phosphonium Salt
Ionic Liquids. J. Org. Chem. 2008, 73, 3530−3534.
(22) Bhowmik, A.; Yadav, M.; Fernandes, R. A. Room Temperature
Nickel-Catalyzed Cross-Coupling of Aryl-Boronic Acids with
Thiophenols: Synthesis of Diarylsulfides. Org. Biomol. Chem. 2020,
18, 2447−2458.
10837
https://doi.org/10.1021/acs.joc.1c01117
J. Org. Chem. 2021, 86, 10829−10837