Selective Thiolative Lactonization of Internal Alkynes Bearing a Hydroxyl Group with Carbon Monoxide and Organic Disulfides Catalyzed by Transition-Metal Complexes

Article abstract of DOI:10.1021/acs.joc.5b00977

Although many transition-metal catalysts are ineffective for the addition and carbonylative addition of organic disulfides to internal alkynes, dicobalt octacarbonyl and palladium complexes such as Pd(PPh₃)₄ and Pd(OAc)₂ w

Full text of DOI:10.1021/acs.joc.5b00977

Article
pubs.acs.org/joc
Selective Thiolative Lactonization of Internal Alkynes Bearing
a Hydroxyl Group with Carbon Monoxide and Organic
Disulfides Catalyzed by Transition-Metal Complexes
Shinya Higashimae, Taichi Tamai, Akihiro Nomoto, and Akiya Ogawa*
Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, 1-1 Gakuen-cho, Nakaku, Sakai,
Osaka 599-8531, Japan
S
* Supporting Information
ABSTRACT: Although many transition-metal catalysts are
ineffective for the addition and carbonylative addition of
organic disulfides to internal alkynes, dicobalt octacarbonyl
and palladium complexes such as Pd(PPh3)4 and Pd(OAc)2
were found to exhibit excellent catalytic activity for the
thiolative lactonization of internal alkynes bearing a hydroxyl
group. In the presence of the cobalt or palladium catalyst, internal alkynes bearing a hydroxy group, such as homopropargyl
alcohol derivatives, successfully undergo thiolative carbonylation with carbon monoxide and an organic disulfide regio- and
stereoselectively to afford the corresponding thio group bearing-lactones in good yields. In the Co-catalyzed reaction, the cobalt−
alkyne complex from dicobalt octacarbonyl and internal alkyne acts as a key species, making it possible to attain thiolative
lactonization of internal alkynes with a hydroxyl group. In the Pd-catalyzed reaction, the coordination of the hydroxy group to the
palladium catalyst plays an important role for the thiolative lactonization.
1. INTRODUCTION
Transition-metal-catalyzed simultaneous introduction of hetero-
atom functional groups and carbon monoxide into organic
molecules is one of the most important tools for the direct
synthesis of heteroatom-functionalized carbonyl compounds.1
Organosilicon compounds, such as hydrosilanes, are widely
employed for this purpose.2
These reactions (eqs 1−3) are assumed to proceed via the
initial formation of metal−sulfide complexes, followed by their
coordination by alkynes. In contrast to Pd or Rh complexes,
cobalt carbonyl (Co2(CO)8) easily complexes internal alkynes to
give cobalt−alkyne complexes. This coordination property of
Co2(CO)8 may make it possible to attain novel thiolative
carbonylation of internal alkynes. On the basis of this idea, we
have recently developed a method for the cobalt-catalyzed
thiolative mono- and double carbonylation of internal alkynes
with CO and disulfides or thiols. (eqs 4 and 5).8,9 During the
course of this study, we also found that, in the case of internal
alkynes bearing a hydroxyl group, novel thiolative carbonylation
took place regioselectively to afford the corresponding thiolated
lactone derivatives bearing an exo-methylene group.
Organosulfur compounds are useful synthetic intermediates;
however, only a very limited number of examples of transition-
metal-catalyzed carbonylation with concurrent introduction of
sulfur functional groups have been reported.3,4 We previously
reported a series of transition-metal-catalyzed carbonylations of
terminal alkynes with CO and organosulfur compounds, such as
thiols and disulfides. For example, the palladium-catalyzed
reaction of terminal alkynes with CO and (ArS)2 affords the
corresponding β-(arylthio)-α,β-unsaturated thioesters regio-
and stereoselectively (eq 1).5 Rhodium complexes catalyze the
regio- and stereoselective thioformylation of terminal alkynes
with CO and ArSH (eq 2),6 whereas platinum complexes
catalyze the hydrothioesterification of terminal alkynes with CO
and R’SH regioselectively (eq 3).7 However, these thiolative
carbonylation reactions could not be applied to internal alkynes,
most probably due to the increased steric hindrance around
them.
In this paper, we report the cobalt-catalyzed thiolative
lactonization of internal alkynes bearing a hydroxyl group with
CO and disulfides. In addition, a comparison of this thiolative
Received: May 2, 2015
Published: June 15, 2015
© 2015 American Chemical Society
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Table 1. Co2(CO)8-Catalyzed Thiolative Lactonization of 3-Hexyn-1-ol with Diphenyl Disulfide
a
entry
catalyst
CO, MPa
solvent
temp, °C
yield, %
b
1
Co2(CO)8
Co2(CO)8
Co2(CO)8
Co2(CO)8
Co2(CO)8
Co2(CO)8
Co2(CO)8
Co2(CO)8
Co2(CO)8
Co2(CO)8
Co2(CO)8
Co2(CO)8
Co2(CO)8
Co(acac)2·2H2O
CoCl2·6H2O
2
2
2
3
1
0.1
2
2
2
2
2
2
2
2
2
2
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
toluene
CH3CN
toluene
toluene
toluene
toluene
140
140
140
140
140
140
120
110
100
140
140
140
140
140
140
30
c
2
52
3
4
5
6
7
8
9
82 (71)
80
68
6
62
54
30
d
10
80
e
11
78
12
60
f
13
50
gh
,
14
15
16
64
i
i
trace
Co(OAc)2·4H2O
140
d
N.R.
a
b
c
e
1
Determined by H NMR (isolated). 3-Hexyn-1-ol (1.0 mmol) was used. 3-Hexyn-1-ol (1.5 mmol) was used. Reaction time (40 h). Catalyst
(3 mol %). 1,2-Bis(diphenylphosphino)ethane (dppe, 18 mol %) was added. Catalyst (5 mol %). Regioisomeric carbonylation byproduct 4aa was
f
g
h
obtained.
i
Catalyst (18 mol %).
lactonization to the corresponding palladium-catalyzed carbon-
ylation is reported (eq 6).
reaction time to 40 h does not influence the yield (Table 1,
entry 10). Decreasing the amount of the catalyst to 3 mol %
results in a decrease of the yield of 3aa (Table 1, entry 11). With
a polar solvent (CH3CN), the yield of 3aa slightly decreases
(Table 1, entry 12). Addition of 1,2-bis(diphenylphosphino)-
ethane (dppe) decreases the yield (Table 1, entry 13). Some
other cobalt catalysts were investigated, and Co(acac)2 also
shows catalytic activity in this thiolative lactonization (Table 1,
entry 14). However, with this catalyst, a regioisomeric
carbonylation derivative 4aa is also obtained. The optimum
result is obtained when the thiolative carbonylation is performed
under 2 MPa of CO in toluene at 140 °C for 20 h (Table 1,
entry 3).
Next, the thiolative lactonization was examined using several
hydroxyalkynes and diaryl disulfides under the optimized
reaction conditions (Table 1, entry 3), and the results are
shown in Table 2. In the cases of diaryl disulfides having an
electron-donating (2b, 2c) or electron-withdrawing group (2d),
the thiolative lactonization proceeded successfully to give the
corresponding γ-lactone derivatives 3ab, 3ac, and 3ad in good
yields (Table 2, entries 2−4). Substituted hydroxyalkynes 1b
and 1c also underwent the thiolative lactonization regio- and
stereoselectively in high yields (Table 2, entries 5 and 6). The
thiolative lactonization of 1d took place to give thiolated lactone
3da in 27% yield along with some byproducts (the conversion of
disulfide was 78%) (Table 2, entry 7). The thiolative
lactonization of terminal alkynes 1e and 1f was also attempted,
and the corresponding γ- and δ-lactone derivatives 3ea and 3fa
were obtained, respectively, although the yield of 3fa was low
2. RESULTS AND DISCUSSION
2.1. Cobalt-Catalyzed Thiolative Lactonization of
Internal Alkynes Bearing a Hydroxy Group with CO and
Disulfides. When the reaction of 3-hexyn-1-ol 1a (1 mmol) with
diphenyl disulfide 2a (1 mmol) under carbon monoxide (2 MPa)
in toluene (10 mL) is conducted using 9 mol % of Co2(CO)8 at
140 °C for 20 h, thiolative lactonization occurs to give the
corresponding γ-lactone derivative 3aa bearing an exo-methylene
group in 30% yield (Table 1, entry 1). The structure of 3aa was
determined unambiguously by X-ray structural analysis (see the
Supporting Information, Figure S1). As can be seen from the
ORTEP representation of 3aa, carbon monoxide is introduced
regioselectively to the acetylenic carbon bonded to the
hydroxyethyl group, and the thio group is located at the cis
position of the carbonyl group. Therefore, the present thiolative
carbonylation of 1a apparently proceeds regio- and stereo-
selectively. The yield of 3aa is dramatically improved with the use
of excess 1a (Table 1, entries 2 and 3). Higher CO pressure
(3 MPa) does not increase the yield of 3aa (Table 1, entry 4);
however, lower CO pressure (1 MPa, 0.1 MPa) decreases the
yield (Table 1, entries 5 and 6). With decreasing temperature, the
yields of 3aa decrease (Table 1, entries 7−9). Prolonging the
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Table 2. Co2(CO)8-Catalyzed Thiolative Lactonization of
Acetylenic Alcohols with Various Disulfides
Scheme 1. A Possible Pathway for the Co2(CO)8-Catalyzed
Thiolative Lactonization
a
Table 3. Transition-Metal-Catalyzed Thiolative Lactonization
of 3-Hexyn-1-ol
a
entry
catalyst
none
yield, %
1
2
N.R.
82
Co2(CO)8
9 mol %
5 mol %
2.5 mol %
5 mol %
5 mol %
5 mol %
5 mol %
5 mol %
18 mol %
5 mol %
5 mol %
2.5 mol %
5 mol %
2 mol %
18 mol %
3
RuHCl(CO)(PPh3)3
Rh2Cl2(cod)2
NiCl2
38
4
30
5
24
6
Ni(acac)2·2H2O
(PPh3)AuNTf2
PdCl2
32
7
N.D.
68
8
9
Pd(OAc)2
58
10
Pd(OAc)2
76
b
11
PdCl2
78
b
12
Pd(OAc)2
82
13
14
15
16
Pd2(dba)3·CHCl3
Pd(PPh3)4
Pd(PPh3)4
Pd(PPh3)4
66
95
78
98
a
b
a
1
Determined by H NMR. PPh3 (10 mol %) was added.
Alkyne (3 mmol), disulfide (1 mmol), CO (2 MPa), toluene
b
1
(10 mL), Co2(CO)8 (9 mol %), 140 °C, 20 h. Determined by H
NMR (isolated).
reacts with acetylenic alcohol 1 to form cobalt−alkyne complex
A. Intramolecular coordination of the hydroxyl group of 1 to the
cobalt atom of complex A and reaction with disulfide 2 leads
to complex B with concomitant formation of the thiol. The
formation of the thiol was confirmed by monitoring the reaction
mixture by 1H NMR. CO insertion gives complex C, followed by
reductive elimination to form complex D. The subsequent
ligand-exchange reaction with substrate 1 affords the desired
thiolated lactone derivative 3 with regeneration of complex A.
(Table 2, entries 8 and 9). In the case of 1f, the (E)-isomer of 3fa
was also obtained in 23% yield.
To gain insight into the reaction pathway for this thiolative
lactonization, the same reaction was examined using a cobalt−
alkyne complex as catalyst (eq 7). As a result, the thiolative
lactonization of 1a proceeded successfully to give 3aa in 81%
yield. The result suggests that the cobalt−alkyne complex is a key
species in this thiolative lactonization. In this Co2(CO)8-
catalyzed thiolative lactonization, most of the catalyst was
soluble in solution (toluene), and therefore, the reaction may
proceed by homogeneous catalysis.10 Although the precise
mechanism for this cobalt-catalyzed thiolative lactonization
requires further detailed mechanistic experiments, an outline of
a possible pathway is shown in Scheme 1. Initially, Co2(CO)8
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catalyst scope of the thiolative lactonization, we next examined
the carbonylation of 3-hexyn-1-ol 1a with CO and diphenyl
disulfide 2a by varying the catalysts, and the results are shown in
Table 3. Among the catalysts examined, ruthenium (Table 3,
entry 3), rhodium (Table 3, entry 4), nickel (Table 3, entries 5
and 6), and palladium (Table 3, entries 8−16) complexes exhibit
catalytic activity in the thiolative carbonylation. Among them,
Pd(PPh3)4 is the best catalyst. Interestingly, increasing the
amount of the catalyst leads to exclusive formation of the desired
3aa (Table 3, entry 16). In the absence of catalyst, no reaction is
observed (Table 3, entry 1).
Further detailed optimization of the thiolative lactonization
conditions was investigated using 5 mol % of Pd(PPh3)4, and the
results are shown in Table 4. Both lower and higher CO pressures
slightly decrease the yield of 3aa (Table 4, entries 1, 2, and 4),
A decrease in the temperature (Table 4, entries 5 and 6) or the
amount of 1a (Table 4, entry 7) dramatically decreases the yield
of 3aa. The thiolative lactonization also proceeds in CH3CN or
PhCN as solvent (Table 4, entries 8 and 9). Even in 10 h, the
thiolative lactonization proceeds well (Table 4, entry 10).
To investigate the scope and limitation of substrates, thiolative
lactonization using a variety of acetylenic alcohols 1 and organic
disulfides 2 was examined, and the results are shown in Table 5.
Table 4. Palladium-Catalyzed Thiolative Lactonization of
3-Hexyn-1-ol with Diphenyl Disulfide
a
entry
CO, MPa
solvent
temp, °C
time, h
yield, %
78
1
2
3
4
5
6
0.5
1
toluene
toluene
toluene
toluene
toluene
toluene
toluene
CH3CN
PhCN
140
140
140
140
120
100
140
140
140
140
20
20
20
20
20
20
20
20
20
10
40
88 (83)
95
2
3
87
2
71
2
8
b
7
2
48
8
9
2
76
1
98
10
11
2
toluene
toluene
91
2
140
84
a
b
1
Determined by H NMR (isolated). 3-Hexyn-1-ol (1.2 mmol).
2.2. Palladium-Catalyzed Thiolative Lactonization of
Internal Alkynes Bearing a Hydroxy Group. To clarify the
a
Table 5. Palladium-Catalyzed Thiolative Lactonization of Acetylenic Alcohols with Various Disulfides
a
b
Alkyne (3 mmol), disulfide (1 mmol), CO (1 MPa), toluene (10 mL), Pd(PPh3)4 (5 mol %), 140 °C, 20 h. Determined by 1H NMR (isolated).
c
CO (2 MPa).
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When the reaction of hydroxyalkyne 1 (3 mmol) with diphenyl
disulfide (1 mmol) was conducted in the presence of Pd(PPh3)4
(5 mol %) in toluene (10 mL) at 140 °C for 20 h, the
corresponding γ-lactone 3 is obtained. Methoxy, chloro, and
nitro groups on the para position of disulfides 2c, 2d, and 2e are
tolerant to the thiolative lactonization (Table 5, entries 3−5).
Similarly, both electron-donating (Table 5, entries 9 and 10) and
electron-withdrawing (Table 5, entry 11) groups on the para
position of acetylenic alcohols 1g, 1h, and 1i are also tolerant to
the reaction conditions. In the case of 1d, the conversion of
disulfide was 56%, and some byproducts were obtained. A similar
result was obtained from 1i. Not only γ-lactones, but also
δ-lactone 3ja, can be synthesized by this thiolative lactonization,
although the yield of 3ja is lower compared with those of the
γ-lactones (Table 5, entry 12).
possible pathway for the palladium-catalyzed thiolative lactoni-
zation of internal alkynes bearing a hydroxy group, as shown in
Scheme 3. In contrast to Co2(CO)8, which forms the alkyne
Scheme 3. A Possible Pathway for Pd(PPh3)4-Catalyzed
Thiolative Lactonization
To obtain insight into the present Pd-catalyzed thiolative
lactonization, we examined the catalytic thiolative lactonization
of acetylenic alcohols using a preformed Pd−sulfide complex
(Scheme 2). Initially, the Pd−sulfide complex was prepared by
Scheme 2. Pd−Sulfide Complex Catalyzed Thiolative
Lactonization
complex initially, in the palladium-catalyzed reaction, oxidative
addition of disulfide 2 to the low-valence palladium complex may
occur initially to form palladium sulfide complex E. Then, the
hydroxyl group of acetylenic alcohol 1 coordinates to the
palladium species E with release of a thiol (R’SH), generating
complex F. The subsequent CO insertion to give complex G,
followed by intramolecular acylpalladation to the carbon−carbon
triple bond of complex G, leads to complex H. Reductive
elimination of the thiolative lactonization product 3 and
oxidative addition of disulfide 2 regenerate the palladium sulfide
complex E.
reaction of Pd(OAc)2 with benzenethiol according to the
literature.11 The reaction of 3-hexyn-1-ol (1a) with diphenyl
disulfide (2a), triphenylphosphine, and CO in the presence of
5 mol % of Pd−sulfide complex as a catalyst afforded the
corresponding γ-lactone derivative (3aa) in 92% yield. This
result suggests that the Pd−sulfide complex is a highly effective
catalyst for the thiolative lactonization of acetylenic alcohols. In
this Pd(PPh3)4-catalyzed thiolative lactonization, large amounts
of a reddish brown solid (most probably Pd−sulfide cluster)
were formed during the reaction. Therefore, the Pd-catalyzed
reaction may proceed by heterogeneous catalysis.12
We have previously reported a similar thiolative lactonization
of terminal alkynes having a hydroxy group using palladium
catalysts such as Pd(PPh3)4 (eq 8).13 This thiolative lactonization
is assumed to proceed via the oxidative addition of (PhS)2 to the
Pd(0) complex to generate the palladium sulfide complex, which
adds regioselectively to the alkyne, followed by CO insertion,
leading to the (Z)-isomer of the corresponding thiolative
carbonylation product. Finally, Z-to-E isomerization, followed
by cyclization, affords the thiolated lactone derivative. The Z-to-
E isomerization gradually proceeded in situ in the presence of a
hydroxyl group, and therefore, this thiolative lactonization
requires a longer reaction time (50 h). The regioselectivity of
this reaction is determined in the thiopalladation stage, where the
more bulky palladium moiety is located at the terminal position.
In the case of internal alkynes, it is reasonable to assume that a
regioisomeric mixture of the thiolated lactone derivatives will be
formed because of the similar bulkiness surrounding both alkyne
carbons. However, the present thiolative lactonization proceeds
regioselectively. This suggests that, in the thiolative lactonization
of internal alkynes, coordination of the hydroxy group to the
palladium catalyst plays an important role. Thus, we propose a
3. CONCLUSION
In summary, we have developed a novel transition-metal-
catalyzed thiolative lactonization of internal alkynes bearing a
hydroxyl group with CO and disulfides, which successfully
affords γ-lactone derivatives bearing exo-methylene and thio
groups with excellent regio- and stereoselectivities. The
procedure can also be applied to δ-lactone synthesis. The
obtained thiolated lactone derivatives are promising as synthetic
intermediates, as the thio group can be displaced by a variety of
nucleophiles, and exo-methylene groups make them a possible
substrate for Michael addition. The mechanistic details and scope
of this thiolative carbonylation are currently under investigation.
4. EXPERIMENTAL SECTION
4.1. General Information. Co2(CO)8 was obtained from
commercial suppliers. Pd(PPh3)4 was synthesized according to the
literature.14 All disulfides and aliphatic alkynes (1a−1c, 1e, and 1f) were
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purchased from a commercial source and used without further
purification. Aromatic alkynes (1d and 1g−1j) were synthesized
according to the literature.15 Toluene was used as solvent after
compound 3ad was obtained in 75% yield (200.8 mg) following the
general procedure. In the presence of Pd(PPh3)4 (57.8 mg, 0.05 mmol),
compound 3ad was obtained in 68% yield (182.8 mg) following the
general procedure. Isolated as a white solid; mp 109−110 °C; 1H NMR
(400 MHz, CDCl3): δ 0.91 (t, J = 7.6 Hz, 3H), 2.18 (q, J = 7.5 Hz, 2H),
2.98 (t, J = 7.6 Hz, 2H), 4.40 (t, J = 7.3 Hz, 2H), 7.34−7.38 (m, 2H),
7.47−7.50 (m, 2H); 13C{1H}NMR (100 MHz, CDCl3): δ 12.4, 27.4,
28.2, 64.9, 115.6, 129.0, 129.3, 135.8, 137.0, 155.1, 169.8; IR (KBr)
3075, 2978, 2935, 2909, 2874, 1723, 1599, 1477, 1465, 1452, 1440,
1373, 1287, 1232, 1146, 1095, 1012, 832, 746, 515 cm−1; HRMS (FAB)
calcd for C13H14O2ClS [M + H]+: 269.0398; found: 269.0382. Anal.
Calcd for C13H13O2ClS: C, 58.10; H, 4.88. found: C, 57.94; H, 4.78.
4.2.5. (Z)-3-{1-(4-Nitrophenylthio)propylidene}dihydrofuran-2-
one (3ae). In the presence of Pd(PPh3)4 (57.8 mg, 0.05 mmol),
compound 3ae was obtained in 74% yield (205.3 mg) following the
general procedure. Isolated as a yellow solid; mp 141−143 °C; 1H NMR
(400 MHz, CDCl3): δ 0.95 (t, J = 7.5 Hz, 3H), 2.25 (q, J = 7.5 Hz, 2H),
3.02 (t, J = 7.4 Hz, 2H), 4.39 (t, J = 7.5 Hz, 2H), 7.58−7.63 (m, 2H),
8.15−8.20 (m, 2H); 13C{1H}NMR (100 MHz, CDCl3): δ 12.4, 28.1,
28.4, 64.8, 120.1, 123.9, 134.3, 140.8, 147.6, 151.2, 169.1; IR (KBr)
3091, 2980, 2935, 2917, 1873, 1715, 1598, 1576, 1441, 1379, 1344,
1301, 1279, 1257, 1235, 1225, 1175, 1148, 1065, 1033, 1011, 962, 861,
850, 747, 730, 690, 668, 572, 503 cm−1; HRMS (FAB) calcd for
C13H14O4NS [M + H]+: 280.0638; found: 280.0641. Anal. Calcd
for C13H13O4NS: C, 55.90; H, 4.69; N, 5.01 found: C, 55.80; H, 4.61;
N, 5.08.
4.2.6. (Z)-3-{1-(Phenylthio)heptylidene}dihydrofuran-2-one (3ba).
In the presence of Pd(PPh3)4 (57.8 mg, 0.05 mmol), compound 3ba was
obtained in 65% yield (188.2 mg) following the general procedure.
Isolated as a colorless oil; 1H NMR (400 MHz, CDCl3): δ 0.80 (t, J = 7.3 Hz,
3H), 0.98−1.03 (m, 4H), 1.10−1.18 (m, 2H), 1.26−1.34 (m, 2H),
2.10−2.16 (m, 2H), 2.97 (t, J = 7.6 Hz, 2H), 4.38 (t, J = 7.6 Hz, 2H),
7.35−7.44 (m, 3H), 7.53−7.56 (m, 2H); 13C{1H}NMR (100 MHz,
CDCl3): δ 13.8, 22.2, 27.7, 28.4, 28.7, 30.9, 34.0, 64.9, 115.0, 128.9,
129.2, 130.2, 135.9, 155.0, 169.8; IR (NaCl) 2955, 2927, 2856, 1734,
1600, 1475, 1457, 1440, 1373, 1239, 1140, 1038, 1024, 967, 831, 751,
705, 692 cm−1; HRMS (EI) calcd for C17H22O2S [M]+: 290.1341;
found: 290.1350.
1
distillation using CaH2. H NMR spectra (400 MHz) and 13C NMR
spectra (100 MHz) were taken in CDCl3 with Me4Si as an internal
standard. Chemical shifts in 1H NMR were measured relative to CDCl3
and converted to δ (Me4Si) values by using δ (CDCl3) 7.26 ppm.
Chemical shifts in 13C NMR were measured relative to CDCl3 and
converted to δ (Me4Si) values by using δ (CDCl3) 77.0 ppm. The use of
broadband decoupling is indicated with braces. IR spectra are reported
in wavenumbers (cm−1). FAB mass spectra were obtained by employing
double focusing mass spectrometers.
4.2. General Procedure for the Synthesis of (Z)-3-{1-(Phenyl-
thio)propylidene}dihydrofuran-2-one (3aa). In a 50 mL stainless
steel autoclave with a magnetic stirring bar under a N2 atmosphere
were sequentially placed catalyst (0.05−0.09 mmol), distilled toluene
(10 mL), alkyne (3.0 mmol), and disulfide (1.0 mmol). The vessel was
purged three times with carbon monoxide and then charged with the
same gas to achieve a pressure of 1−2 MPa. The reaction was conducted
with magnetic stirring for 20 h at 140 °C. After removal of the unreacted
carbon monoxide, the resulting mixture was filtered through Celite with
diethyl ether and concentrated in vacuo to give the crude products.
Purification was performed by silica gel column chromatography
(hexanes:AcOEt, 2:1) followed by recrystallization or recycling
preparative HPLC employing GPC columns with CHCl3 as eluent.
4.2.1. (Z)-3-{1-(Phenylthio)propylidene}dihydrofuran-2-one (3aa).
In the presence of Co2(CO)8 (30.8 mg, 0.09 mmol), compound 3aa was
obtained in 71% yield (167.6 mg) following the general procedure. In
the presence of Pd(PPh3)4 (57.8 mg, 0.05 mmol), compound 3aa was
obtained in 83% yield (195.2 mg) following the general procedure.
1
Isolated as a white solid; mp 111−113 °C; H NMR (400 MHz,
CDCl3): δ 0.90 (t, J = 7.5 Hz, 3H), 2.18 (q, J = 7.5 Hz, 2H), 2.98 (t, J =
7.5 Hz, 2H), 4.39 (t, J = 7.5 Hz, 2H), 7.35−7.44 (m, 3H), 7.54−7.58 (m,
2H); 13C{1H}NMR (100 MHz, CDCl3): δ 12.5, 27.5, 28.3, 64.9, 114.9,
129.1, 129.4, 130.4, 136.0, 156.3, 169.9; IR (KBr) 3058, 2973, 2936,
1724, 1598, 1475, 1452, 1439, 1375, 1231, 1144, 1063, 1021, 965, 931,
853, 754, 708, 695, 672, 526 cm−1; HRMS (FAB) calcd for C13H15O2S
[M + H]+: 235.0787; found: 235.0784. Anal. Calcd for C13H14O2S: C,
66.64; H, 6.02. found: C, 66.52; H, 5.96.
4.2.7. (Z)-5-Methyl-3-{1-(phenylthio)propylidene}dihydrofuran-2-
one (3ca). In the presence of Co2(CO)8 (30.8 mg, 0.09 mmol),
compound 3ca was obtained in 76% yield (189.7 mg) following the
general procedure. In the presence of Pd(PPh3)4 (57.8 mg, 0.05 mmol),
compound 3ca was obtained in 66% yield (164.8 mg) following the
4.2.2. (Z)-3-{1-(p-Tolylthio)propylidene}dihydrofuran-2-one (3ab).
In the presence of Co2(CO)8 (30.8 mg, 0.09 mmol), compound 3ab was
obtained in 64% yield (159.7 mg) following the general procedure. In
the presence of Pd(PPh3)4 (57.8 mg, 0.05 mmol), compound 3ab was
obtained in 81% yield (201.4 mg) following the general procedure.
1
general procedure. Isolated as a white solid; mp 95−96 °C; H NMR
1
(400 MHz, CDCl3): δ 0.89 (t, J = 7.5 Hz, 3H), 1.43 (d, J = 6.2 Hz, 3H),
2.15 (q, J = 7.4 Hz, 2H), 2.53 (dd, J = 6.1, 16.2 Hz, 1H), 3.10 (dd, J = 7.8,
16.2 Hz, 1H), 4.63−4.73 (m, 1H), 7.35−7.44 (m, 3H), 7.53−7.58 (m,
2H); 13C{1H}NMR (100 MHz, CDCl3): δ 12.5, 22.2, 27.4, 36.0, 73.3,
116.1, 129.1, 129.3, 130.4, 135.9, 155.8, 169.5; IR (KBr) 3057, 2973,
2935, 2871, 1718, 1595, 1475, 1438, 1338, 1239, 1148, 1158, 1114,
1027, 955, 934, 912, 889, 826, 753, 708, 664 cm−1; HRMS (FAB) calcd
for C14H17O2S [M + H]+: 249.0944; found: 249.0956.
Isolated as a white solid; mp 126−128 °C; H NMR (400 MHz,
CDCl3): δ 0.90 (t, J = 7.5 Hz, 3H), 2.17 (q, J = 7.5 Hz, 2H), 2.38 (s, 3H),
2.97 (t, J = 7.5 Hz, 2H), 4.38 (t, J = 7.5 Hz, 2H), 7.18 (d, J = 7.8 Hz, 2H),
7.44 (d, J = 7.8 Hz, 2H); 13C{1H}NMR (100 MHz, CDCl3): δ 12.6, 21.3
27.4, 28.3, 64.9, 114.3, 126.7, 129.9, 136.0, 139.7, 157.0, 170.0; IR (KBr)
2977, 2934, 2872, 1721, 1597, 1492, 1461, 1444, 1369, 1243, 1147,
1030, 1019, 970, 856, 812, 750, 679, 541, 517 cm−1; HRMS (FAB) calcd
for C14H17O2S [M + H]+: 249.0944; found: 249.0933. Anal. Calcd for
C14H16O2S: C, 67.71; H, 6.49. found: C, 67.62; H, 6.48.
4.2.8. (Z)-3-{1-Phenyl-1-(phenylthio)methylene}dihydrofuran-2-
one (3da). In the presence of Pd(PPh3)4 (57.8 mg, 0.05 mmol),
compound 3da was obtained in 20% yield (56.4 mg) following the
general procedure. Isolated as a white solid; mp 139−141 °C; 1H NMR
(400 MHz, CDCl3): δ 2.77 (t, J = 7.4 Hz, 2H), 4.33 (t, J = 7.4 Hz, 2H),
6.95−7.14 (m, 8H), 7.16−7.20 (m, 2H); 13C{1H}NMR (100 MHz,
CDCl3): δ 29.9, 65.3, 117.4, 127.9, 128.0, 128.1, 128.2, 130.9, 135.3,
136.8, 153.0, 169.7; IR (KBr) 3055, 2982, 2905,1738, 1729, 1607, 1581,
1588 1473, 1440, 1367, 1214, 1160, 1080, 1028, 967, 897, 749, 699,
684 cm−1; HRMS (FAB) calcd for C17H15O2S [M + H]+: 283.0787;
found: 283.0786.
4.2.3. (Z)-3-{1-(4-Methoxyphenylthio)propylidene}dihydrofuran-
2-one (3ac). In the presence of Co2(CO)8 (30.8 mg, 0.09 mmol),
compound 3ac was obtained in 65% yield (171.0 mg) following the
general procedure. In the presence of Pd(PPh3)4 (57.8 mg, 0.05 mmol),
compound 3ac was obtained in 80% yield (212.3 mg) following the
general procedure. Isolated as a white solid; mp 139−140 °C; 1H NMR
(400 MHz, CDCl3): δ 0.90 (t, J = 7.5 Hz, 3H), 2.15 (q, J = 7.5 Hz, 2H),
2.96 (t, J = 7.5 Hz, 2H), 3.84 (s, 3H), 4.38 (t, J = 7.6 Hz, 2H), 6.89−6.93
(m, 2H), 7.46−7.50 (m, 2H); 13C{1H}NMR (100 MHz, CDCl3):
δ 12.5, 27.2, 28.2, 55.3, 65.0, 113.9, 114.6, 120.6, 137.6, 157.5, 160.7,
170.0; IR (KBr) 2977, 2935, 2873, 2842, 1719, 1597, 1568, 1492, 1459,
1438, 1375, 1288, 1246, 1148, 1031, 1020, 970, 855, 837, 811, 799, 748,
674, 619, 531 cm−1; HRMS (FAB) calcd for C14H17O3S [M + H]+:
265.0893; found: 265.0905. Anal. Calcd for C14H16O3S: C, 63.61; H,
6.10. found: C, 63.51; H, 6.06.
4.2.9. (Z)-3-{(Phenylthio)methylene}dihydrofuran-2-one (3ea). In
the presence of Co2(CO)8 (30.8 mg, 0.09 mmol), compound 3ea was
obtained in 51% yield (107.3 mg) following the general procedure.
1
Isolated as a white solid; mp 125−126 °C; H NMR (400 MHz,
CDCl3): δ 3.00 (td, J = 2.3, 7.6 Hz, 2H), 4.42 (t, J = 7.5 Hz, 2H), 7.12 (t,
J = 2.0 Hz, 1H), 7.32−7.41 (m, 3H), 7.47−7.51 (m, 2H); 13C{1H}NMR
(100 MHz, CDCl3): δ 28.7, 66.6, 118.2, 128.3, 129.4, 131.1, 135.5,
4.2.4. (Z)-3-{1-(4-Chlorophenylthio)propylidene}dihydrofuran-2-
one (3ad). In the presence of Co2(CO)8 (30.8 mg, 0.09 mmol),
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Article
141.1, 170.2; IR (KBr) 2994, 2978, 2919, 1729, 1610, 1478, 1443, 1434,
1373, 1318, 1260, 1188, 1176, 1164, 1095, 1018, 963, 850, 835, 762, 745,
693, 664 cm−1; HRMS (EI) calcd for C11H10O2S [M]+: 206.0402;
found: 206.0390.
The mixture was stirred for 24 h at room temperature under a N2
atmosphere. The resulting mixture was concentrated in vacuo. The
purification was performed by silica gel column chromatography
(hexanes:AcOEt, 2:1).
4.2.10. (Z)-3-{(Phenylthio)methylene}tetrahydropyran-2-one
(3fa). In the presence of Co2(CO)8 (30.8 mg, 0.09 mmol), compound
3fa was obtained in 19% yield (40.9 mg) following the general
procedure. Isolated as a white solid; mp 148−150 °C; 1H NMR
(400 MHz, CDCl3): δ 1.91−1.98 (m, 2H), 2.65 (dt, J = 1.4, 6.3 Hz, 2H),
4.37 (t, J = 5.5 Hz, 2H), 7.12 (t, J = 1.6 Hz, 1H), 7.33−7.40 (m, 3H),
7.48−7.53 (m, 2H); 13C{1H}NMR (100 MHz, CDCl3): δ 23.0, 28.9,
69.3, 117.8, 128.2, 129.3, 131.2, 137.0, 148.5, 165.2; IR (KBr) 2970,
2937, 2898, 1683, 1558, 1472, 1439, 1432, 1398, 1341, 1314, 1274,
1228, 1189, 1176, 1132, 1071, 980, 959, 882, 835, 828, 756, 693,
502 cm−1; HRMS (FAB) calcd for C12H13O2S [M + H]+: 221.0631;
found: 221.0612.
4.2.11. (Z)-3-{1-(Phenylthio)-1-(p-tolyl)methylene}dihydrofuran-
2-one (3ga). In the presence of Pd(PPh3)4 (57.8 mg, 0.05 mmol),
compound 3ga was obtained in 62% yield (185.2 mg) following the
general procedure. Isolated as a pale yellow solid; mp 107−109 °C; 1H
NMR (400 MHz, CDCl3): δ 2.20 (s, 3H), 2.78 (t, J = 7.5 Hz, 2H), 4.31
(t, J = 7.5 Hz, 2H), 6.85−6.94 (m, 4H), 7.00−7.11 (m, 3H), 7.16−7.19
(m, 2H); 13C{1H}NMR (100 MHz, CDCl3): δ 21.1, 30.0, 65.2, 117.5,
128.0, 128.1, 128.2, 128.7, 131.2, 133.9, 135.1, 137.9, 153.2, 169.7; IR
(KBr) 3034, 2974, 2914, 1736, 1601, 1508, 1478, 1438, 1376, 1220,
1208, 1194, 1083, 1029, 968, 906, 810, 747, 691, 678, 538 cm−1; HRMS
(EI) calcd for C18H16O2S [M]+: 296.0871; found: 296.0867.
4.2.12. (Z)-3-{1-(4-Methoxyphenyl)-1-(phenylthio)methylene}-
dihydrofuran-2-one (3ha). In the presence of Pd(PPh3)4 (57.8 mg,
0.05 mmol), compound 3ha was obtained in 83% yield (258.3 mg)
following the general procedure. Isolated as a yellow solid; mp 117−
119 °C; 1H NMR (400 MHz, CDCl3): δ 2.81 (t, J = 7.4 Hz, 2H), 3.70 (s,
3H), 4.31 (t, J = 7.4 Hz, 2H), 6.65 (d, J = 6.8 Hz, 2H), 6.94 (d, J = 6.8 Hz,
2H), 7.01−7.11 (m, 3H), 7.15−7.19 (m, 2H); 13C{1H}NMR
(100 MHz, CDCl3): δ 30.0, 55.1, 65.1, 113.3, 117.6, 127.9, 128.2,
129.1, 129.7, 131.4, 134.8, 152.7, 159.1, 169.7; IR (KBr) 3058, 2978,
2959, 2909, 2831, 1723, 1606, 1591, 1506, 1462, 1440, 1413, 1369,
1293, 1246, 1216, 1175, 1088, 1032, 972, 905, 835, 815, 744, 702, 683,
643, 590, 544, 525 cm−1; HRMS (FAB) calcd for C18H17O3S [M + H]+:
313.0893; found: 313.0884.
4.2.13. (Z)-3-[1-(Phenylthio)-1-{4-(trifluoromethyl)phenyl}methyl-
ene]dihydrofuran-2-one (3ia). In the presence of Pd(PPh3)4 (57.8 mg,
0.05 mmol), compound 3ia was obtained in 27% yield (94.1 mg)
following the general procedure. Isolated as a white solid; mp 130−
132 °C; 1H NMR (400 MHz, CDCl3): δ 2.75 (t, J = 7.5 Hz, 2H), 4.35 (t,
J = 7.5, 2H), 7.01−7.07 (m, 2H), 7.08−7.13 (m, 3H), 7.15−7.19 (m,
2H), 7.36−7.41 (m, 2H); 13C{1H}NMR (100 MHz, CDCl3): δ 29.8,
65.3, 118.2, 123.6 (q, JC−F = 272 Hz), 125.1 (q, JC−F = 3.8 Hz), 128.5,
128.6, 128.7, 130.0 (q, JC−F = 32.7 Hz), 130.2, 135.5, 140.5, 151.3, 169.4;
19F{1H}NMR (376 MHz, CDCl3): δ −62.8; IR (KBr) 3073, 3056, 2977,
ASSOCIATED CONTENT
* Supporting Information
X-ray crystal structures (ORTEP) of 3aa, the details of the
experiment about the catalytic system, characterization data for
all new compounds, and a CIF file giving crystallographic data for
3aa. The Supporting Information is available free of charge on
the ACS Publications website at DOI: 10.1021/acs.joc.5b00977.
■
S
AUTHOR INFORMATION
Corresponding Author
*Tel.: +81-72-254-9290. Fax: +81-72-254-9910. E-mail:
ogawa@chem.osakafu-u.ac.jp.
Notes
■
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
This research was supported by a Grant-in-Aid for Exploratory
Research (26620149), from the Ministry of Education, Culture,
Sports, Science and Technology, Japan. The authors thank Osaka
University and the Nara Institute of Science and Technology
(NAIST) of the Kyoto-Advanced Nanotechnology Network for
their assistance with the elemental analyses, EI mass spectrom-
etry measurements, and X-ray crystal structural analysis.
REFERENCES
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(10) To gain insight into the catalytic system of cobalt for the thiolative
lactonization (homogeneous or heterogeneous?), the reaction was
conducted for 1 h, and small amounts of precipitate catalyst were filtered
off. Then, the reaction was continued using the resulting homogeneous
solution. The thiolative lactonization proceeded to afford the desired
lactone 3aa in 87% yield. As the thiolative lactonization cannot proceed
in the absence of catalyst, the results strongly suggest that the reaction
proceeds by homogeneous catalysis (see the Supporting Information,
Scheme S1).
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Sonoda, N. J. Am. Chem. Soc. 1992, 114, 5902. (b) Kondoh, A.;
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DOI: 10.1021/acs.joc.5b00977
J. Org. Chem. 2015, 80, 7126−7133