Cobalt-catalyzed thiolative lactonization of alkynes with double Co incorporation

Article abstract of DOI:10.1021/om200248f

When the Co₂(CO)₈-catalyzed reaction of alkynes with thiols is conducted under the pressure of carbon monoxide, a novel thiolative lactonization with simultaneous introduction of two carbon monoxide molecules into the carbon-carbon triple bonds takes place successfully to afford α,β-unsaturated γ-thio-γ-lactones with excellent regioselectivity.

Full text of DOI:10.1021/om200248f

ARTICLE
pubs.acs.org/Organometallics
Cobalt-Catalyzed Thiolative Lactonization of Alkynes with
Double CO Incorporation
Yoshihiro Higuchi,† Shingo Atobe,† Michiru Tanaka,‡ Ikuyo Kamiya,‡ Takuya Yamamoto,†
Akihiro Nomoto,† Motohiro Sonoda,† and Akiya Ogawa*,†
†Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, 1-1 Gakuen-cho,
Nakaku, Sakai, Osaka 599-8531, Japan
‡Department of Chemistry, Faculty of Science, Nara Women’s University, Kitauoyanishi-machi, Nara 630-8506, Japan
S Supporting Information
b
ABSTRACT: When the Co2(CO)8-catalyzed reaction of alkynes
with thiols is conducted under the pressure of carbon monoxide,
a novel thiolative lactonization with simultaneous introduction
of two carbon monoxide molecules into the carbonꢀcarbon
triple bonds takes place successfully to afford R,β-unsaturated
γ-thio-γ-lactones with excellent regioselectivity.
’ INTRODUCTION
conditions7 attained the high-yield formation of the double-carbony-
lation product 3aa: 3aa/4aa = 78/22 (50% yield) for CH3CN
(3 mL) (entry 3), 87/13 (53% yield) for CH3CN (5 mL) (entry 5),
and 89/11 (76% yield) for CH3CN (10 mL) (entry 7).
Under the conditions of entry 7 in Table 1, the thiolative
lactonization of 1-octyne was examined using several cobalt catalysts
Transition-metal-catalyzed carbonylation with simultaneous
introduction of heteroatom functions is one of the most powerful
tools to synthesize carbonyl compounds bearing heteroatom
functional groups.1 Organosilicon compounds such as hydrosilanes
have been employed frequently for this purpose.2 Although orga-
nosulfur compounds are useful synthetic intermediates, only very
limited examples of transition-metal-catalyzed carbonylation with
simultaneous introduction of sulfur functions have been reported
hitherto.3 Recently we have developed a series of transition-metal-
catalyzed additions of organosulfur compounds to carbonꢀcarbon
unsaturated bonds.4 Since sulfur compounds are generally believed
to be catalyst poisons,5 these catalytic reactions open up a new field
of transition-metal-catalyzed reactions of organosulfur compounds.
Herein we report a novel cobalt carbonyl catalyzed thiolative
lactonization of alkynes 1 with thiols 2 with incorporation of two
molecules of carbon monoxide, which affords R,β-unsaturated
γ-thio-γ-lactones regioselectively (eq 1).6
Table 1. Co2(CO)8-Catalyzed Carbonylation of 1-Octyne
with c-HexSHa
yield (%)c
entry CO pressure (MPa) amt of solvent (mL) 3aa 4aa total
1
3
3
4
4
4
4
4
1
3
9
12
39
41
46
47
68
5
5
14
17
50
53
53
56
76
2
3
4b
3
11
12
7
’ RESULTS AND DISCUSSION
3
When the reaction of 1-octyne (1a) with cyclohexanethiol
(2a) was conducted under pressure of CO (3 MPa) in the
presence of dicobalt octacarbonyl as a catalyst, the novel thiola-
tive lactonization product 3aa, which incorporated two mol-
ecules of CO, was obtained in 9% yield, along with the formation
of thiolative monocarbonylation product 4aa (Table 1, entry 1).
When the pressure of CO was increased (4 MPa), the yields of
the carbonylation products (3aa and 4aa) wereimproved (entry 3).
A prolonged time was not effective for improvement of the
yields of carbonylation products (entry 4). However, dilution
5
5
6
7
9
7
10
8
a Reaction conditions: 1a (3 mmol), 2a (1 mmol), Co2(CO)8 (9 mol %).
b 40 h. c Determined by 1H NMR.
Received: March 22, 2011
Published: August 11, 2011
r
2011 American Chemical Society
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Table 2. Thiolative Lactonization Using Several Thiolsa
(eq 2). Mononuclear cobalt complexes such as CpCo(CO)3 and
Co(acac)2 2H2O exhibited lower catalytic activity toward the desired
3
thiolative lactonization. In contrast, the combination of Co2(CO)8 and
phosphines resulted in the selective formation of the desired thiolative
lactonization. In particular, the catalytic carbonylation in the presence
of Co2(CO)8/1,2-bis(diphenylphosphino)ethane (dppe) was cleaner
than the carbonylation using Co2(CO)8 alone, and the monocarbo-
nylation product 4aa was not formed in this catalytic system.
Next, we examined the Co2(CO)8-catalyzed thiolative lacto-
nization of 1-octyne with several aliphatic and aromatic thiols,
and the results are summarized in Table 2. In all cases, the
thiolative lactonization proceeded regioselectively. The substit-
uents of thiols intensively influenced on the efficiency of the
thiolative lactonization. Among the thiols examined, ethanethiol
(2c) is the most suitable thiol for this thiolative lactonization of
1-octyne with CO, and the corresponding thiolative lactonization
product (3ac) was obtained in 70% yield (entry 2). Aromatic
thiols were relatively less effective, and the monocarbonylation
products were obtained as the major byproduct (entries 3ꢀ5).
(For details of the Co2(CO)8-catalyzed carbonylation of 1-oc-
tyne with PhSH, see the Supporting Information.)
a Reaction conditions; acetylene (3 mmol), thiol (1 mmol), CH3CN
(10 mL), Co2(CO)8 (9 mol %), 140 °C, 17 h, CO (4 MPa). b 1H NMR
yields. c Co2(CO)8 (15 mol %). d CH3CN (1.5 mL). e Isolated yield.
product 3aa was obtained in 60% yield, along with the mono-
carbonylation product 4aa (29%)8 (eq 3). Furthermore, an
equimolar reaction of cobalt carbonyl 1-octyne complex with
cyclohexanethiol under the pressure of CO (3 MPa) afforded the
thiolative lactonization product 3aa in 33% yield (eq 4). These
results strongly suggest that the cobalt alkyne complex acts as a
key species for this thiolative lactonization.9
Table 3 shows the results of the double carbonylation of
several alkynes using cyclohexanethiol (2a) as the thiol in the
presence of Co2(CO)8 as catalyst. The reaction conditions of
entry 7 in Table 1 could be employed with 5-methyl-1-hexyne
(1b), and the corresponding thiolative lactonization product 3ba
was obtained in 68% yield with excellent regioselectivity (entry 2).
Functional groups such as hydroxy and cyano groups did not
affect the present thiolative lactonization (entries 3 and 4). An
alkyne having a benzyl group also afforded the corresponding
R,β-unsaturated γ-thio-γ-lactone 3ea in moderate yield (entry 5).
When benzenethiol (2d) was employed for the carbonylation of
1b or 1d, the desired lactones 3bd (29%) and 3dd (26%) were
obtained, along with the corresponding monocarbonylated pro-
ducts 4bd (26%) and 4dd (26%), respectively.
The structure of the thiolative lactonization product was
determined unambiguously by X-ray analysis (Figure 1).
To gain insight into the reaction pathway, stoichiometric and
catalytic reactions using cobalt alkyne complexes were examined,
as shown in eqs 3 and 4. When the reaction of 1a with 2a and CO
(3 MPa) was performed in the presence of a catalytic amount of
cobalt carbonyl-1-octyne complex, the desired thiolative lactonization
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Table 3. Co2(CO)8-Catalyzed Thiolative Lactonization of
Alkynes with Double CO Incorporationa
Scheme 1. Possible Catalytic Cycle for the Co2(CO)8-Cata-
lyzed Thiolative Lactonization
molecules of CO into alkynes, regioselectively. Further details of
the mechanism are now under investigation.
a Reaction conditions; acetylene (3 mmol), thiol (1 mmol), CH3CN
(10 mL), Co2(CO)8 (9 mol %), 140 °C, 17 h, CO (4 MPa). b 1H NMR
yields (isolated yield in parentheses).
’ EXPERIMENTAL SECTION
General Comments. All reagents were purified by distillation
before use, and freshly distilled acetonitrile was used. The catalyst was
purchased from a commercial source and used without further purifica-
1
tion. H NMR spectra were recorded on JEOL JNM-GSX-270 (270
MHz), JEOL JNM-AL 400 (400 MHz), and Varian GEMINI 2000 (300
MHz) spectrometers using CDCl3 as the solvent with Me4Si as the
internal standard. 13C NMR spectra were taken on JEOL JNM-GSX-270
(68 MHz), JEOL JNM-GSX-400 (100 MHz), and Varian GEMINI 2000
(75 MHz) spectrometers using CDCl3 as the solvent. 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) 77.16 ppm. IR spectra were determined on a Perkin-Elmer
Model 1600 spectrometer or JASCO FT/IR-8900 μ Fourier Transform
Infrared Microsampling System. Mass spectra were obtained on a JEOL
JMS-DX303 instrument in the analytical section of Osaka University.
Elemental analyses were performed in the analytical section of Osaka
University. Purification of the product was carried out by using a
recycling preparative HPLC (Japan Analytical Industry Co. Ltd., Model
LC-908) equipped with JAIGEL-1H and -2H columns (GPC) using
CHCl3 as an eluent.
General Procedure for the Cobalt-Catalyzed Thiolative
Lactonization. In a 50 mL stainless steel autoclave with a magnetic
stirring bar under N2 atmosphere were placed Co2(CO)8 (0.09 mmol),
freshly distilled acetonitrile (1ꢀ10 mL), alkyne (3.0 mmol),10 and thiol
(1.0 mmol), in that order. Carbon monoxide was purged three times and
then charged at 2ꢀ5 MPa. The reaction was conducted with magnetic
stirring for 17 h upon heating at 120ꢀ140 °C. After carbon monoxide
was purged, the resulting mixture was filtered through Celite with Et2O
and concentrated in vacuo to give a brown-black oil. Purification was
performed by silica gel column chromatography (hexanes/AcOEt 4/1)
Figure 1. X-ray analysis of the thiolative lactonization product 3ea.
Although the clarification of the precise pathway for this
carbonylation should wait for further detailed mechanistic in-
vestigations, a possible catalytic cycle is shown in Scheme 1: (i)
the formation of the cobalt alkyne complex and the reaction with
R0SH lead to the cobalt hydrideꢀcobalt sulfide complex A;
(ii) CO insertion and reductive elimination form complex B; (iii)
further CO insertion generates the acylcobalt complex C; (iv)
cyclization and reductive elimination afford the double-carbonyla-
tion product 3 with recovery of the cobalt alkyne complex.
’ CONCLUSION
In summary, we have developed a novel thiolative lactoniza-
tion of terminal alkynes with thiols and CO. This process
provides a useful method for the catalytic introduction of two
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ARTICLE
followed by a recycling preparative LC equipped with GPC columns
(JAIGEL-1H and -2H) with CHCl3 as eluent.
26.9, 27.9, 34.2, 36.0, 44.3, 86.5, 116.9, 171.0, 172.1; IR (KBr) 2930, 2855,
2352, 1759, 1636, 1448 cmꢀ1; MS (EI) m/z 268 (M+); HRMS calcd for
C15H24O2S 268.1497, found 268.1497.
Preparation of Cobalt Alkyne Complex A. In a flask (30 mL)
equipped with a magnetic stirring bar were placed Co2(CO)8 (2.0
mmol), freshly distilled acetonitrile (1 mL), and 1-octyne (2.0 mmol).
The mixture was stirred for 24 h at room temperature under an N2
atmosphere. The resulting mixture was concentrated in vacuo. The
purification was performed by preparative TLC on Wakogel B-5F silica
gel with hexanes as eluent.
5-Cyclohexylthio-4-(3-hydroxypropyl)-5H-furan-2-one (3ca):.pale yellow
1
oil; H NMR (400 MHz, CDCl3) δ 1.22ꢀ1.57 (m, 6H), 1.59ꢀ1.64
(m, 2H), 1,74ꢀ1.95 (m, 4H), 2.00ꢀ2.10 (m, 2H), 2.44ꢀ2.55 (m, 1H),
2.59ꢀ2.70 (m, 1H) 2.93ꢀ3.02(m, 1H) 3.73(t,J= 6.0 Hz, 1H), 5.93 (s, 1H),
6.03 (s, 1H); 13C NMR (100 MHz, CDCl3) δ 25.4, 25.6, 26.0, 29.9, 34.2,
44.4, 61.8, 86.6, 117.2, 170.1, 171.9; IR (KBr) 3400, 2934, 2853, 2065, 1635,
1541, 1448, 1263 cmꢀ1; MS (EI) m/z 256 (M+); HRMS calcd for
C13H20O3S 256.1133, found 256.1132.
Spectral and Analytical Data. 5-Cyclohexylthio-4-hexyl-5H-
1
furan-2-one (3aa): pale yellow oil; H NMR (400 MHz, CDCl3) δ
5-Cyclohexylthio-4-(3-cyanopropyl)-5H-furan-2-one (3da): pale brown
0.90 (t, J = 6.8 Hz, 3H), 1.25ꢀ1.50 (m, 12H), 1.56ꢀ1.64 (m, 2H),
1.76ꢀ1.80 (m, 2H), 2.00ꢀ2.06 (m, 2H), 2.34ꢀ2.36 (m, 1H), 2.48ꢀ2.50
(m, 1H), 2.93ꢀ2.98 (m, 1H), 5.89 (s, 1H), 5.99 (s, 1H); 13C NMR (100
MHz, CDCl3) δ 14.1, 22.6, 25.6, 26.0, 26.1, 27.0, 28.9, 29.0, 31.5, 34.2,
44.3, 86.5, 117.0, 170.8, 172.0; IR (KBr) 2927, 2855, 2353, 1790, 1759,
1636, 1448, 968 cmꢀ1; MS (EI) m/z 282 (M+); HRMS calcd for
C16H26O2S 282.1653, found 282.1652. Anal. Calcd for C16H26O2S: C,
68.04; H, 9.28. Found: C, 68.22; H, 9.40.
1
oil; H NMR (400 MHz, CDCl3) δ 1.22ꢀ1.67 (m, 4H), 1.75ꢀ1.82
(m, 2H), 1.91ꢀ2.05 (m, 4H), 2.31ꢀ2.77 (m, 6H), 2.96ꢀ3.02 (m, 1H),
5.95 (s, 1H), 6.02 (s, 1H); 13C NMR (100 MHz, CDCl3) δ 17.1, 23.0, 25,6,
26.0, 27.7, 34.1, 44.8, 86.4, 118.0, 118,6, 167.6, 171.2; IR (KBr) 2923, 2844,
2245, 1789, 1755, 1637, 1452, 1168, 966, 895 cmꢀ1; HRMS calcd for
C14H19NO2S 265.1136, found 265.1135.
5-Cyclohexylthio-4-phenylmethyl-5H-furan-2-one (3ea): pale brown
1
5-(1-Dodecylthio)-4-hexyl-5H-furan-2-one (3ab): yellow oil; 1H
NMR (400 MHz, CDCl3) δ 0.88 (t, J = 6.9 Hz, 3H), 0.90 (t, J = 6.9
Hz, 3H), 1.22ꢀ1.41 (m, 24H), 1.52ꢀ1.66 (m, 4H), 2.28ꢀ2.39 (m, 1H),
2.45ꢀ2.69 (m, 3H), 5.88 (s, 1H), 5.90 (dd, J = 3.2, 1.8 Hz, 1H); 13C
NMR (100 MHz, CDCl3) δ 13.9, 14.1, 22.4, 22.6, 26.9, 28.6, 28.77,
28.82, 29.1, 29.3, 29.4, 29.51, 29.58 (overlap), 31.4, 31.9, 86.9, 116.8,
170.4, 171.6; IR (NaCl) 2923, 2855, 1790, 1763, 1636, 1466, 1377,
1288, 1165, 972 cmꢀ1; HRMS (EI) calcd for C22H40O2S: 368.2749,
found: 368.2762.
solid; H NMR (400 MHz, CDCl3) δ 1.20ꢀ1.68 (m, 6H), 1.73ꢀ1.79
(m, 2H), 2.00 (m, 2H), 2.93ꢀ3.00 (m, 1H), 3.63 (d, J = 16.6 Hz, 1H),
3.87 (d, J = 16.6 Hz, 1H), 5.79 (s, 1H), 5.92 (s, 1H), 7.18ꢀ7.39 (m, 5H);
13C NMR (100 MHz, CDCl3) δ 25.6, 26.0, 34.1, 35.4, 44.4, 86.2, 118.4,
127.6, 129.1, 129.2, 135.8, 169.3, 171.6; IR (KBr) 2928, 2850, 2345, 1744,
1633, 1450, 1163, 976, 847, 702 cmꢀ1; HRMS calcd for C17H20O2S
288.1184, found 288.1184.
’ ASSOCIATED CONTENT
5-Ethylthio-4-hexyl-5H-furan-2-one (3ac): yellow oil; 1H NMR (400
MHz, CDCl3) δ 0.90 (t, J = 6.9 Hz, 3H), 1.29ꢀ1.40 (m, 9H), 1.53ꢀ1.69
(m, 2H), 2.28ꢀ2.40 (m, 1H), 2.45ꢀ2.55 (m, 1H), 2.56ꢀ2.66 (m, 2H),
5.91 (s, 2H); 13C NMR (100 MHz, CDCl3) δ 13.9, 14.7, 22.4, 23.8, 26.8,
28.5, 28.8, 31.3, 86.7, 116.8, 170.4, 171.6; IR (NaCl) 2958, 2932, 2868,
1790, 1759, 1636, 1454, 1377, 1288, 1265, 1165, 972 cmꢀ1; HRMS (EI)
calcd for C12H20O2S 228.1184, found 228.1163.
S
Supporting Information. Text, tables, and figures giving
b
experimental detailsandcharacterizationdataforallnewcompounds
and a CIF file giving crystallographic data for 3ea. This material is
available free of charge via the Internet at http://pubs.acs.org.
’ AUTHOR INFORMATION
5-Phenylthio-4-hexyl-5H-furan-2-one (3ad): pale brown oil; 1H
NMR (400 MHz, CDCl3) δ 0.90 (t, J = 6.8 Hz, 3H), 1.23ꢀ1.40 (m,
6H), 1.44ꢀ1.64 (m, 2H), 2.34ꢀ2.43 (m, 1H), 2.48ꢀ2.57 (m, 1H), 5.73
(d, J = 2.0 Hz, 1H), 6.01 (s, 1H), 7.29ꢀ7.35 (m, 3H), 7.50ꢀ7.52 (m,
2H); 13C NMR (100 MHz, CDCl3) δ 14.0, 22.5, 26.8, 28.6, 28.9, 31.4,
88.5, 117.4, 129.17, 129.18, 129.21, 134.1, 169.4, 171.4; IR (NaCl) 2924,
2862, 1790, 1759, 1636, 1535, 1466, 1165, 972 cmꢀ1; MS (EI) m/z 276
(M+); HRMS calcd for C16H20O2S 276.1184, found 276.1184.
Corresponding Author
*E-mail: ogawa@chem.osakafu-u.ac.jp.
’ ACKNOWLEDGMENT
This work was supported by a Grant-in-Aid for Scientific
Research on Scientific Research (C, 23550057), from the
Ministry of Education, Culture, Sports, Science and Technology
of Japan and in part by the Leading-edge Research Infrastructure
Program (Tohoku University). We also thank Mr. Shin-ichi
Kawaguchi, Mr. Masayuki Daito, Mr. Yoshimasa Tsuneda, Mr.
Yuki Suzuki, Mr. Taichi Tamai, and Mr. Kunimasa Marui for their
experimental support.
1
5-(4-Tolylthio)-4-hexyl-5H-furan-2-one (3ae): pale yellow oil; H
NMR (400 MHz, CDCl3) δ 0.91 (t, J = 6.8 Hz, 3H), 1.24ꢀ1.40 (m,
6H), 1.42ꢀ1.64 (m, 2H), 2.33 (s, 3H), 2.34ꢀ2.41 (m, 1H), 2.45ꢀ2.57
(m, 1H), 5.71 (s, 1H), 5.97 (s, 1H), 7.12 (d, J = 7.2 Hz, 2H), 7.38 (d, J =
7.2 Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 14.0, 21.2, 22.5, 26.8, 28.6,
28.9, 31.4, 88.6, 117.2, 125.2, 129.9, 134.5, 139.6, 169.5, 171.5; IR
(NaCl) 2958, 2928, 2858, 1786, 1755, 1636, 1436, 1458, 1289, 1165,
976 cmꢀ1; HRMS (EI) calcd for C17H22O2S 290.1340, found 290.1318.
5-(4-Chlorophenylthio)-4-hexyl-5H-furan-2-one (3af): pale brown
oil; 1H NMR (400 MHz, CDCl3) δ (t, J = 6.8 Hz, 3H), 1.31ꢀ1.37 (m,
6H), 1.45ꢀ1.64 (m, 2H), 2.33ꢀ2.41 (m, 1H), 2.46ꢀ2.55 (m, 1H), 5.75
(s, 1H), 5.98 (s, 1H), 7.30 (d, J = 7.8 Hz, 2H), 7.38 (d, J = 7.8 Hz, 2H);
13C NMR (100 MHz, CDCl3) δ 14.1, 22.6, 26.9, 28.7, 29.0, 31.5, 88.3,
117.7, 127.6, 129.5, 135.6, 135.9, 169.3, 171.2; IR (NaCl) 2928, 2858,
1790, 1759, 1636, 1477, 1389, 1288, 1096, 976 cmꢀ1; HRMS (EI) calcd
for C16H19ClO2S 310.0794, found 310.0781.
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1
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clave at higher temperature (140 °C). Therefore, when small amounts of
CH3CN were used for this carbonylation, most of the solvent was
vaporized and CO could not dissolve the solvent. This results in a
decrease in the yields of the carbonylation products.
(8) When the monocarbonylation product 4aa was used as
the substrate for the double carbonylation, the corresponding thiolative
lactonization product 3aa was not obtained at all. Therefore, the
monocarbonylation product 4aa is not a key intermediate for the
thiolative lactonization.
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(10) The present thiolative lactonization requires excess amounts of
alkynes. The equimolar reaction of alkyne with thiol resulted in a
decrease in the yields of the carbonylation products. Excess amounts
of alkynes inhibit the poisoning of the catalyst with thiols, probably by
regeneration of the catalyst (cobalt alkyne complex) in the catalytic cycle.
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