Palladium-Catalyzed Carbonylative Lactonization of Propargyl Alcohols with Organic Dichalcogenides and Carbon Monoxide

Article abstract of DOI:10.1021/jo970973q

The reaction of propargylic alcohols with diaryl disulfides and carbon monoxide in the presence of tetrakis(triphenylphosphine)palladium leads to a novel thiolative lactonization to afford β-(arylthio)-α,β,-unsaturated lactones in moderate to good yields.

Full text of DOI:10.1021/jo970973q

J . Org. Chem. 1997, 62, 8361-8365
8361
P a lla d iu m -Ca ta lyzed Ca r bon yla tive La cton iza tion of P r op a r gyl
Alcoh ols w ith Or ga n ic Dich a lcogen id es a n d Ca r bon Mon oxid e
Akiya Ogawa,*,† Hitoshi Kuniyasu,† Noboru Sonoda,*,‡ and Toshikazu Hirao†
Department of Applied Chemistry, Faculty of Engineering, Osaka University, Suita, Osaka 565, J apan,
Department of Applied Chemistry, Faculty of Engineering, Kansai University, Suita, Osaka 564, J apan
Received J une 2, 1997X
The reaction of propargylic alcohols with diaryl disulfides and carbon monoxide in the presence of
tetrakis(triphenylphosphine)palladium leads to a novel thiolative lactonization to afford â-(arylthio)-
R,â-unsaturated lactones in moderate to good yields. Similar conditions can be employed with
homopropargylic alcohols, giving the corresponding δ-lactones with a â-arylthio group successfully.
The reaction using diaryl diselenides in lieu of diaryl disulfides also attains a similar one-pot
thiolation/lactonization sequence to provide the corresponding â-selenobutenolides (7).
In tr od u ction
reactions ineffective. On the contrary, we have recently
revealed a series of reactions involving such a mis-
matched combination of chalcogen compounds and tran-
sition metal catalysts.5 These reactions clearly demon-
strate the efficacy of the transition metal catalysts in the
synthetic reactions of organic sulfides and selenides. For
example, diaryl dichalcogenides add stereoselectively to
terminal acetylenes in the presence of palladium(0)
catalyst, as shown in eq 1.5i When the same reaction is
carried out under the pressure of carbon monoxide, the
carbonylative addition of diaryl dichalcogenides to acetyl-
enes takes place with excellent regio- and stereoselec-
tivity (eq 2).5i
Although the utility of transition metal catalysts for
effecting a wide variety of synthetic transformations
using heteroatom compounds, such as organic silicon,1
tin,2 and boron3 compounds, is well established, the use
of these catalysts for synthetic reactions of group 16
heteroatom compounds has remained largely unex-
plored.4 This is partly due to the widespread belief that
sulfur and selenium compounds often bind strongly to
the catalysts, thus poisoning them and making catalytic
† Osaka University.
‡ Kansai University.
X Abstract published in Advance ACS Abstracts, November 1, 1997.
(1) For example, see: (a) Hiyama, T.; Kusumoto, T. In Comprehen-
sive Organic Synthesis; Trost, B. M., Ed.; Pergamon: Oxford, 1991;
Vol. 8, p 763. (b) Ojima, I. In The Chemistry of Organic Silicon
Compounds; Patai, S., Rappoport, Z., Eds.; J ohn Wiley & Sons:
Chichester, 1989; Part 2, p 1479. (c) Hevesi, L. In Comprehensive
Organic Functional Group Transformations; Katritzky, A. R., Meth-
Cohn, O., Rees, C. W., Eds.; Elsevier Science: Cambridge, 1995; Vol.
2, p 899. (d) Murai, S.; Chatani, N. J . Synth. Org. Chem., J pn. 1993,
51, 421. (e) Recatto, C. A. Aldrichimica Acta 1995, 28, 85.
(2) (a) Stille, J . K. Angew. Chem., Int. Ed. Engl. 1986, 25, 508. (b)
Mitchell, T. N. Synthesis 1992, 803. (c) Pereyre, M.; Quintard, J .-P.;
Rahm, A. Tin in Organic Synthesis; Butterworths: London, 1987. (d)
Harrison, P. G. Chemistry of Tin; Blackie & Son: New York, 1989.
(3) (a) Burgess, K.; Ohlmeyer, M. J . Chem. Rev. (Washington, D.C.)
1991, 91, 1179. (b) Beletskaya, I.; Pelter, A. Tetrahedron 1997, 53,
4957. (C) Suzuki, A.; Miyaura, N. J . Synth. Org. Chem., J pn. 1993,
51, 1043.
(4) (a) Murahashi, S.-I.; Yano, T. J . Am. Chem. Soc. 1980, 102, 2456.
(b) Okamura, H.; Miura, M.; Kosugi, K.; Takei, H. Tetrahedron Lett.
1980, 21, 87. (c) Dzhemilev, U. M.; Kunakova, R. V.; Gaisin, R. L. Izv.
Akad. Nauk SSSR, Ser. Khim. 1981, 11, 2655. (d) Hutchins, R. O.;
Learn, K. J . Org. Chem. 1982, 47, 4380. (e) McKervey, M. A.;
Ratananukul, P. Tetrahedron Lett. 1982, 23, 2509. (f) Godleski, S. A.;
Villhauer, E. B. J . Org. Chem. 1984, 49, 2246. (g) Antebi, S.; Alper, H.
Tetrahedron Lett. 1985, 26, 2609. (h) Auburn, P. R.; Whelan, J .;
Bosnich, B. J . Chem. Soc., Chem. Commun. 1986, 146. (i) Cristau, H.
J .; Chabaud, B.; Labaudiniere, R.; Christol, H. J . Org. Chem. 1986,
51, 875. (j) Antebi, S.; Alper, H. Organometallics 1986, 5, 596. (k) Goux,
C.; Lhoste, P.; Sinou, D. Tetrahedron Lett. 1992, 33, 8099. (l) Taka-
hashi, H.; Ohe, K.; Uemura, S.; Sugita, N. J . Organomet. Chem. 1987,
334, C43. (m) Osakada, K.; Yamamoto, T.; Yamamoto, A. Tetrahedron
Lett. 1987, 28, 6321. (n) Carpita, A.; Rossi, R.; Scamuzzi, B. Tetrahe-
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(p) Fukuzawa, S.; Fujinami, T.; Sakai, S. Chem. Lett. 1990, 927. (q)
Kano, K.; Takeuchi, M.; Hashimoto, S.; Yoshida, Z. Chem. Lett. 1990,
1381. (r) Ishiyama, T.; Nishijima, K.; Miyaura, N.; Suzuki, A. J . Am.
Chem. Soc. 1993, 115, 7219. (s) Keim, W.; Herwig, J . J . Chem. Soc.,
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35, 9609. (x) Han, L.-B.; Choi, N.; Tanaka, M. J . Am. Chem. Soc. 1996,
118, 7000.
In the case of acetylenes possessing a hydroxyl group
in the “R” of acetylenes at a proper position, double bond
isomerization, followed by intramolecular cyclization, has
been found to take place, giving R,â-unsaturated â-chal-
cogenolactones (6 and 7) successfully (eq 3). Reported
herein is a novel thiolative lactonization of propargylic
(5) (a) Ogawa, A.; Kawakami, J .; Sonoda, N.; Hirao, T. J . Org. Chem.
1996, 61, 4161. (b) Ogawa, A.; Sonoda, N. J . Synth. Org. Chem., J pn.
1996, 54, 894. (c) Ogawa, A.; Takeba, M.; Kawakami, J .; Ryu, I.;
Kambe, N.; Sonoda, N. J . Am. Chem. Soc. 1995, 117, 7564. (d) Ogawa,
A.; Sonoda, N. J . Synth. Org. Chem., J pn. 1993, 51, 815. (e) Kuniyasu,
H.; Ogawa, A.; Sonoda, N. Tetrahedron Lett. 1993, 34, 2491. (f)
Kuniyasu, H.; Ogawa, A.; Sato, K.; Ryu, I.; Kambe, N.; Sonoda, N. J .
Am. Chem. Soc. 1992, 114, 5902. (g) Kuniyasu, H.; Ogawa, A.; Sato,
K.; Ryu, I.; Sonoda, N. Tetrahedron Lett. 1992, 33, 5525. (h) Kuniyasu,
H.; Ogawa, A.; Higaki, K.; Sonoda, N. Organometallics 1992, 11, 3937.
(i) Kuniyasu, H.; Ogawa, A.; Miyazaki, S.; Ryu, I.; Kambe, N.; Sonoda,
N. J . Am. Chem. Soc. 1991, 113, 9796.
S0022-3263(97)00973-0 CCC: $14.00 © 1997 American Chemical Society

8362 J . Org. Chem., Vol. 62, No. 24, 1997
Ogawa et al.
Ta ble 1. Ca r bon yla tive La cton iza tion of P r op a r gyl a n d
Hom op r op a r gyl Alcoh ols w ith Dia r yl Disu lfid es a n d
Diselen id esa
alcohols, which has also been attained by the combination
of organic dichalcogenides and palladium catalysts.6
Resu lts a n d Discu ssion
The reaction of 2-propyn-1-ol (1a ) with diphenyl disul-
fide and carbon monoxide in the presence of tetrakis-
(triphenylphosphine)palladium at 100 °C for 50 h pro-
vided 43% of 3-(phenylthio)-2-buten-4-olide (6a ) with the
formation of (Z)-1,2-bis(phenylthio)-3-hydroxy-1-propene
((Z)-2a , 35%) (entry 1 in Table 1). However, 1,3-bis-
(phenylthio)-4-hydroxy-2-buten-1-one (4a ) was not de-
tected at all under these reaction conditions.
The scope and limitations of this palladium-catalyzed
carbonylative lactonization of a series of hydroxyacetyl-
enes are summarized in Table 1. When diphenyl di-
selenide was used in place of diphenyl disulfide, a similar
lactonization took place to provide 3-(phenylseleno)-2-
buten-4-olide (7a ) (entry 2). Pd(PPh3)2Cl2 was also
effective as a catalyst for this carbonylative lactonization
with (PhSe)2 (entry 3).7 Introduction of a trifluoromethyl
group on the para position of diaryl diselenide improved
the yield of the butenolide (entry 5).
When diphenyl disulfide was used, the carbonylative
lactonization of R,R-disubstituted propargyl alcohols 6c
and 6d proceeded in poor yields, and instead, (Z)-4c and
(Z)-4d were formed as the major products, in 38% and
58% yields, respectively (entries 8 and 10). In contrast,
the corresponding reaction between 1c and (PhSe)2 gave
the desired lactone 7c in moderate yield (entry 9).
Spirocyclic lactones with a â-arylseleno group (7d and
7e) could also be prepared upon similar treatment of 1d
and 1e (entries 11 and 12). The present one-pot lacton-
ization was then applicable to a homopropargyl alcohol
(1f), which provided the corresponding δ-lactones (6f and
7f) in good yields (entries 13 and 14).
A mechanistic pathway of this one-pot lactonization is
likely to involve the following processes (Scheme 1): (i)
(PhS)2 adds oxidatively to low-valent palladium complex
to form “Pd(SPh)2Ln”;8 (ii) insertion of acetylene (1a ) into
the Pd-S bond forms a cis-vinylpalladium (10a ) regio-
and stereoselectively; (iii) introduction of carbon monox-
ide into the palladium-carbon bond of 10a provides
acylpalladium intermediate ((Z)-8a ) (carbonylation step);
(iv) double bond isomerization of (Z)-8a forms (E)-8a
(isomerization step); and (v) (E)-8a cyclizes intramolecu-
larly to give lactone (6a ) and benzenethiol with the
regeneration of the catalyst (cyclization step).
To obtain some information about the reaction path-
way, the following experiments were made. When the
palladium-catalyzed reaction of homopropargyl alcohol
(1f) with (PhS)2 in the presence of CO was carried out
under controlled conditions (80 °C, 30 h), a stereoisomeric
mixture of 4f was formed in 28% yield besides lactone 6f
(46%) (entry 1 in Table 2; eq 4).9,10 Upon subjection to
(6) For some examples of transition-metal-catalyzed carbonylative
lactonization of olefinic or acetylenic alcohols, see: (a) Matsuda, I.;
Ogiso, A.; Sato, S. J . Am. Chem. Soc. 1990, 112, 6120. (b) Matin, L.
D.; Stille, J . K. J . Org. Chem. 1982, 47, 3630. (c) Cowell, A.; Stille, J ,
K. J . Am. Chem. Soc. 1980, 102, 4193. (d) Ali, B. E.; Alper, H. J . Org.
Chem. 1991, 56, 5357. (e) Alper, H.; Leonard, D. J . Chem. Soc., Chem.
Commun. 1985, 511. (f) Murray, T. F.; Varma, V.; Norton, J . R. J . Org.
Chem. 1978, 43, 353. (g) Murray, T. F.; Varma, V.; Norton, J . R. J .
Am. Chem. Soc. 1977, 99, 8085.
(8) The oxidative addition of (PhS)2 to Pd(PPh3)4 easily proceeds even
at room temperature, see: (a) Zanella, R.; Ros, R.; Graziani, M. Inorg.
Chem. 1973, 12, 2736. (b) Rauchfuss, T. B.; Shu, J . S.; Roundhill, D.
M. Inorg. Chem. 1976, 15, 2096.
(7) In the case of (PhS)2, Pd(PPh3)2Cl2 was ineffective (the yield of
6a was 17%).

Pd-Catalyzed Carbonylative Lactonization of Progargyl Alcohols
J . Org. Chem., Vol. 62, No. 24, 1997 8363
Sch em e 1. A P r op osed Rea ction P a th w a y for th e
P a lla d iu m -Ca ta lyzed La cton iza tion of 1a w ith
(P h S)2 a n d CO
disulfides (or diselenides) to acetylenes bearing no hy-
droxy group provides Z-isomers of 4 (or 5) with excellent
stereoselectivity (eq 2), these results may indicate that
the presence of a hydroxyl group in 4 (or 5) is crucial for
the isomerization of (Z)-isomers into (E)-isomers.8
To elucidate whether the palladium catalyst is es-
sential for the isomerization step and/or the cyclization
step, the palladium(0)-catalyzed reaction of isolated (Z)-
4f was carried out in the presence of carbon monoxide
(eq 5). When a solution of (Z)-4f in benzene was heated
at 100 °C for 5 h in the presence of Pd(PPh3)4 under
pressurized CO,12 lactone 6f was obtained in 19% yield
along with small amounts of (E)-4f. Since the oxidative
addition of thioester 4f to palladium(0) species proceeds
very slowly under the conditions employed, the yields
were not very high, but both isomerization and cyclization
were observed. On the other hand, a similar reaction in
the absence of the palladium(0) catalyst resulted in
almost quantitative recovery of the starting (Z)-4f.
Although the precise mechanism of the double bond
isomerization remains unclear, a possible pathway may
include the formation of ketene species (11a ), in which
the palladium would undergo intramolecular coordina-
tion by the hydroxyl group (see Scheme 1).
Ta ble 2. P a lla d iu m -Ca ta lyzed Rea ction of
Hyd r oxya cetylen es w ith CO a n d (P h Y)2 (Y ) S, Se)a
In conclusion, the palladium-catalyzed reactions of
propargyl alcohols with diaryl disulfides and diselenides
under pressurized carbon monoxide allow the one-pot
preparation of butenolides possessing ArS and ArSe
groups at the â position, respectively, which result should
be applicable to the development of further transforma-
tions.13 This paper again demonstrates the utility of
transition metal catalysts in the synthetic reactions of
chalcogen compounds.
yield %b
substrate conditions lactone chalcogenoester
(PhY)2,
equiv
entry
1
2
3
1 (Y ) S)
1 (Y ) S)
1 (Y ) Se)
1f
1g
1g
80 °C, 30 h 46
100 °C, 50 h trace 41 (E/Z ) 62/38)
100 °C, 50 h trace 56 (E/Z ) 36/64)
28 (E/Z ) 47/53)
a
Substrate (1 mmol), (PhS)2 (1 or 4 mmol), CO (60 atm), and
b
Pd(PPh3)4 (2 mol %). Determined by 1H NMR.
the lactonization conditions, 4-pentyn-1-ol (1g) did not
provide the corresponding seven-membered lactone (6g),
but instead the carbonylation product 4g was formed as
a mixture of E- and Z-isomers (62/38) (entry 2). A similar
result was obtained in the reaction using (PhSe)2 (entry
3).11 Considering that the carbonylative addition of
Exp er im en ta l Section
Acetylenes and palladium complexes were obtained com-
mercially, and the former were purified by distillation if
necessary. Diaryl disulfides were obtained commercially and
were purified by recrystallization from EtOH or n-hexane and
dried in vacuo. Diphenyl diselenide was prepared according
to the literature14 and was recrystallized from n-hexane.
A
(9) The palladium-catalyzed carbonylative addition of disulfides and
diselenides to acetylenes bearing no hydroxyl group proceeded with
high stereoselectivity. For example, the reaction of 1-octyne (1 mmol)
with (PhS)2 (1 mmol) in the presence of Pd(PPh3)4 (0.02 mmol) under
pressure of CO (60 atm) at 80 °C for 39 h gave (Z)-1,3-bis(phenylthio)-
2-nonen-1-one stereoselectively in 84% yield; see ref 5i.
(10) When the carbonylative thiolation of propargyl alcohols such
as 1a was carried out at 100 °C for 24 h, the formation of (Z)-4a (17%)
and 6a (25%) was confirmed. In this case, however, no (E)-4a was
detected at all by 1H NMR spectrometer, probably because five-
membered cyclization proceeded very smoothly, compared with the six-
membered cyclization.
similar procedure was employed for the syntheses of bis(p-
methylphenyl) diselenide and bis(p-trifluoromethylphenyl)
(12) In the absence of carbon monoxide, palladium-catalyzed decar-
bonylation occurred competitively. For a relating report, see: Wenkert,
E.; Chianelli, D. J . Chem. Soc., Chem. Commun. 1991, 627 and ref 4m.
(13) (a) Tanikaga, R.; Yamasita, H.; Kaji, A. Synthesis 1986, 416.
(b) Barua, N. C.; Schmidt, R. R. Synthesis 1986, 1067. (c) Trost, B. M.;
Lavoie, A. C. J . Am. Chem. Soc. 1983, 105, 5075. (d) Magnus, P.;
Quagliato, D. J . Org. Chem. 1985, 50, 1621. (e) Comasseto, J . V. J .
Organomet. Chem. 1983, 253, 131. (f) Paulmier, C. Selenium Reagents
and Intermediates in Organic Synthesis; Pergamom Press: Oxford,
1986.
(11) The carbonylative addition of (PhSe)2 to 1-octyne under similar
reaction conditions (100 °C, 50 h) gave 1,3-bis(phenylseleno)-2-nonen-
1-one in 57% yield (E/Z ) 1/99) with the concomitant formation of some
unidentified materials.
(14) Reich, H. J .; Renga, J . M.; Reich, I. L. J . Am. Chem. Soc. 1975,
97, 5434.

8364 J . Org. Chem., Vol. 62, No. 24, 1997
Ogawa et al.
diselenide. Benzene was purified by distillation from sodium
(>8%)-lead alloy before use. 1H NMR spectra of CDCl3
solutions were recorded on a J EOL J NM-GSX-270 (270 MHz)
spectrometer. 13C NMR spectra of CDCl3 solutions were also
recorded on a J EOL J NM-GSX-270 (68 MHz) spectrometer.
Chemical shifts in the 1H NMR and 13C NMR spectra were
determined relative to Me4Si. IR spectra were recorded on a
Perkin-Elmer Model 1600 spectrometer. Mass spectra were
recorded on a J EOL J MS-DX303 apparatus. Purification of
products was performed by using MPLC with Merck 25-40
mm mesh silica gel (Art 9390) and preparative TLC with
Wakogel B-5F silica gel (or recycling preparative HPLC (J apan
Analytical Industry Co., Ltd. Model LC-908, J AIGEL-1H and
-2H (GPC), length 600 mm, i.d. 20 mm, eluent CHCl3)). High-
resolution mass spectra (HRMS) and combustion analyses
were performed in the Instrumental Analysis Center of the
Faculty of Engineering, Osaka University. Registry numbers
are provided by the author.
P a lla d iu m -Ca ta lyzed On e-P ot Ca r bon yla tive La cton i-
za tion : Gen er a l P r oced u r e (Ta ble 1, en tr y 1). To a 50
mL stainless steel autoclave equipped with a magnetic stirring
bar were placed diphenyl disulfide (1.0 mmol), 2-propyn-1-ol
(1a ) (1.0 mmol), tetrakis(triphenylphosphine)palladium (Pd-
(PPh3)4) (0.02 mmol), and benzene (1 mL). The apparatus was
charged with carbon monoxide at 60 atm, and the mixture was
heated at 100 °C for 50 h with magnetic stirring. The resulting
brown precipitate was removed by filtration through Celite,
and the filtrate was concentrated under reduced pressure. The
crude mixture was analyzed by using a 1H and 13C NMR
spectrometer and then was separated by MPLC (silica gel, 25-
40 mm, length 310 mm, i.d. 25 mm, n-hexane/ether as eluent)
followed by HPLC to provide 83 mg of 3-(phenylthio)-2-buten-
4-olide (6a ) (43%, CA Registry No. 57061-30-0).15
4-Meth yl-3-(p h en ylselen o)-2-bu ten -4-olid e (7b) (Ta ble
1, en tr y 7): yellow oil; 1H NMR (270 MHz, CDCl3) δ 1.51 (d,
J ) 6.8 Hz, 3 H), 5.10 (q, J ) 6.8 Hz, 1 H), 5.48 (s, 1 H), 7.39-
7.48 (m, 3 H), 7.62-7.65 (m, 2 H); 13C NMR (68 MHz, CDCl3)
δ 20.23, 80.72, 115.70, 124.49, 130.11, 130.22, 135.91, 170.84;
IR (NaCl) 3057, 2982, 2929, 1746, 1571, 1163, 1056, 931, 743,
692 cm-1; mass spectrum (EI) m/z 254 (M+, 100). Anal. Calcd
for C11H10O2Se: C, 52.19; H, 3.98. Found: C, 52.23; H, 4.02.
4, 4-Dim eth yl-3-(ph en ylth io)-2-bu ten -4-olide (6c) (Table
1, en tr y 8): CA Registry No. 84246-67-3.17 13C NMR (68 MHz,
CDCl3) δ 26.62, 86.30, 109.66, 128.02, 130.14, 130.46, 134.60,
170.02, 177.98; mass spectrum (EI) m/z 220 (M+, 100).
1,3-Bis(p h en ylt h io)-4-m et h yl-4-h yd r oxy-2-p en t en -1-
on e ((Z)-4c): mp 103-104 °C (yellow solid); 1H NMR (270
MHz, CDCl3) δ 1.53 (s, 6 H), 2.27 (s, 1 H), 6.91 (s, 1 H), 7.09-
7.36 (m, 10 H) (NOE experiment: Irradiation of methyl singlet
at δ 1.53 resulted in a 23% enhancement at δ 6.91 (vinyl
singlet)); 13C NMR (68 MHz, CDCl3) δ 29.19, 75.20, 125.56,
126.87, 127.67, 128.96, 129.04, 129.22, 130.10, 134.38, 134.90,
157.41, 186.57; IR (KBr) 3496, 2979, 1672, 1585, 1479, 1440,
1037, 762, 746, 689 cm-1
. Anal. Calcd for C18H18O2S2: C,
65.42; H, 5.49; S, 19.40. Found: C, 65.05; H, 5.32; S, 19.32.
4,4-Dim et h yl-3-(p h en ylselen o)-2-b u t en -4-olid e (7c)
(Ta ble 1, en tr y 9): oil; 1H NMR (270 MHz, CDCl3) δ 1.57 (s,
6 H), 5.29 (s, 1 H), 7.41-7.47 (m, 3 H), 7.61-7.64 (m, 2 H);
13C NMR (68 MHz, CDCl3) δ 26.89, 87.52, 114.46, 124.59,
130.06, 130.17, 135.98, 169.87, 176.02; IR (NaCl) 3058, 2980,
1749, 1573, 1240, 1117, 980, 923, 812, 835, 744, 691 cm-1; mass
spectra (CI), m/z 269 (M+ + 1, 100). Anal. Calcd for C12H12O2-
Se: C, 53.94; H, 4.53. Found: C, 53.76; H, 4.70.
4-(P h en ylth io)-1-oxaspir o[4.4]-3-n on en -2-on e (6d) (Table
1, en tr y 10): mp 59-61 °C (a white solid); 1H NMR (270 MHz,
CDCl3) δ 1.79-2.38 (m, 8 H), 5.16 (s, 1 H), 7.46-7.57 (m, 5
H); 13C NMR (68 MHz, CDCl3) δ 25.15, 38.66, 96.36, 110.66,
128.12, 130.20, 130.40, 134.77, 170.31, 175.44; IR (KBr) 2966,
1754, 1572, 1472, 1440, 1270, 1148, 938, 832, 762, 598, 586
cm-1; mass spectrum (EI) m/z 246 (M+, 61). Anal. Calcd for
C14H14O2S: C, 68.27; H, 5.73; S, 13.02. Found: C, 68.33, H,
5.69; S, 12.96.
1,3-Bis(ph en ylth io)-3-(1′-h ydr oxycyclopen tyl)-2-pr opan -
1-on e (4d ): mp 87-88 °C (a light yellow solid); 1H NMR (270
MHz, CDCl3) δ 1.62-1.95 (m, 6 H), 2.04 (s, 1 H), 2.07-2.14
(m, 2 H), 6.96 (s, 1 H), 7.10-7.35 (m, 10 H); 13C NMR (68 MHz,
CDCl3) δ 24.16, 39.97, 85.80, 125.97, 126.81, 127.68, 128.95,
129.02, 129.18, 129.93, 134.36, 135.06, 155.81, 186.49; IR (KBr)
3489, 3055, 2949, 1669, 1582, 1478, 1440, 1043, 1008, 754, 702,
579, 487 cm-1; mass spectrum (EI), m/z 247 (M+ - 109, 67).
Anal. Calcd for C20H20O2S2; C, 67.38; H, 5.65; S 17.99.
Found: C, 67.67; H, 5.68; S, 17.93.
The following compounds were prepared according to the
general procedure. The reaction listed in Table 2 was also
carried out under similar reaction conditions. The structures
of lactones obtained were characterized unambiguously on the
basis of analytical and spectral data.
3-(P h en ylselen o)-2-bu ten -4-olid e (7a ) (Ta ble 1, en tr y
2): yellow oil; 1H NMR (270 MHz, CDCl3) δ 4.72 (s, 2 H), 5.76
(s, 1 H), 7.39-7.48 (m, 3 H), 7.63-7.66 (m, 2 H); 13C NMR (68
MHz, CDCl3) δ 73.51, 115.60, 123.32, 130.01, 130.10, 136.00,
164.50, 171.80; IR (NaCl) 3058, 2932, 1770, 1742, 1567, 1440,
1249, 1150, 1008, 884, 845, 744, 692 cm-1; mass spectra (EI)
m/z 240 (M+, 100). Anal. Calcd for C10H8O2Se: C, 50.23; H,
3.37. Found: C, 49.98; H, 3.41.
3-[(p-Meth ylph en yl)selen o]-2-bu ten -4-olide (7a ′) (Table
1
1, en tr y 4): yellow oil; H NMR (270 MHz, CDCl3) δ 2.39 (s,
3 H), 4.70 (d, J ) 1.7 Hz, 2 H), 5.75 (t, J ) 1.7 Hz, 1 H), 7.21
(d, J ) 7.9 Hz, 2 H), 7.51 (d, J ) 7.9 Hz, 2 H); 13C NMR (68
MHz, CDCl3) δ 21.22, 73.61, 115.46, 119.73, 130.88, 136.05,
140.62, 165.09, 172.00; IR (NaCl) 3024, 2924, 1774, 1743, 1569,
1490, 1249, 1149, 1007, 883, 846, 807, 725, 697 cm-1; mass
spectrum (EI) m/z 254 (M+, 100). Anal. Calcd for C11H10O2Se:
C, 52.19; H, 3.98. Found: C, 52.37; H, 4.08.
4-(P h en ylselen o)-1-oxa sp ir o[4.4]-3-n on en -2-on e (7d )
1
(Ta ble 1, en tr y 11): mp 85-89 °C (a white solid); H NMR
(270 MHz, CDCl3) δ 1.82-2.18 (m, 8 H), 5.33 (s, 1 H), 7.42-
7.50 (m, 3 H), 7.60-7.70 (m, 2 H); 13C NMR (68 MHz, CDCl3)
δ 25.09, 38.90, 97.61, 115.41, 124.67, 130.08, 130.22, 136.11,
170.14, 173.44; IR (KBr) 2966, 1736, 1564, 1442, 1246, 1149,
946, 922, 834, 752, 692, 578, 478 cm-1; mass spectrum (EI),
m/z 294 (M+, 70). Anal. Calcd for C14H14O2Se: C, 57.35; H,
4.81. Found: C, 57.18; H, 4.80.
3-[[(p -T r iflu o r o m e t h y l)p h e n y l]s e le n o ]-2-b u t e n -4-
olid e (7a ′) (Ta ble 1, en tr y 5): mp 48-49 °C (a white solid);
1H NMR (270 MHz, CDCl3) δ 4.78 (s, 2 H), 5.80 (s, 1 H), 7.69
(d, J ) 7.7 Hz, 2 H), 7.82 (d, J ) 7.7 Hz, 2 H); 13C NMR (68
MHz, CDCl3) δ 73.52, 116.61, 123.43 (q, J ) 273 Hz), 126.89
(q, J ) 3.8 Hz), 128.06, 132.30 (q, J ) 33 Hz), 136.31, 162.71,
171.45; IR (KBr) 3067, 2970, 1783, 1736, 1571, 1249, 1166,
1124, 1006, 834, 702, 596, 500, 438 cm-1; mass spectrum (EI)
m/z 308 (M+, 100). Anal. Calcd for C11H7O2F3Se: C, 43.02; H,
2.30. Found: C, 43.24; H, 2.43.
4-(P h en ylselen o)-1-oxa sp ir o[5.4]-3-d eca n -2-on e (7e)
(Ta ble 1, en tr y 12): mp 101-106 °C (a white solid); 1H NMR
(270 MHz, CDCl3) δ 1.65-2.05 (m, 10 H), 5.28 (s, 1 H), 7.35-
7.51 (m, 3 H), 7.61-7.64 (m, 2 H); 13C NMR (68 MHz, CDCl3)
δ 22.06, 24.46, 36.21, 89.27, 114.36, 124.73, 130.08, 130.22,
136.11, 170.36, 176.22; IR (KBr) 3044, 2932, 1740, 1568, 1269,
1251, 1211, 931, 888, 835, 754, 694, 578, 478 cm-1; mass
spectrum (EI), m/z 308 (M+, 100). Anal. Calcd for C15H16O2-
Se: C, 58.64; H, 5.25. Found: C, 54.43; H, 5.36.
3-(P h en ylt h io)-2-p en t en -5-olid e (6f) (Ta b le 1, en t r y
13): mp 71-73 °C (a yellow solid); 1H NMR (270 MHz, CDCl3)
δ 2.59 (t, J ) 6.1 Hz, 2 H), 4.39 (t, J ) 6.1 Hz, 2 H), 5.32 (s, 1
H), 7.46-7.52 (m, 5 H); 13C NMR (68 MHz, CDCl3) δ 28.67,
65.68, 110.15, 127.03, 130.03, 130.49, 135.37, 161.06, 163.18;
IR (KBr) 3056, 2893, 1708, 1591, 1472, 1398, 1290, 1210, 1202,
4-Meth yl-3-(p h en ylth io)-2-bu ten -4-olid e (6b) (Ta ble 1,
en tr y 6): CA Registry No. 75717-37-2.16 13C NMR (68 MHz,
CDCl3) δ 20.00, 79.20, 110.75, 127.86, 130.15, 130.48, 134.48,
170.95, 173.73; mass spectrum (EI), m/z 206 (M+, 100).
(15) (a) Andre`s, D. F.; Dietrich, U.; Laurent, E. G.; Marquet, B. S.
Tetrahedron 1997, 53, 647. (b) Hollingworth, G. J .; Perkins, G.;
Sweeney, J . J . Chem. Soc., Perkin Trans. 1 1996, 1913. (c) Townsend,
C. A.; Christensen, S. B.; Davis, S. G. J . Chem. Soc., Perkin Trans. 1
1988, 839.
(16) (a) Xiao, W.-J .; Alper, H. J . Org. Chem. 1997, 62, 3422. (b)
Bakuzis, P.; Bakuzis, M. L. F. J . Org. Chem. 1981, 46, 235.
(17) Barbier, P.; Benezra, C. Tetrahedron Lett. 1982, 23, 3511.

Pd-Catalyzed Carbonylative Lactonization of Progargyl Alcohols
J . Org. Chem., Vol. 62, No. 24, 1997 8365
1078, 1050, 746, 694, 631 cm-1; mass spectrum (EI), m/z 206
(M+, 100). Anal. Calcd for C11H10O2S: C, 64.06; H, 4.89; S,
15.54. Found: C, 63.80; H, 5.03; S, 15.50.
1,3-Bis(p h en ylselen o)-6-h yd r oxy-2-h exen -1-on e (5g)
(Ta ble 2, en tr y 3): (Z)-isomer: mp 98-100 °C (a light yellow
solid); 1H NMR (270 MHz, CDCl3) δ 1.55 (quintet, J ) 6.1 Hz,
7.6 Hz, 2 H), 1.70 (br s, 1 H), 2.26 (t, J ) 7.6 Hz, 2 H), 3.29 (t,
J ) 6.1 Hz, 2 H), 6.71 (s, 1 H), 7.30-7.65 (m, 10 H) (NOE
experiment: Irradiation of the methylene triplet at δ 2.26
resulted in a 21% enhancement of the signal at δ 6.71 (vinyl
singlet)); 13C NMR (68 MHz, CDCl3) δ 32.35, 33.99, 61.06,
122.49, 126.58, 127.08, 128.83, 129.24, 129.29, 129.45, 135.74,
137.23, 161.95, 187.69; IR (KBr) 3326, 3055, 2937, 1664, 1546,
1532, 1085, 809, 742, 693 cm-1; mass spectrum (CI), m/z 427
(M+ + 1, 8). Anal. Calcd for C18H18O2Se2: C, 50.96; H, 4.27.
Found: C, 51.01; H, 4.34.
(E)-Isomer could not be obtained in pure form, so only
spectral analyses were performed. (E)-isomer: 1H NMR (270
MHz, CDCl3) δ 1.87 (quintet, J ) 5.9, 7.3 Hz, 2 H), 2.07 (br s,
1 H), 2.88 (t, 2 H, J ) 7.3 Hz), 3.62 (t, 2 H, J ) 5.9 Hz), 5.94
(s, 1 H), 7.30-7.66 (m, 10 H); 13C NMR (68 MHz, CDCl3) δ
31.69, 32.55, 61.09, 123.48, 126.03, 126.87, 128.88, 129.32,
129.94, 130.07, 135.69, 136.72, 163.43, 187.74; IR (NaCl) 3368,
3056, 2942, 2874, 1693, 1564, 1557, 1476, 1438, 1338, 1038,
1020, 738, 690 cm-1; mass spectrum (CI), m/z 427 (M+ + 1, 8).
Cycliza tion of (Z)-4f in th e P r esen ce of P d (P P h 3)4 (eq
5). In a 50-mL stainless steel autoclave equipped with a
magnetic stirring bar were placed (Z)-4f (14.4 mg, 0.05 mmol),
Pd(PPh3)4 (1.2 mg, 0.001 mmol), and benzene (0.1 mL). The
apparatus was charged with carbon monoxide (60 atm), the
resulting mixture was heated at 100 °C for 5 h, and the
reaction mixture was filtered through Celite and evaporated
in vacuo. The formation of 6f (19%) was confirmed by 1H NMR
spectroscopy.
3-(P h en ylselen o)-2-p en ten -5-olid e (7f) (Ta ble 1, en tr y
1
14): yellow oil; H NMR (270 MHz, CDCl3) δ 2.61 (t, J ) 6.1
Hz, 2 H), 4.37 (t, J ) 6.1 Hz, 2 H), 5.64 (s, 1 H), 7.37-7.49 (m,
3 H), 7.58-7.61 (m, 2 H); 13C NMR (68 MHz, CDCl3) δ 29.65,
65.88, 114.99, 124.18, 129.98, 129.98, 136.50, 159.02, 162.43;
IR (NaCl) 3057, 2990, 2945, 2894, 1715, 1590, 1284, 1214,
1080, 1048, 1022, 856, 743 cm-1; mass spectrum (EI) m/z 254
(M+, 19). Anal. Calcd for C11H10O2Se: C, 52.19; H, 3.98.
Found: C, 51.93; H, 4.12.
(Z)-1,3-Bis(p h en ylth io)-5-h yd r oxy-2-p en ten -1-on e ((Z)-
4f) (Ta ble 2, en tr y 1): CA Registry No. 148787-89-7.5e This
compound was prepared under more moderate reaction condi-
tions (80 °C, 24 h) than those of listed in Table 2. The attempt
to isolate (E)-4f was unsuccessful, because it gradually de-
composed to 6f and PhSH during purification by preparative
TLC. mp 110-112 °C (a white solid); 1H NMR (270 MHz,
CDCl3) δ 1.46 (t, J ) 5.4 Hz, 1 H), 2.41 (t, J ) 6.4 Hz, 2 H),
3.58, (q, J (average) ) 5.9 Hz, 2 H), 6.35 (s, 1 H), 7.34-7.55
(m, 10 H) (NOE experiment: Irradiation at methylene triplet
of δ 2.41 resulted in a 28% enhancement at δ 6.35 (vinyl
singlet)); 13C NMR (68 MHz, CDCl3) δ 39.20, 60.95, 118.64,
127.93, 129.05, 129.23, 129.27, 129.69, 130.07, 134.60, 135.62,
157.15, 185.16; IR (KBr) 3531, 2872, 1641, 1537, 1476, 1439,
1111, 1073, 1046, 842, 748, 706 cm-1; mass spectrum (CI), m/z
317 (M+ + 1, 100). Anal. Calcd for C17H16O2S2: C, 64.53; H,
5.10; S, 20.26. Found: C, 64.46; H, 5.09; S, 20.12.
(Z)-1,3-Bis(p h en ylth io)-6-h yd r oxy-2-h exen -1-on e ((Z)-
1
4g) (Ta ble 2, en tr y 2): pale yellow oil; H NMR (270 MHz,
CDCl3) δ 1.42 (br s, 1 H), 1.57 (quint, J ) 7.6, 6.1 Hz, 2 H),
2.23 (t, J ) 7.6 Hz, 2 H), 3.36 (t, J ) 6.1 H, 2 H), 6.30 (s, 1 H),
7.36-7.53 (m, 10 H) (NOE experiment: Irradiation of meth-
ylene triplet at δ 2.23 resulted in a 25% enhancement at δ
6.30 (vinyl singlet)); 13C NMR (68 MHz, CDCl3) δ 32.03, 32.76,
61.19, 117.47, 128.07, 129.00, 129.13, 129.13, 129.60, 130.13,
134.61, 135.71, 161.03, 185.06; IR (NaCl) 3398, 3057, 2943,
1667, 1548, 1477, 1440, 1111, 1078, 1023, 828, 748, 707, 690
cm-1; mass spectrum (EI), m/z 330 (M+, 2), 221 (M+ - SPh,
100). Anal. Calcd for C18H18O2S2: C, 65.42; H, 5.49; S, 19.40.
Found: C, 65.21; H, 5.51; S, 19.12. This compound was
prepared under more moderate reaction conditions (80 °C, 24
h) than those of listed in Table 2.
Ack n ow led gm en t. This research was supported in
part by a Grant-in-Aid for Scientific Research on Prior-
ity Areas “Chemistry of Inter-element Linkage” No.
09239102 from the Ministry of Education, Science and
Culture, J apan. A.O. is grateful to the Ogasawara
Foundation for the Promotion of Science & Engineering
for financial support. Thanks are due to the Instrumen-
tal Analysis Center, Faculty of Engineering, Osaka Uni-
versity, for assistance in obtaining mass spectra with a
J EOL J MS-DX303 instrument and elemental analyses.
J O970973Q