Scandium-catalyzed propargylation of 1,3-diketones with propargyl alcohols bearing sulfur or selenium functional groups: Useful transformation to furans and pyrans

Article abstract of DOI:10.1248/cpb.58.1180

Propargylations of 1,3-diketones using 3-sulfanyl and 3-selanylpropargyl alcohols 1 in MeNO₂-H₂O gave alkynyl ketones 2a-m, 2o-v and 6,7-dihydro-5H-cyclohexa[b]pyran-5-ones 3k-n. With some bases, the useful propargylated 1,3-diketone

Full text of DOI:10.1248/cpb.58.1180

1180
Regular Article
Chem. Pharm. Bull. 58(9) 1180—1186 (2010)
Vol. 58, No. 9
Scandium-Catalyzed Propargylation of 1,3-Diketones with Propargyl
Alcohols Bearing Sulfur or Selenium Functional Groups: Useful
Transformation to Furans and Pyrans
a
a
b
b
,a
*
Katsuki OHTA, Taira KOBAYASHI, Genzoh TANABE, Osamu MURAOKA, and Mitsuhiro YOSHIMATSU
a Department of Chemistry, Faculty of Education, Gifu University; 1–1 Yanagido, Gifu 501–1193, Japan: and b School of
Pharmacy, Kinki University; 3–4–1 Kowakae, Higashi-osaka, Osaka 577–8502, Japan.
Received April 20, 2010; accepted June 7, 2010; published online June 8, 2010
Propargylations of 1,3-diketones using 3-sulfanyl and 3-selanylpropargyl alcohols 1 in MeNO2–H2O gave
alkynyl ketones 2a—m, 2o—v and 6,7-dihydro-5H-cyclohexa[b]pyran-5-ones 3k—n. With some bases, the useful
propargylated 1,3-diketones underwent intramolecular cyclization to give 6,7-dihydro-5H-benzofuran-4-ones
4a—i or 4,5,6,7-tetrahydrobenzofurans 5p, 6p—v.
Key words C–C bond formation; 1,3-diketone; furan; cyclization
Alkynyl and allenyl ketones have been widely used to analogs, and the results are shown in Table 1. The reaction of
form substituted furans and pyrans by methods such as acid- 1a with 2,4-pentanedione gave the product 2b in 47% yield
mediated1—11) and metal-catalyzed12—20) cyclizations. Be- (entry 2); however, the reaction of 1a with ethyl acetoacetate
cause of the wide utility of these furans and pyrans as build- gave rise to a complex mixture (entry 3). We also explored
ing blocks for natural products and pharmaceuticals,21,22) ex- the reactions of the propargyl alcohols bearing a variety of
tending the list of ketones starting materials known to be aromatic groups at the a-position of the hydroxyl group, as
suitable for their creation is important. Useful examples of shown in entries 4 and 5. In addition, we found that the sele-
the synthesis of propargylated ketones exist,23—26) but it is nium-substituted propargyl alcohols 1e—j also gave the
questionable whether the ketones obtained are indeed practi- adducts 2e—j in high yields (entries 6—11 of Table 1).
cal for the synthesis of furans and pyrans.27—29) Recently, we However, the reactions of both 1,3-cyclohexanedione and cy-
developed a method for highly regioselective C–C bond for- clopentanedione gave 6,7-dihydro-5H-cyclohexa[b]pyran-5-
mation using propargyl alcohols with nucleophiles catalyzed one 3k, l and the cyclopentane derivative 3n, respectively, not
by scandium triflate in MeNO2.30,31) This unique reaction is the propanediones (entries 12, 13, 15 of Table 1).32,33) The re-
achieved via the two-phase condition, and is effectively stabi- action of 2-methyl-1,3-hexanedione gave propargylated 1,3-
lized by a-sulfanyl and a-selanyl functional groups. During propanedione 2m (entry 14). The modes of this cyclization
our on going study of catalytic reactions, we investigated in are reported to be fruitful because of the cycloalkanediones
the formation of C–C bonds in propargyl alcohols with 1,3- consumed.32) We also examined the reactions of the similar
diketones and their base-promoted transformations to hetero- propargyl alcohols with 1,3-cyclohexanedione, and found
cycles. In this article, we describe the formation of propargy- that most of the products were bicyclic pyrans 3k, l and 3n
lated 1,3-diketones by Lewis-acid catalytic reactions, which except for the reaction of 2,4,6-trimethylphenyl propargyl al-
easily yield furans and benzofurans under basic conditions.
cohol 1o. These results indicate that stereoelectronic effects
are very important in determining whether the reaction
would give the normal adducts or the 6,7-dihydro-5H-benzo-
Results and Discussion
First, we prepared the propargylated 1,3-diketones via our furan-4-ones, which are obtained by further proceeding to
original method that uses sulfur-substituted propargyl alco- the intramolecular cyclization. In addition, Cadierno et al. re-
hol 1a with 1,3-diphenylpropanedione under the optimized ported that the production of furans versus pyrans is due to
conditions of 5 mol% scandium triflate, 10 mol% Bu4NHSO4, the size of the cyclic 1,3-diketone.32) We further examined
MeNO2–H2O (10 : 1). The reaction was completed within the reactions with 2-acetylcyclohexanone and -cyclopen-
10 min and the product was obtained as 2-benzoyl-3-(p- tanone, and found that, as shown in entries 17—23 of Table
methoxyphenyl)-1-phenyl-5-(phenylsulfanyl)pent-4-yn-1- 1, the products are not 6,7-dihydro-5H-cyclohexa[b]pyran-5-
one (2a) in 77% yield. The structure of 2a was determined ones but the normal adducts 2p—v.
from its spectral features, which consist of the acetylenic in-
Because sulfanyl and selanylalkynyl groups are known to
frared absorption at 2189 cmϪ1 and a pair of doublets at 5.16 be good nucleophiles and electrophiles,34—45) we attempted to
and 5.86 (Jϭ10 Hz) in the 1H-NMR spectra, and a molecular reactions of propargylated 1,3-diketones with some bases
ion peak at m/z 476 (C31H24O3S) in the mass spectrum. This and found that they undergo intramolecular cyclization using
result indicates that 1,3-diketone was added to the propargyl sodium methoxide. The results are shown in Table 2. The
cation, not the allenic cation. We next investigated reactions typical example, p-methoxyphenyl 1,3-diphenylpropane-
of propargyl alcohols with other 1,3-diketones and similar dione 2a, with sodium methoxide gave furan 4a via an an-
ionic 5-exo-mode cyclization (entry 1 of Table 2).46—48) From
an analysis of its spectral features, we estimate the structure
of 4a to be 3-benzoyl-2-phenyl-5-(phenylsulfanylmethyl)furan.
3,4-Dimethoxyphenyl and benzodioxol-5-yl 2b—c gave
4b—c in high yields (entries 2, 3), and treatment of 1-(p-
∗ To whom correspondence should be addressed. e-mail: yoshimae@gifu-u.ac.jp
© 2010 Pharmaceutical Society of Japan

September 2010
1181
Table 1. Scandium-Catalyzed Propargylations of 1,3-Diketones
Table 2. Base-Promoted Cyclization of 1,3-Diketones to Furans
Products
(% yields)
Run
Alcohol 1 R1 (Y)
p-MeOC6H4 (S)
Nucleophile
1
2
3
4
5
6
7
8
9
(PhCO)2CH2
Ac2CH2
2a (77)
2b (47)
—
AcCH2CO2Et
(PhCO)2CH2
(PhCO)2CH2
(PhCO)2CH2
(PhCO)2CH2
(PhCO)2CH2
(PhCO)2CH2
(PhCO)2CH2
(PhCO)2CH2
Products
(% yields)
Run
Ketone 2 R1 (Y)
p-MeOC6H4 (S)
3,4-(MeO)2C6H3 (S)
3,4-(OCH2O)2C6H3 (S)
p-ClC6H4 (S)
p-MeOC6H4 (Se)
3,4-(OCH2O)2C6H3 (Se)
p-FC6H4 (Se)
Benzodioxol-5-yl (S)
p-ClC6H4 (S)
p-MeOC6H4 (Se)
Benzodioxol-5-yl (Se)
1-Naphthyl (Se)
p-FC6H4 (Se)
2c (quant.)
2d (71)
2e (71)
2f (80)
2g (82)
2h (83)
2i (88)
2j (88)
1
2
3
4
5
6
7
8
9
4a (90)
4b (85)
4c (93)
4d (88)
4e (93)
4f (80)
4g (99)
4h (74)
4i (quant.)
10
11
2-Thienyl (Se)
2-Furyl (Se)
2-Thienyl (Se)
2-Furyl (Se)
12
13
p-MeOC6H4 (S)
3k (73)
3l (77)
1-Naphthyl (S)
and the results are shown in Table 3. The acetyl cycloalka-
nones have two reactive sites in the molecules, one is the car-
bonyl of the acetyl group and the other is the carbonyl of cy-
cloalkanone. The reaction of 2p (Arϭp-MeOC6H4) using
sodium methoxide in THF–MeOH gave the deacetylated
product 5p in 45% yield (entry 1 in Table 3). However, using
other weak bases such as Bu4NF, CsCO3, K2CO3, and NaH
provides 9-acetyl-3-(p-methoxyphenyl)-2-(phenyl-sulfanyl-
methyl)-4,5,6,7-tetrahydrobenzofuran (6p) in high yield, ac-
companied by furan 6p (entries 2, 3). The reactions of the
other acetyl cyclohexanones also provide the bicyclic com-
pounds 6r, s which easily converted to the corresponding
4,5,6,7-tetrahydrobenzofuran 7r (Chart 1). Cyclopentanone
derivatives 2q and 2v also provided the oxabicyclo-
[3,3,0]octa-3,8-dienes in good yields. In summary, we have
described a simple and convenient propargylation of 1,3-
ketones from sulfur- and selenium-substituted propargyl al-
cohols with 1,3-diketones. The successive base-promoted
intramolecular cyclization of the propargylated ketones gave
a wide variety of furans and tetrahydrobenzofurans in high
yields.
14
15
p-MeOC6H4 (S)
p-MeOC6H4 (S)
2m (73)
3n (59)
16
2,4,6-Me3C6H2 (S)
2o (99)
17
18
p-MeOC6H4 (S)
p-MeOC6H4 (S)
2p (95)a)
2q (75)b)
19
20
21
2-Thienyl (S)
2r (99)c)
2s (75)d)
2t (72)
Benzodioxol-5-yl (S)
Benzodioxol-5-yl (Se)
Experimental
Melting points were determined by a Yanagimoto micro-melting point ap-
paratus and uncorrected. Elemental analyses were determined by using
Micro Corder (MT-6) of J Science Lab. at the Life Science Research Center,
Gifu University. 1H- and 13C-NMR spectra were determined on JEOL ECA-
600 (600 MHz), ECA-500 (500 MHz) and ECA-400 (400 MHz) spectrome-
ter. IR spectra were recorded with a JASCO FT-IR 460PLUS infrared spec-
trometer and are expressed in reciprocal centimeters. Electron ionization
(EI) mass spectra (MS) were obtained using a JEOL MS-700 spectrometer
with a direct-insertion probe at 70 eV. All high-resolution mass spectra were
obtained using a JMSD300 JMA2000 on-line system.
22
23
2-Thienyl (Se)
2-Thienyl (Se)
2u (64)
2v (70)
Preparation of 1,3-Diphenyl-2-[1-(4-methoxyphenyl)-3-(phenylsulfa-
nyl)prop-2-ynyl]propanedione (2a) To a solution of MeNO2 (0.80 ml)
and H2O (0.08 ml) of 1-(p-methoxyphenyl)-3-(phenylsulfanyl)propargyl
alcohol (1a) (50.0 mg, 0.18 mmol) was added 1,3-diphenylpropane-
dione (83 mg, 0.57 mmol), tetrabutylammonium hydrogensulfate (6.3 mg,
0.02 mmol), and scandium triflate (44 mg, 9.0 mmol). The reaction mixture
was heated under reflux condition. The cooled mixture (50 ml) was poured
into a saturated NaHCO3 (50 ml). The organic layer was separated and the
aqueous layer was extracted with ether. The combined organic layer was
dried over MgSO4. The solvent was removed under reduced pressure. The
residue was purified by preparative TLC on silica gel eluting with AcOEt–n-
hexane (1 : 5) to give 1,3-diphenyl-2-[1-(4-methoxyphenyl)-3-(phenylsulfa-
nyl)prop-2-ynyl]propanedione (2a) (68 mg, 77%) as a yellow oil.
a—d) The diastereoisomer ratio is 46 : 54 (2p)/53 : 47 (2q)/57 : 43 (2r)/54 : 46
(2s)/55 : 45 (2t)/62 : 38 (2u)/54 : 46 (2v).
chlorophenyl)propargyl alcohols 2d with sodium methoxide
quantitatively transforms to the substituted furan 4d. The re-
actions of the similar selenium-substituted alcohols 2e—i
also gave the phenylselanylmethylfurans 4e—i (entries 5—9
of Table 2).
2a: IR (KBr, cmϪ1) n: 1695, 1662, 1609, 1595, 1581, 1510, 1478, 1446,
We further investigated the intramolecular cyclizations of
the propargylated cycloalkanones 2 in some basic conditions 1323, 1303, 1256, 1178, 1111, 1031, 985, 835, 764, 740, 687; 1H-NMR

1182
Vol. 58, No. 9
Table 3. Preparation of 4,5,6,7-Tetrahydrobenzofurans
Products
Run
Ketones 1 Ar
Condition
5 (% yield)
6 (% yield)
1
2
3
4
5
6
7
p-MeOC6H4, nϭ2
NaOMe (5 eq), dioxane, reflux
Bu4NF (3 eq), DMF, reflux
DBU, dioxane, reflux
DBU, dioxane, reflux
DBU, dioxane, reflux
DBU, dioxane, reflux
DBU, dioxane, reflux
5p (45)
5p (10)
6p (87)
6p (71)
6s (quant.)
6r (70)
6q (76)
6v (74)
Benzodioxol-5-yl, nϭ2
2-Thienyl, nϭ2
p-MeOC6H4, nϭ1
2-Thienyl, nϭ1
Reagents: i) DBU/dioxane/reflux/10 min; ii) TsOH–H2O/dioxane/reflux/10 min.
(1H, m, ArH), 7.52—7.55 (1H, m, ArH), 7.74 (2H, d, Jϭ8 Hz, ArH), 8.02
(2H, d, Jϭ8 Hz, ArH); 13C-NMR (150 MHz, CDCl3) d: 39.2 (d), 63.2 (d),
71.2 (s), 97.7 (s), 126.1 (dϫ2), 126.3 (d), 128.5 (dϫ2), 128.7 (dϫ2), 128.8
(dϫ2), 128.8 (dϫ2), 128.9 (dϫ2), 129.0 (dϫ2), 129.9 (dϫ2), 132.4 (s),
133.4 (s), 133.7 (d), 133.7 (d), 136.1 (s), 136.4 (s), 136.9 (s), 192.3 (s),
192.8 (s); MS m/z: 480 (Mϩ), 375 (MϩϪCOPh), 371 (MϩϪSPh). Anal.
Calcd for C30H21O2ClS: C, 74.91; H, 4.40. Found: C, 75.16; H, 4.61.
1,3-Diphenyl-2-[4-(methoxyphenyl)-3-(phenylselanyl)prop-2-
ynyl]propanedione (2e): mp 92—94 °C, IR (KBr, cmϪ1) n: 3903, 3854,
3735, 3648, 3566, 2925, 2361, 1698, 1671, 1577, 1558, 1541, 1509, 1475,
1456, 1361, 1254, 1176, 1033, 835, 764, 738, 688; 1H-NMR (600 MHz,
CDCl3) d: 3.70 (3H, s, Me), 5.15 (1H, d, Jϭ10 Hz, CH), 5.84 (1H, d,
Jϭ10 Hz, CH), 6.75 (2H, d, Jϭ7 Hz, ArH), 7.14—7.15 (3H, m, ArH),
7.25—7.30 (4H, m, ArH), 7.37—7.44 (5H, m, ArH), 7.51—7.53 (1H, m,
ArH), 7.73 (2H, d, Jϭ8 Hz, ArH), 8.01 (2H, d, Jϭ7 Hz ArH); 13C-NMR
(150 MHz, CDCl3) d: 39.3 (d), 55.2 (q), 63.6 (d), 63.7 (s), 103.5 (s), 114.0
(dϫ2), 126.7 (d), 128.5 (dϫ2), 128.6 (dϫ2), 128.7 (s), 128.8 (dϫ4), 129.0
(dϫ2), 129.3 (dϫ2), 129.6 (dϫ2), 130.4 (s), 133.4 (d), 133.5 (d), 136.4 (s),
136.7 (s), 158.9 (s), 192.7 (s), 193.1 (s); MS m/z: 524 (Mϩ), 419
(MϩϪCOPh). High-resolution mass Calcd for C31H24O3Se: 524.0890, Found
m/z: 536.0870.
Reagents: i, DBU/dioxane/reflux/10 min, ii, TsOH-H2O/dioxane/reflux/10 min
Chart 1. Conversion to Tetrahydrobenzofuran 7r
(600 MHz, CDCl3) d: 3.69 (3H, s, OMe), 5.16 (1H, d, Jϭ10 Hz, CH), 5.86
(1H, d, Jϭ10 Hz, CH), 6.75 (2H, d, Jϭ9 Hz, ArH), 7.09—7.13 (1H, m,
ArH), 7.15 (5H, br s, ArH), 7.26—7.29 (2H, m, ArH), 7.37—7.44 (4H, m,
ArH), 7.49—7.52 (1H, m, ArH), 7.73 (2H, d, Jϭ9 Hz, ArH), 8.02 (2H, d,
Jϭ9 Hz, ArH); 13C-NMR (150 MHz, CDCl3) d: 39.1 (d), 55.2 (q), 63.6 (d),
70.3 (s), 98.7 (s), 114.0 (dϫ2), 125.9 (dϫ2), 126.1 (d), 128.5 (dϫ2), 128.6
(dϫ2), 128.8 (dϫ2), 128.9 (dϫ2), 129.0 (dϫ2), 129.5 (dϫ2), 130.2 (s),
132.7 (s), 133.7 (d), 136.3 (s), 136.6 (s), 158.9 (s), 192.7 (s), 193.1 (s); MS
m/z: 476 (Mϩ), 371 (MϩϪCOPh). Anal. Calcd for C31H24O3S: C, 77.16; H,
5.15. Found: C, 77.34; H, 5.19.
1,3-Diphenyl-2-[1-(benzodioxol-5-yl)-3-(phenylselanyl)prop-2-
ynyl]propanedione (2f): IR (KBr, cmϪ1) n: 3058, 2891, 1697, 1666, 1595,
1578, 1503, 1485, 1446, 1321, 1246, 1234, 1196, 1181, 1102, 1038, 999,
933, 809, 794, 761, 736, 687, 633; 1H-NMR (600 MHz, CDCl3) d: 5.12 (1H,
dd, Jϭ3, 9 Hz, CH), 5.85 (2H, d, Jϭ9 Hz, CH2), 6.63 (1H, d, Jϭ8 Hz, CH),
6.91 (1H, d, Jϭ8 Hz, ArH), 6.99 (1H, s, ArH), 7.13—7.14 (3H, m, ArH),
7.24—7.30 (5H, m, ArH), 7.38—7.44 (3H, m, ArH), 7.50—7.52 (1H, m,
ArH), 7.76 (2H, d, Jϭ8 Hz, ArH), 8.01 (2H, d, Jϭ8 Hz, ArH); 13C-NMR
(150 MHz, CDCl3) d: 39.7 (d), 63.4 (d), 63.9 (s), 101.0 (t), 103.1 (s), 108.2
(d), 108.8 (d), 122.0 (d), 126.7 (d), 128.5 (dϫ2), 128.6 (dϫ2), 128.7 (dϫ3),
128.9 (dϫ2), 129.2 (dϫ2), 132.0 (s), 133.4 (d), 133.5 (d), 136.3 (s), 136.6
(s), 146.8 (s), 147.6 (s), 171.0 (s), 192.5 (s), 193.0 (s); MS m/z: 538 (Mϩ),
433 (MϩϪCOPh), 381 (MϩϪSePh). High-resolution mass Calcd for
C31H22O4Se: 538.0683, Found m/z: 538.0642.
2-[1-(4-Methoxyphenyl)-3-(phenylsulfanyl)prop-2-ynyl]-2,4-pentane-
dione (2b): A yellow oil, IR (KBr, cmϪ1) n: 1732, 1702, 1609, 1583, 1511,
1478, 1442, 1357, 1304, 1178, 1152, 1033, 835, 741, 689; 1H-NMR
(600 MHz, CDCl3) d: 1.93 (3H, s, Me), 2.32 (3H, s, Me), 3.79 (3H, s, OMe),
4.20 (1H, d, Jϭ11 Hz, CH), 4.64 (1H, d, Jϭ11 Hz, CH), 6.86 (2H, d,
Jϭ8 Hz, ArH), 7.21 (2H, d, Jϭ8 Hz, ArH), 7.26—7.36 (6H, m, ArH); 13C-
NMR (150 MHz, CDCl3) d: 29.0 (q), 31.0 (q), 38.2 (d), 55.3 (q), 70.6 (s),
75.4 (d), 97.5 (s), 114.3 (dϫ2), 126.2 (dϫ2), 126.5 (d), 129.2 (dϫ2), 129.2
(dϫ2), 129.5 (s), 132.6 (s), 159.1 (s), 201.4 (s); MS m/z: 352 (Mϩ), 309
(MϩϪCOMe); high resolution mass Calcd for C21H20O3S: 352.1128, Found
m/z 352.1149.
1,3-Diphenyl-2-[1-(benzodioxol-5-yl)-3-(phenylsulfanyl)prop-2-
ynyl]propanedione (2c): IR (KBr, cmϪ1) n: 3060, 2921, 1698, 1667, 1594,
1580, 1504, 1486, 1446, 1321, 1246, 1235, 1196, 1038, 932, 794, 741, 687;
1H-NMR (600 MHz, CDCl3) d: 5.12 (1H, d, Jϭ9 Hz, CH), 5.84 (2H, s,
CH2), 6.64 (1H, d, Jϭ9 Hz, CH), 6.91 (1H, dd, Jϭ9, 2 Hz, ArH), 6.99 (1H,
d, Jϭ2 Hz, ArH), 7.16—7.19 (5H, m, ArH), 7.24—7.32 (2H, m, ArH),
7.39—7.41 (2H, m, ArH), 7.43—7.46 (1H, m, ArH), 7.51—7.53 (1H, m,
ArH), 7.76 (2H, dd, Jϭ9, 1 Hz, ArH), 8.01 (2H, dd, Jϭ8, 1 Hz, ArH); 13C-
NMR (150 MHz, CDCl3) d: 39.5 (d), 63.4 (d), 70.7 (s), 98.3 (s), 101.0 (t),
108.2 (d), 108.9 (d), 122.0 (d), 126.0 (dϫ2), 126.2 (d), 128.5 (dϫ2), 128.6
(dϫ2), 128.8 (dϫ2), 128.9 (dϫ2), 129.0 (dϫ2), 131.9 (s), 132.6 (s), 133.5
(d), 133.6 (d), 136.3 (s), 136.5 (s), 146.9 (s), 147.7 (s), 192.5 (s), 193.0 (s);
MS m/z: 490 (Mϩ), 385 (MϩϪCOPh), 381 (MϩϪSPh). Anal. Calcd for
C31H22O4S: C, 75.96; H, 4.52. Found: C, 75.84; H, 4.59.
1,3-Diphenyl-2-[1-(1-naphthyl)-3-(phenylselanyl)prop-2-ynyl]propane-
dione (2g): A yellow oil, IR (KBr, cmϪ1) n: 3057, 2924, 1696, 1666, 1595,
1578, 1511, 1477, 1447, 1391, 1320, 1274, 1274, 1180, 1071, 999, 779,
1
734, 686; H-NMR (600 MHz, CDCl3) d: 5.89 (1H, d, Jϭ9 Hz, CHCOPh),
6.23 (1H, d, Jϭ9 Hz, CH), 7.11—7.15 (5H, m, ArH), 7.16—7.29 (4H, m,
ArH), 7.32—7.35 (1H, m, ArH), 7.37—7.40 (2H, m, ArH), 7.45—7.48 (1H,
m, ArH), 7.51—7.53 (1H, m, ArH), 7.55—7.58 (1H, m, ArH), 7.60 (2H, d,
Jϭ8 Hz, ArH), 7.64 (1H, d, Jϭ8 Hz, ArH), 7.77 (1H, d, Jϭ8 Hz, ArH), 7.97
(2H, d, Jϭ8 Hz, ArH), 8.45 (1H, d, Jϭ8 Hz, ArH); 13C-NMR (150 MHz,
CDCl3) d: 36.8 (d), 61.3 (d), 64.4 (s), 103.1 (s), 123.7 (d), 125.1 (d), 125.7
(d), 126.4 (d), 126.6 (d), 126.8 (d), 128.2 (dϫ2), 128.3 (dϫ2), 128.4 (dϫ2),
128.6 (d), 128.7 (dϫ3), 128.9 (dϫ2), 128.9 (dϫ2), 129.2 (dϫ2), 130.7 (s),
133.2 (s), 133.5 (s), 134.0 (s), 136.0 (s), 136.7 (s), 192.8 (s), 193.5 (s); MS
m/z: 544 (Mϩ), 387 (MϩϪSePh). Anal. Calcd for C34H24O2Se: C, 75.13; H,
4.45. Found: C, 74.86; H, 4.49.
1,3-Diphenyl-2-[1-(4-chlorophenyl)-3-(phenylsulfanyl)prop-2-
ynyl]propanedione (2d): mp 90—92 °C, IR (KBr, cmϪ1) n: 3061, 2361,
1695, 1667, 1595, 1580, 1541, 1489, 1447, 1407, 1321, 1267, 1198, 1179,
1091, 1016, 989, 835, 809, 762, 739, 710, 686; 1H-NMR (600 MHz, CDCl3)
d: 5.18 (1H, d, Jϭ10 Hz, CH), 5.84 (1H, d, Jϭ10 Hz, CH), 7.12—7.24 (6H,
m, ArH), 7.29—7.31 (2H, m, ArH), 7.40—7.43 (5H, m, ArH), 7.44—7.47
1,3-Diphenyl-2-[1-(4-fluorofhenyl)-3-(phenylselanyl)prop-2-
ynyl]propanedione (2h): mp 85 °C, IR (KBr, cmϪ1) n: 3060, 2362, 1697,

September 2010
1183
1666, 1595, 1578, 1508, 1477, 1197, 1179, 1159, 1099, 1067, 1021, 985, (dϫ2), 130.3 (dϫ2), 133.0 (s), 159.2 (s), 208.9 (s), 209.3 (s); MS m/z: 378
838, 763, 736, 687; H-NMR (600 MHz, CDCl3) d: 5.18 (1H, d, Jϭ10 Hz,
CH), 5.84 (1H, dd, Jϭ10, 5 Hz, CH), 6.88—6.91 (2H, m, ArH), 7.13—7.16 Found: C, 71.96; H, 6.55.
(Mϩ), 269 (MϩϪSPh). Anal. Calcd for C23H22O3S: C, 72.41; H, 6.61.
1
(3H, m, ArH), 7.24—7.30 (4H, m, ArH), 7.39—7.45 (5H, m, ArH), 7.51—
2-[1-(4-Methoxyphenyl)-3-(phenylsulfanyl)prop-2-yn-1-yl]-1,3-cyclopen-
7.54 (1H, m, ArH), 7.72 (2H, d, Jϭ1 Hz, ArH), 8.01 (2H, d, Jϭ7 Hz, ArH); tanedione (3n): mp 149 °C, IR (KBr, cmϪ1) n: 3058, 2928, 2835, 2357,
13C-NMR (150 MHz, CDCl3) d: 39.3 (d), 63.4 (d), 64.3 (s), 102.9 (s), 115.4 1703, 1664, 1610, 1583, 1509, 1479, 1462, 1440, 1377, 1328, 1302, 1251,
(d), 115.5 (d), 126.8 (d), 128.5 (dϫ2), 128.7 (dϫ2), 128.8 (dϫ2), 128.9 1176, 1121, 1082, 1033, 997, 878, 862, 829, 743, 690, 613; 1H-NMR
(dϫ2), 129.0 (dϫ2), 129.3 (dϫ2), 130.2 (d), 130.3 (d), 133.6 (dϫ2), 134.2 (600 MHz, CDCl3) d: 2.35—2.44 (2H, m, CH2), 2.55—2.66 (2H, m, CH2),
(s), 136.2 (s), 136.6 (s), 162.0 (d, Jϭ248 Hz), 192.5 (s), 192.9 (s); MS m/z: 3.77 (3H, s, OMe), 4.35 (1H, d, Jϭ4 Hz, CH), 5.69 (1H, d, Jϭ4 Hz, CH),
512 (Mϩ), 407 (MϩϪCOPh), 355 (MϩϪSePh). Anal. Calcd for 6.85 (2H, d, Jϭ9 Hz, ArH), 7.17 (2H, d, Jϭ9 Hz, ArH), 7.25—7.27 (1H, m,
C30H21O2FSe: C, 70.45; H, 4.14. Found: C, 70.66; H, 4.32.
ArH), 7.28—7.35 (2H, m, ArH), 7.41—7.43 (2H, m, ArH); 13C-NMR
1,3-Diphenyl-2-[1-(2-thienyl)-3-(phenylselanyl)prop-2-ynyl]propanedione (150 MHz, CDCl3) d: 25.3 (t), 33.4 (t), 36.1 (d), 55.2 (q), 114.0 (dϫ2),
(2i): A yellow oil, IR (KBr, cmϪ1) n: 3060, 2359, 1697, 1668, 1595, 1577, 116.1 (d), 116.8 (s), 127.5 (d), 1289.0 (dϫ2), 129.2 (dϫ2), 129.7 (dϫ2),
1476, 1447, 1321, 1261, 1181, 1020, 983, 762, 735, 687; 1H-NMR
(600 MHz, CDCl3) d: 5.54 (1H, d, Jϭ10 Hz, CH), 5.90 (1H, dd, Jϭ1, 9 Hz,
132.3 (s), 134.4 (s), 144.4 (s), 158.6 (s), 178.8 (s), 202.5 (s); MS m/z: 350
(Mϩ), 241 (MϩϪSPh). High-resolution mass Calcd for C21H18O3S:
CH), 6.79 (1H, t, Jϭ4 Hz, ArH), 6.99 (1H, d, Jϭ3 Hz, ArH), 7.10 (1H, d, 350.0977, Found m/z 350.0982.
Jϭ5 Hz, ArH), 7.16 (3H, m, ArH), 7.27—7.33 (3H, m, ArH), 7.37—7.40
2-[1-(2,4,6-Trimethylphenyl)-3-(phenylsulfanyl)prop-2-yn-1-yl]-1,3-cy-
(3H, m, ArH), 7.44—7.47 (1H, m, ArH), 7.50—7.53 (1H, m, ArH), 7.80 clohexanedione (2o): IR (KBr, cmϪ1) n: 2950, 2923, 2357, 1726, 1662,
(2H, d, Jϭ5 Hz, ArH), 8.00 (2H, dd, Jϭ7, 1 Hz, ArH); 13C-NMR (150 MHz,
1636, 1583, 1479, 1455, 1439, 1384, 1219, 1199, 1177, 1156, 1137, 1116,
CDCl3) d: 35.2 (d), 63.6 (d), 64.6 (s), 102.1 (s), 124.9 (d), 126.7 (d), 126.9 1085, 1053, 1024, 991, 907, 879, 852, 818, 741, 690, 621, 560; 1H-NMR
(d), 128.3 (s), 128.5 (dϫ2), 128.7 (dϫ2), 128.8 (dϫ2), 128.9 (dϫ2), 129.0 (600 MHz, CDCl3) d: 2.08 (3H, s, Me), 2.09—2.15 (2H, m, CH2), 2.22 (3H,
(dϫ4), 129.3 (dϫ2), 133.6 (d), 136.2 (s), 136.5 (s), 141.3 (s), 192.4 (s),
192.5 (s); MS m/z: 339 (MϩϪSePh). Anal. Calcd for C28H20O2SSe: C,
67.20; H, 4.23. Found: C, 67.13; H, 4.22.
s, Me), 2.32—2.35 (2H, m, CH2), 2.50 (3H, s, Me), 2.63—2.68 (2H, m,
CH2), 5.24 (1H, d, Jϭ3 Hz, CH), 5.41 (1H, d, Jϭ2 Hz, CH), 6.76 (1H, s,
ArH), 6.86 (1H, s, ArH), 7.13—7.16 (1H, s, ArH), 7.23 (4H, d, Jϭ4 Hz,
1,3-Diphenyl-2-[1-(2-furyl)-3-(phenylselanyl)prop-2-ynyl]propanedione ArH); 13C-NMR (150 MHz, CDCl3) d: 19.1 (q), 20.8 (d), 21.4 (qϫ2), 21.6
(2j): IR (KBr, cmϪ1) n: 3059, 2923, 2361, 1698, 1670, 1595, 1578, 1502, (t), 23.3 (t), 36.9 (t), 44.0 (d), 95.1 (d), 126.2 (d), 128.3 (dϫ2), 128.9 (dϫ2),
1477, 1447, 1322, 1261, 1196, 1180, 1147, 1067, 1011, 918, 885, 789, 763, 129.2 (d), 130.9 (d), 132.2 (s), 135.9 (s), 136.5 (s), 136.6 (s), 137.1 (s),
736, 687; H-NMR (600 MHz, CDCl3) d: 5.31 (1H, d, Jϭ10 Hz, CH), 6.04 159.9 (s), 173.3 (s), 193.3 (s); MS m/z: 376 (Mϩ), 267 (MϩϪSPh). Anal.
(1H, d, Jϭ10 Hz, CH), 6.17 (1H, dd, Jϭ1, 3 Hz, ArH), 6.22 (1H, d, Jϭ3 Hz, Calcd for C24H24O2S: C, 76.56; H, 6.42. Found: C, 76.37; H, 6.56.
1
ArH), 7.16—7.17 (5H, m, ArH), 7.18—7.29 (1H, m, ArH), 7.29—7.30 (1H,
2-Acetyl-2-[1-(p-methoxyphenyl)-3-(phenylsulfanyl)-2-propyn-1-yl]cy-
m, ArH), 7.35—7.37 (2H, m, ArH), 7.38—7.40 (2H, m, ArH), 7.48—7.53 clohexanone (2p): Yellow powders, mp 120—124 °C, IR (KBr, cmϪ1) n:
(1H, m, ArH), 7.85 (2H, d, Jϭ7 Hz, ArH), 7.98 (2H, d, Jϭ7 Hz, ArH); 13C- 3224, 2939, 1720, 1699, 1551, 1478, 1441, 1254, 1178, 1033, 836, 741,
1
NMR (150 MHz, CDCl3) d: 33.8 (d), 59.9 (d), 63.9 (s), 100.1 (s), 108.2 (d),
689; H-NMR (600 MHz, CDCl3) d: 1.52—1.62 (2H, m, CH2), 1.93 (3H, s,
110.6 (d), 126.8 (d), 128.5 (s), 128.6 (dϫ2), 128.7 (dϫ2), 128.8 (dϫ2), COMe), 1.94—1.98 (4H, m, CH2), 2.13—2.18 (2H, m, CH2), 2.52—2.57
128.9 (dϫ2), 129.0 (dϫ2), 129.3 (dϫ2), 133.5 (d), 133.6 (d), 135.9 (s), (2H, m, CH2), 3.77 (3H, s, OMe), 4.92 (1H, s, CH), 6.81 (2H, d, Jϭ8 Hz,
136.4 (s), 142.1 (d), 150.1 (s), 192.4 (s), 192.6 (s); MS m/z: 407 (MϩϪPh),
ArH), 7.18—7.26 (1H, m, ArH), 7.30—7.33 (2H, m, ArH), 7.38 (2H, d,
479 (MϩϪCOPh). Anal. Calcd for C28H20O3Se: C, 69.57; H, 4.17. Found: C, Jϭ8 Hz, ArH); 13C-NMR (150 MHz, CDCl3) d: 22.4 (t), 25.9 (t), 27.3 (q),
66.15; H, 4.19.
29.9 (t), 42.0 (t), 42.5 (t), 55.2 (q), 697.0 (s), 72.0 (s), 98.5 (s), 113.3 (dϫ2),
2-[1-(4-Methoxyphenyl)-3-(phenylsulfanyl)prop-2-yn-1-yl]-1,3-cyclo- 126.0 (dϫ2), 126.2 (d), 127.6 (s), 129.1 (dϫ2), 130.1 (dϫ2), 133.3 (s),
hexanedione (3k): mp 162 °C, IR (KBr, cmϪ1) n: 3059, 2996, 295, 2834,
1657, 1615, 1582, 1509, 1478, 1459, 1440, 1375, 1329, 1301, 1253, 1181,
1126, 1070, 1040, 999, 970, 916, 883, 863, 830, 744, 690, 629, 610; 1H-
159.2 (s), 204.4 (s), 206.8 (s); MS m/z: 392 (Mϩ), 349 (MϩϪCOMe). Anal.
Calcd for C24H24O3S: C, 73.44; H, 6.16. Found: C, 73.44; H, 6.23.
Yellow powders, mp 87—91 °C, IR (KBr, cmϪ1) n: 2947, 1698, 1608,
1
NMR (600 MHz, CDCl3) d: 1.88—2.07 (2H, m, CH2), 2.28—2.53 (4H, m, 1582, 1510, 1441, 1305, 1255, 1178, 1125, 1033, 836, 741, 539; H-NMR
CH2), 3.77 (3H, s, OMe), 4.41 (1H, d, Jϭ5 Hz, CH), 5.72 (1H, d, Jϭ5 Hz, (600 MHz, CDCl3) d: 1.34—1.47 (2H, m, CH2), 1.67—1.85 (2H, m, CH2),
CH), 6.81—6.84 (2H, m, ArH), 7.18—7.20 (2H, m, ArH), 7.24—7.25 (1H, 2.04—2.14 (2H, m, CH), 2.24 (3H, s, COMe), 2.41—2.43 (1H, m, CH),
m, ArH), 7.27—7.33 (2H, m, ArH), 7.39 (2H, d, Jϭ7 Hz, ArH); 13C-NMR
(150 MHz, CDCl3) d: 20.6 (t), 27.4 (t), 35.9 (d), 37.0 (t), 55.2 (q), 113.6 (s),
2.47—2.50 (1H, m, CH), 3.79 (3H, s, OMe), 5.14 (1H, s, CH), 6.82 (2H, d,
Jϭ8 Hz, ArH), 7.19—7.22 (1H, m, ArH), 7.31—7.38 (6H, m, ArH); 13C-
113.9 (dϫ2), 116.9 (d), 127.3 (d), 129.0 (dϫ2), 129.1 (dϫ2), 129.6 (dϫ2), NMR (150 MHz, CDCl3) d: 22.0 (t), 25.4 (t), 26.7 (q), 29.3 (t), 41.2 (d),
132.8 (s), 136.5 (s), 142.3 (s), 158.4 (s), 166.8 (s), 197.2 (s); MS m/z: 364 42.2 (t), 55.2 (q), 70.9 (s), 72.8 (s), 97.3 (s), 113.4 (dϫ2), 126.3 (dϫ2),
(Mϩ), 257 (MϩϪC6H4Me). Anal. Calcd for C22H20O3S: C, 72.50; H, 5.53. 126.4 (d), 128.4 (s), 129.2 (dϫ2), 131.4 (dϫ2), 132.9 (s), 158.9 (s), 202.7
Found: C, 72.72; H, 5.58.
(s), 207.4 (s), MS m/z: 392 (Mϩ). Anal. Calcd C24H24O3S: C, 73.44; H, 6.16.
Found: C, 73.59; H, 6.18.
2-[1-(1-Naphthyl)-3-(phenylsulfanyl)prop-2-yn-1-yl]-1,3-cyclohexane-
dione (3l): IR (KBr, cmϪ1) n: 3057, 2925, 1658, 1616, 1582, 1509, 1479,
2-Acetyl-2-[1-(p-methoxyphenyl)-3-(phenylsulfanyl)-2-propyn-1-yl]cy-
1439, 1382, 1333, 1273, 1243, 1188, 1167, 1130, 1070, 1043, 1024, 970, clopentanone (2q): A yellow oil, IR (KBr, cmϪ1) n: 2959, 1739, 1705, 1609,
917, 888, 852, 798, 778, 742, 689, 657, 630; 1H-NMR (600 MHz, CDCl3) d: 1582, 1512, 1478, 1442, 1357, 1304, 1255, 1179, 1137, 1033, 843, 741,
1
2.03—2.06 (2H, m, CH2), 2.31—2.41 (2H, m, CH2), 2.48—2.53 (1H, m, 689, 555; H-NMR (600 MHz, CDCl3) d: 1.67—1.69 (1H, m, CH), 1.72—
CH2), 2.59—2.64 (1H, m, CH2), 5.29 (1H, d, Jϭ4 Hz, CH), 5.90 (1H, d, 2.02 (1H, m, CH), 2.17 (3H, COMe), 2.17—2.25 (1H, m, CH), 2.32—2.42
Jϭ4 Hz, CH), 7.21—7.34 (6H, m, ArH), 7.39—7.42 (1H, m, ArH), 7.46— (2H, m, CH2), 2.53—2.68 (1H, m, CH), 3.78 (3H, s, OMe), 4.90 (1H, s,
7.49 (1H, m, ArH), 7.54—7.56 (1H, m, ArH), 7.71 (1H, d, Jϭ8 Hz, ArH), CH), 6.82 (2H, d, Jϭ8 Hz, ArH), 7.18—7.22 (3H, m, ArH), 7.30—7.35 (4H,
7.85 (1H, d, Jϭ8 Hz, ArH), 8.29 (1H, d, Jϭ8 Hz, ArH); 13C-NMR
(150 MHz, CDCl3) d: 20.4 (t), 27.5 (t), 32.3 (d), 36.9 (t), 112.7 (s), 117.1
m, ArH); 13C-NMR (150 MHz, CDCl3) d: 19.7 (t), 26.6 (q), 28.2 (t), 38.9
(t), 43.2 (d), 55.2 (q), 70.9 (s), 73.9 (s), 97.3 (s), 114.1 (dϫ2), 126.1 (dϫ2),
(d), 123.0 (d), 125.2 (d), 125.6 (dϫ2), 126.3 (d), 127.1 (d), 127.4 (d), 128.8 126.5 (d), 128.3 (s), 129.2 (dϫ2), 129.3 (dϫ2), 132.8 (s), 159.2 (s), 201.1
(d), 129.1 (dϫ2), 129.2 (dϫ2), 130.6 (s), 132.9 (s), 133.9 (s), 140.2 (s),
(s), 213.7 (s); MS m/z: 378 (Mϩ), 360 (MϩϪH2O), 335 (MϩϪCOMe). High
141.9 (s), 168.0 (s), 196.9 (s); MS m/z: 384 (Mϩ). Anal. Calcd for resolution mass Calcd for C23H22O3S: 378.1289, Found m/z: 378.1301.
C25H20O2S: C, 78.11; H, 5.24. Found: C, 78.06; H, 5.24.
Yellow powders, mp 63—64 °C, IR (KBr, cmϪ1) n: 2960, 1738, 1705,
2-[1-(4-Methoxyphenyl)-3-(phenylsulfanyl)prop-2-yn-1-yl]-2-methyl-1,3- 1609, 1582, 1510, 1478, 1442, 1356, 1305, 1247, 1180, 1139, 1033, 969,
cyclohexanedione (2m): A yellow oil, IR (KBr, cmϪ1) n: 2925, 1697, 1609, 839, 741, 689; 1H-NMR (600 MHz, CDCl3) d: 1.30—1.37 (1H, m, CH),
1541, 1509, 1457, 1304, 1252, 1178, 1026, 837, 742, 690; 1H-NMR 1.63—1.71 (2H, m, CH2), 1.87—1.92 (1H, m, CH), 2.11—2.17 (1H, m,
(600 MHz, CDCl3) d: 1.32 (3H, s, Me), 1.48—1.76 (3H, m, CH2), 2.41— CH), 2.47 (3H, s, Me), 2.78—2.82 (1H, m, CH), 3.79 (3H, s, OMe), 5.01
2.62 (3H, m, CH2), 3.78 (3H, s, Me), 4.50 (1H, s, CH), 6.80—6.82 (2H, d, (1H, s, CH), 6.84 (2H, d, Jϭ9 Hz, ArH), 7.21—7.25 (1H, m, ArH), 7.27
Jϭ9 Hz, ArH), 7.15 (2H, d, Jϭ9 Hz, ArH), 7.20—7.25 (1H, m, ArH),
7.33—7.35 (2H, m, ArH), 7.46—7.48 (2H, m, ArH); 13C-NMR (150 MHz,
CDCl3) d: 16.8 (t), 19.6 (d), 39.3 (t), 39.5 (t), 45.0 (d), 55.2 (q), 67.9 (s),
(2H, d, Jϭ9 Hz, ArH), 7.32—7.36 (4H, m, ArH); 13C-NMR (150 MHz,
CDCl3) d: 19.2 (t), 25.8 (t), 25.9 (q), 39.5 (t), 42.6 (d), 55.2 (q), 71.3 (s),
74.2 (s), 96.5 (s), 113.8 (dϫ2), 126.3 (dϫ2), 126.6 (d), 127.7 (s), 129.2
71.3 (s), 96.8 (s), 113.7 (dϫ2), 126.3 (dϫ2), 126.4 (d), 128.2 (s), 129.2 (dϫ2), 130.5 (dϫ2), 132.6 (s), 159.2 (s), 201.1 (s), 213.6 (s); MS m/z: 378

1184
Vol. 58, No. 9
(Mϩ), 360 (MϩϪH2O), 335 (MϩϪCOMe). Anal. Calcd for C23H22O3S: C,
72.99; H, 5.86. Found: C, 72.98; H, 5.92.
42.1 (t), 64.3 (s), 72.9 (s), 101.1 (t), 107.7 (d), 110.8 (d), 123.8 (d), 127.1
(d), 128.6 (s), 129.2 (dϫ2), 129.5 (dϫ2), 130.2 (s), 146.9 (s), 147.3 (s),
202.5 (s), 207.3 (s); MS m/z: 436 (MϩϪH2O), 411 (MϩϪCOMe).
2-Acetyl-2-[1-(2-thienyl)-3-(phenylsulfanyl)-2-propyn-1-yl]cyclohexan-
one (2r): Yellow prisms, mp 110—112 °C, IR (KBr, cmϪ1) n: 2941, 2865,
1699, 1582, 1478, 1440, 1353, 1261, 1177, 1124, 1086, 1024, 742, 690; 1H-
NMR (600 MHz, CDCl3) d: 1.58—1.64 (2H, m, CH2), 1.87—1.94 (1H, m,
CH), 1.96—1.99 (1H, m, CH), 2.05 (3H, s, COMe), 2.08—2.13 (1H, m,
CH), 2.20—2.26 (1H, m, CH), 2.55—2.58 (1H, m, CH), 2.70—2.73 (1H, m,
CH), 5.28 (1H, s, CH), 6.89—6.91 (2H, m, ArH), 7.19—7.23 (2H, m, ArH),
7.30—7.33 (2H, m, ArH), 7.39—7.40 (2H, m, ArH); 13C-NMR (150 MHz,
CDCl3) d: 22.4 (t), 26.1 (t), 27.0 (q), 30.8 (t), 38.4 (d), 41.9 (t), 70.7 (s),
72.1 (s), 97.2 (s), 125.6 (d), 126.1 (dϫ2), 126.3 (d), 126.5 (d), 127.2 (d),
129.1 (dϫ2), 132.8 (s), 138.2 (s), 203.8 (s), 206.8 (s); MS m/z: 325
(MϩϪCOMe). Anal. Calcd for C21H20O2S2: C, 68.45; H, 5.47. Found: C,
68.17; H, 5.43.
2-Acetyl-2-[3-(phenylselanyl)-1-(2-thienyl)-2-propyn-1-yl]cyclohexanone
(2u): Yellow needles, mp 109—111 °C, IR (KBr, cmϪ1) n: 2948, 1698,
1577, 1476, 1439, 1360, 1179, 1125, 847, 737, 626; 1H-NMR (500 MHz,
CDCl3) d: 1.58—1.67 (2H, m, alkyl H), 1.86—1.88 (1H, m, alkyl H),
1.96—1.99 (1H, m, alkyl H), 2.04—2.13 (1H, m, alkyl H), 2.05 (3H, s, Me),
2.18—2.26 (1H, m, alkyl H), 2.55—2.57 (1H, m, alkyl H), 2.69—2.72 (1H,
m, alkyl H), 5.29 (1H, s, CH), 6.89—6.91 (2H, m, ArH), 7.19 (1H, dd, Jϭ1,
5 Hz, ArH), 7.23—7.26 (1H, m, ArH), 7.29—7.32 (2H, m, ArH), 7.50 (2H,
d, Jϭ8 Hz, ArH); 13C-NMR (125 MHz, CDCl3) d: 22.5 (t), 26.1 (t), 27.0 (q),
30.9 (t), 38.6 (d), 42.0 (t), 64.1 (s), 72.2 (s), 101.9 (s), 125.6 (d), 126.5 (d),
127.0 (d), 127.2 (d), 128.8 (s), 129.0 (dϫ2), 129.4 (dϫ2), 138.4 (s), 203.9
(s), 206.9 (s); MS m/z: 398 (MϩϪH2O), 373 (MϩϪCOMe).
Yellow needles, mp 60—70 °C, IR (KBr, cmϪ1) n: 2942, 1698, 1577,
1477, 1439, 1357, 1286, 1221, 1176, 1125, 1021, 848, 756, 737, 707, 688;
1H-NMR (500 MHz, CDCl3) d: 1.38—1.47 (2H, m, alkyl H), 1.70—1.73
(1H, m, alkyl H), 1.79—1.91 (2H, m, alkyl H), 2.08—2.17 (1H, m, alkyl H),
2.22 (3H, s, Me), 2.51—2.55 (2H, m, alkyl H), 5.49 (1H, s, CH), 6.92 (1H,
dd, Jϭ3, 5 Hz, ArH) 7.08 (1H, d, Jϭ3 Hz, ArH), 7.19 (1H, dd, Jϭ4, 5 Hz,
ArH), 7.21—7.33 (3H, m, ArH), 7.48—7.50 (2H, m, ArH); 13C-NMR
(125 MHz, CDCl3) d: 22.1 (t), 25.3 (t), 26.2 (q), 28.5 (t), 38.0 (d), 42.0 (t),
65.0 (s), 73.4 (s), 99.9 (s), 125.7 (d), 126.3 (d), 127.2 (d), 128.4 (sϩd),
129.3 (dϫ2), 129.5 (dϫ2), 139.3 (s), 202.0 (s), 207.2 (s); MS m/z: 398
(MϩϪH2O), 373 (MϩϪCOMe). Anal. Calcd for C21H20O2SSe: C, 60.72; H,
4.85. Found: C, 60.28; H, 4.86.
Yellow powders, mp 77—79 °C, IR (KBr, cmϪ1) n: 2944, 2870, 1702,
1581, 1478, 1440, 1358, 1287, 1228, 1176, 1124, 1089, 1023, 970, 851,
741, 707, 627, 525, 466; 1H-NMR (600 MHz, CDCl3) d: 1.40—1.47 (2H, m,
CH2), 1.71—1.74 (1H, m, CH), 1.79—1.85 (1H, m, CH), 1.86—1.91 (1H,
m, CH), 2.09—2.15 (1H, m, CH), 2.23 (3H, s, Me), 2.52—2.55 (2H, m,
CH2), 5.49 (1H, s, CH), 6.93 (1H, dd, Jϭ4, 5 Hz, ArH), 7.09 (1H, d,
Jϭ4 Hz, ArH), 7.21—7.24 (2H, m, ArH), 7.33—7.36 (2H, m, ArH), 7.39
(2H, br d, Jϭ8 Hz, ArH); 13C-NMR (150 MHz, CDCl3) d: 22.4 (t), 26.1 (t),
27.0 (q), 30.8 (t), 38.4 (d), 41.9 (t), 71.7 (s), 73.4 (s), 95.6 (s), 125.8 (d),
126.3 (dϫ2), 126.4 (d), 126.7 (d), 128.4 (d), 129.2 (dϫ2), 132.4 (s), 139.3
(s), 202.0 (s), 207.2 (s); MS m/z: 325 (MϩϪCOMe). Anal. Calcd for
C21H20O2S2: C, 68.45; H, 5.47. Found: C, 68.30; H, 5.46.
2-Acetyl-2-[3-(phenylselanyl)-1-(2-thenyl)-2-propyn-1-yl]cyclopentanone
2-Acetyl-2-[1-(benzodioxol-5-yl)-3-(phenylsulfanyl)-2-propyn-1-yl]cy-
(2v): Yellow powders, mp 70—72 °C, IR (KBr, cmϪ1) n: 2925, 1740, 1703,
clohexanone (2s): Colorless needles, mp 131—133 °C, IR (KBr, cmϪ1) n:
1
1
1577, 1477, 1439, 1400, 1279, 1197, 1136, 1021, 737, 689, 442; H-NMR
2941, 1699, 1504, 1489, 1442, 1362, 1248, 1220, 1038, 930, 741, 689; H-
(600 MHz, CDCl3) d: 1.75—1.85 (1H, m, alkyl H), 1.98—2.07 (1H, m,
alkyl H), 2.19—2.28 (1H, m, alkyl H), 2.24 (3H, s, Me), 2.32—2.45 (2H, m,
alkyl H), 2.69—2.73 (1H, m, alkyl H), 5.26 (1H, s, CH), 6.90 (1H, dd, Jϭ3,
5 Hz, ArH), 6.92 (1H, d, Jϭ3 Hz, ArH), 7.18—7.20 (1H, m, ArH), 7.23—
7.27 (3H, m, ArH), 7.46—7.47 (2H, m, ArH); 13C-NMR (150 MHz, CDCl3)
d: 19.8 (t), 26.3 (q), 28.0 (t), 38.9 (t), 39.6 (d), 64.8 (s), 74.0 (s), 100.8 (s),
125.4 (d), 126.4 (d), 126.7 (d), 127.2 (d), 128.3 (s), 129.2 (dϫ2), 129.5
(dϫ2), 139.1 (s), 200.7 (s), 212.8 (s); MS m/z: 359 (MϩϪCOMe). Anal.
Calcd for C20H18O2SeS: C, 59.85; H, 4.52. Found: C, 59.16; H, 4.39.
Synthesis of 3-Benzoyl-4-(4-methoxyphenyl)-2-phenyl-5-(phenylsulfa-
nylmethyl)furan (4a), Typical Procedure To a tetrahydrofuran (THF)–
MeOH (2.0 ml, 1 : 1) solution of 1,3-diphenyl-2-[1-(4-methoxyphenyl)-
3-(phenylsulfanyl)prop-2-ynyl]propanedione (2a) (0.10 g, 0.21 mmol) was
added 5 M sodium methoxide (0.20 ml, 1.0 mmol) at room temperature. The
reaction mixture was stirred for 5 min and poured into water (50 ml). The
organic layer was separated and the aqueous layer was extracted with ether.
The combined organic layer was dried over MgSO4. The solvent was
removed under reduced pressure. The residue was purified by preparative TLC
on silica gel eluting with AcOEt–n-hexane (1 : 20) to give 4a (89 mg, 90%)
as a yellow oil.
NMR (600 MHz, CDCl3) d: 1.54—1.64 (2H, m, alkyl H), 1.85—1.88 (2H,
m, alkyl H), 1.97 (3H, s, Me), 2.04—2.19 (2H, m, alkyl H), 2.55—2.57 (2H,
m, alkyl H), 4.89 (1H, s, CH), 5.94 (2H, s, OCH2O), 6.67 (1H, d, Jϭ7 Hz,
CH), 6.70 (1H, d, Jϭ7 Hz, CH), 6.80 (1H, d, Jϭ1 Hz, CH), 7.19—7.21 (1H,
m, ArH), 7.31—7.33 (2H, m, ArH), 7.37—7.39 (2H, m, ArH); 13C-NMR
(600 MHz, CDCl3) d: 22.4 (t), 25.9 (t), 27.3 (q), 29.9 (t), 42.0 (t), 42.9 (d),
70.3 (s), 72.1 (s), 98.1 (s), 101.2 (t), 108.0 (d) 109.5 (d), 122.4 (d), 126.0
(dϫ2), 126.3 (d), 129.1 (dϫ2), 129.3 (s), 133.2 (s), 147.2 (s), 147.7 (s),
204.2 (s), 206.7 (s); MS m/z: 388 (MϩϪH2O), 363 (MϩϪCOMe). Anal.
Calcd for C24H22O4S: C, 70.91; H, 5.46. Found: C, 70.27; H, 5.42.
Pale yellow plates, IR (KBr, cmϪ1) n: 2944, 1698, 1582, 1503, 1488,
1442, 1360, 1248, 1236, 1173, 1125, 1039, 817, 705, 689; 1H-NMR
(600 MHz, CDCl3) d: 1.37—1,47 (2H, m, alkyl H), 1.62—1.79 (2H, m,
alkyl H), 1.84—1.86 (1H, m, alkyl H), 2.04—2.14 (1H, m, alkyl H), 2.23
(3H, s, Me), 2.43—2.49 (2H, m, alkyl H), 5.13 (1H, s, CH), 5.94 (2H, d,
Jϭ3 Hz, OCH2O), 6.73 (1H, d, Jϭ8 Hz, CH), 6.90 (1H, dd, Jϭ2, 8 Hz, CH),
6.96 (1H, d, Jϭ1 Hz, CH), 7.20—7.22 (1H, m, ArH), 7.31—7.37 (4H, m,
ArH); 13C-NMR (600 MHz, CDCl3) d: 21.9 (t), 25.4 (t), 26.7 (q), 29.4 (t),
41.5 (d), 42.1 (t), 71.2 (s), 72.8 (s), 97.0 (s), 101.1 (t), 107.8 (d), 110.7 (d),
123.8 (d), 126.3 (dϫ2), 126.5 (d), 129.2 (dϫ2), 130.0 (s), 132.7 (s), 146.9
(s), 147.3 (s), 202.5 (s), 207.2 (s); MS m/z: 407 (Mϩ), 388 (MϩϪH2O), 363
(MϩϪCOMe). Anal. Calcd for C24H22O4S: C, 70.91; H, 5.46. Found: C,
70.30; H, 5.35.
4a: IR (KBr, cmϪ1) n: 3058, 2932, 2835, 1659, 1596, 1579, 1560, 1510,
1485, 1446, 1386, 1327, 1290, 1249, 1177, 1030, 991, 902, 837, 766, 742,
1
691, 605; H-NMR (600 MHz, CDCl3) d: 3.66 (3H, s, OMe), 4.17 (2H, s,
CH2), 6.69 (2H, d, Jϭ9 Hz, ArH), 6.98 (2H, d, Jϭ9 Hz, ArH), 7.12—7.26
(8H, m, ArH), 7.33—7.36 (1H, m, ArH), 7.39—7.40 (2H, m, ArH), 7.49—
7.50 (2H, m, ArH), 7.73—7.75 (2H, m, ArH); 13C-NMR (150 MHz, CDCl3)
d: 30.6 (t), 55.0 (q), 113.7 (dϫ2), 121.6 (s), 123.3 (s), 125.5 (s), 125.8 (s),
126.2 (dϫ2), 127.2 (d), 128.2 (dϫ2), 128.3 (dϫ2), 128.8 (dϫ2), 129.4 (s),
129.7 (dϫ2), 130.2 (dϫ2), 131.8 (dϫ2), 133.2 (d), 134.7 (s), 137.2 (s),
146.4 (s), 151.5 (s), 158.7 (s), 193.4 (s); MS m/z: 476 (Mϩ), 371
(MϩϪCOPh), 367 (MϩϪSPh). High-resolution mass Calcd for C31H24O3S:
476.1446, Found m/z: 467.1772.
2-Acetyl-2-[1-(benzodioxol-5-yl)-3-(phenylselanyl)-2-propyn-1-yl]cyclo-
hexanone (2t): mp 120—122 °C, IR (KBr, cmϪ1) n: 2942, 1721, 1699, 1577,
1503, 1488, 1441, 1361, 1249, 1124, 1038, 930, 814, 737, 689; 1H-NMR
(400 MHz, CDCl3) d: 1.53—1.67 (3H, m, alkyl H), 1.85—1.88 (1H, m,
alkyl H), 1.96 (3H, s, Me), 2.10—2.20 (2H, m, alkyl H), 2.53—2.57 (2H, m,
alkyl H), 4.90 (1H, s, CH), 5.94—5.97 (2H, s, CH2), 6.65 (1H, dd, Jϭ2,
8 Hz, ArH), 6,70 (1H, d, Jϭ8 Hz, ArH), 6.80 (1H, d, Jϭ2 Hz, ArH, CH),
7.22—7.32 (3H, m, ArH), 7.47—7.49 (2H, m, ArH); 13C-NMR (150 MHz,
CDCl3) d: 22.4 (t), 25.8 (t), 27.4 (q), 29.8 (t), 42.1 (t), 43.1 (d), 63.5 (s),
72.1 (s), 101.2 (t), 102.8 (s), 108.0 (d), 109.5 (d), 122.4 (d), 126.9 (d), 128.9
(dϫ2), 129.0 (s), 129.4 (dϫ2), 129.5 (s), 147.2 (s), 147.6 (s), 204.2 (s),
206.7 (s); MS m/z: 436 (MϩϪH2O), 411 (MϩϪCOMe). Anal. Calcd for
C24H22O4Se: C, 63.58; H, 4.89. Found: C, 63.23; H, 4.80.
3-Benzoyl-4-(3,4-dimethoxyphenyl)-2-phenyl-5-(phenylsulfanyl-
methyl)furan (4b): IR (KBr, cm-1) n: 3058, 2935, 2834, 1660, 1596, 1580,
1559, 1515, 1490, 1462, 1448, 1420, 1332, 1256, 1238, 1171, 1073, 1025,
1
904, 876, 809, 766, 740, 692; H-NMR (600 MHz, CDCl3) d: 3.66 (3H, s,
Yellow plates, mp 112—116 °C, IR (KBr, cmϪ1) n: 2943, 1698, 1577,
1503, 1487, 1440, 1360, 1289, 1247, 1173, 1125, 1039, 932, 872, 816, 736,
688; 1H-NMR (600 MHz, CDCl3) d: 1.38—1.44 (2H, m, alkyl H), 1.59 (1H,
s, alkyl H), 1.70—1.85 (2H, m, alkyl H), 2.07—2.13 (1H, m, alkyl H), 2.22
(3H, s, Me), 2.42—2.48 (2H, m, alkyl H), 5.15 (1H, s, CH), 5.94 (2H, br s,
CH2), 6.72 (1H, d, Jϭ8 Hz, ArH), 6.90 (1H, dd, Jϭ2, 8 Hz, ArH), 6.95 (1H,
d, Jϭ2 Hz, ArH), 7.24—7.32 (3H, m, ArH), 7.47—7.48 (2H, m, ArH); 13C-
NMR (150 MHz, CDCl3) d: 22.0 (t), 25.4 (t), 26.7 (q), 29.2 (t), 41.7 (d),
Me), 3.79 (3H, s, Me), 4.22 (2H, s, CH2), 6.65 (1H, d, Jϭ8 Hz, ArH), 6.67
(1H, s, ArH), 6.69 (1H, d, Jϭ8 Hz, ArH), 7.24—7.29 (8H, m, ArH), 7.39—
7.43 (3H, m, ArH), 7.51—7.52 (2H, m, ArH), 7.77 (2H, d, Jϭ8 Hz, ArH);
13C-NMR (150 MHz, CDCl3) d: 30.76 (t), 55.66 (q), 55.73 (q), 111.00 (d),
112.28 (d), 121.46 (d), 121.58 (s), 123.80 (s), 125.71 (s), 126.16 (dϫ2),
127.27 (d), 128.34 (dϫ2), 128.47 (dϫ2), 128.86 (d), 128.93 (dϫ2), 129.45
(s), 129.72 (dϫ2), 131.78 (dϫ2), 133.42 (d), 134.82 (s), 137.30 (s), 146.42
(s), 148.23 (s), 148.55 (s), 151.43 (s), 193.67 (s); MS m/z: 506 (Mϩ), 401

September 2010
1185
(MϩϪCOPh), 397 (M+-SPh). Anal. Calcd for C32H26O4S: C, 75.87; H, 5.17. 21.8 (t), 118.2 (s), 121.5 (s), 125.8 (d), 126.1 (dϫ2), 127.2 (d), 127.3 (d),
Found: C, 75.74; H, 5.12. 127.9 (d), 128.3 (dϫ2), 128.4 (dϫ2), 128.5 (d), 128.9 (s), 129.0 (dϫ2),
3-Benzoyl-4-(benzodioxol-5-yl)-2-phenyl-5-(phenylsulfanylmethyl)furan 129.1 (s), 129.7 (dϫ2), 131.7 (s), 133.5 (d), 135.0 (dϫ2), 137.1 (s), 148.8
(4c): IR (KBr, cmϪ1) n: 3058, 2892, 1661, 1596, 1580, 1559, 1488, 1444,
1394, 1339, 1320, 1239, 1175, 1129, 1101, 1072, 1039, 1001, 935, 906,
887, 810, 766, 743, 692; 1H-NMR (600 MHz, CDCl3) d: 4.17 (2H, s, CH2S),
5.85 (2H, s, OCH2O), 6.49 (1H, d, Jϭ1 Hz, ArH), 6.52 (1H, dd, Jϭ2, 8 Hz,
(s), 151.1 (s), 193.1 (s); MS m/z: 343 (MϩϪSePh). Anal. Calcd for
C28H20O2SSe: C, 67.33; H, 4.04. Found: C, 67.48; H, 4.03.
3-Benzoyl-4-(2-furyl)-2-phenyl-5-(phenylselanylmethyl)furan (4i): IR
(KBr, cmϪ1) n: 3057, 2361, 1664, 1596, 1579, 1541, 1490, 1476, 1448,
ArH), 6.61 (1H, d, Jϭ8 Hz, ArH), 7.20—7.29 (8H, m, ArH), 7.39—7.42 1366, 1320, 1229, 1176, 1155, 1129, 1073, 1023, 999, 906, 809, 764, 736,
(3H, m, ArH), 7.48—7.49 (2H, m, ArH), 7.73—7.75 (2H, m, ArH); 13C- 716, 690; H-NMR (600 MHz, CDCl3) d: 4.41—4.44 (2H, m, CH2Se), 6.05
1
NMR (150 MHz, CDCl3) d: 30.7 (t), 101.0 (t), 108.3 (d), 109.5 (d), 121.5 (1H, d, Jϭ3 Hz, ArH), 6.20 (1H, t, Jϭ3 Hz, ArH), 7.18—7.26 (7H, m, ArH),
(s), 122.8 (d), 124.8 (s), 125.6 (s), 126.3 (dϫ2), 127.4 (d), 128.3 (dϫ2), 7.31—7.34 (2H, m, ArH), 7.40—7.48 (3H, m, ArH), 7.59—7.60 (2H, m,
128.4 (dϫ2), 128.4 (d), 128.9 (dϫ2), 129.4 (s), 129.7 (dϫ2), 132.1 (dϫ2), ArH), 7.83 (2H, d, Jϭ8 Hz, ArH); 13C-NMR (150 MHz, CDCl3) d: 22.7 (t),
133.3 (d), 134.6 (s), 137.2 (s), 146.7 (s), 146.9 (s), 147.4 (s), 151.6 (s), 193.3 108.1 (d), 111.0 (d), 115.2 (s), 119.4 (s), 126.1 (dϫ2), 127.9 (d), 128.4
(s); MS m/z: 489 (MϩϪ1), 386 (MϩϪSPh). Anal. Calcd for C31H22O4S: C,
(dϫ2), 128.5 (dϫ2), 128.9 (dϫ2), 129.0 (s), 129.1 (s), 129.5 (d), 129.4 (d),
129.7 (dϫ2), 133.6 (d), 134.9 (d), 137.1 (s), 141.7 (s), 145.5 (s), 148.3 (s),
75.96; H, 4.52. Found: C, 75.74; H, 4.57.
3-Benzoyl-4-(4-chlorophenyl)-2-phenyl-5-(phenylsulfanylmethyl)furan 151.1 (s), 193.2 (s); MS m/z: 483 (Mϩ), 327 (MϩϪSePh). High-resolution
(4d): Yellow powders, mp 162 °C, IR (KBr, cmϪ1) n: 3057, 2924, 1660, mass Calcd for C28H20O3Se: 484.0577, Found m/z: 484.0548.
1595, 1579, 1556, 1491, 1447, 1407, 1326, 1234, 1193, 1174, 1124, 1089,
Reaction of 2p with Bu4NF in N,N-Dimethylformamide (DMF), Typi-
cal Procedure One molar tetrabutylammonium fluoride (0.38 ml,
1
1073, 1042, 1021, 996, 907, 869, 841, 770, 744, 712; H-NMR (600 MHz,
CDCl3) d: 4.14 (2H, s, CH2S), 6.94 (2H, d, Jϭ9 Hz, ArH), 7.12 (2H, d, 0.38 mmol) was added to
Jϭ9 Hz, ArH), 7.21—7.27 (8H, m, ArH), 7.37—7.48 (3H, m, ArH), 7.49— 0.13 mmol) at room temperature. The reaction mixture was refluxed for
7.50 (2H, m, ArH), 7.73 (2H, d, Jϭ7 Hz, ArH); 13C-NMR (150 MHz,
5 min and poured into water (50 ml). The organic layer was separated and
a DMF (0.50 ml) solution of 2p (50 mg,
CDCl3) d: 30.8 (t), 121.2 (s), 124.8 (s), 126.3 (dϫ2), 127.6 (d), 128.3 the aqueous layer was extracted with ether. The combined organic layer was
(dϫ2), 128.4 (dϫ2), 128.5 (dϫ2), 128.6 (d), 129.0 (dϫ2), 129.2 (s), 129.6 dried over MgSO4. The solvent was removed under reduced pressure. The
(s), 129.7 (dϫ2), 130.3 (dϫ2), 132.3 (dϫ2), 133.3 (s), 133.4 (d), 134.3 (s),
residue was purified by preparative TLC on silica gel eluting with AcOEt–n-
137.0 (s), 147.0 (s), 152.0 (s), 192.9 (s); MS m/z: 480 (Mϩ), 375 hexane (1 : 20) to give 6p (43 mg, 87%) and 5p (4 mg, 10%) as a yellow oil.
(MϩϪCOPh), 371 (MϩϪSPh). Anal. Calcd for C30H21O2ClS: C, 74.91; H,
9-Acetyl-3-(p-methoxyphenyl)-2-(phenylsulfanylmethyl)-4,5,6,7-tetrahy-
4.40. Found: C, 75.16; H, 4.61.
drobenzofuran (6p): IR (KBr, cmϪ1) n: 2936, 1703, 1607, 1513, 1440, 1354,
3-Benzoyl-4-(p-methoxyphenyl)-2-phenyl-5-(phenylselanylmethyl)furan 1286, 1247, 1180, 1102, 1086, 1035, 972, 741, 691, 607; 1H-NMR
(4e): IR (KBr, cmϪ1) n: 3057, 2931, 2834, 1660, 1596, 1578, 1559, 1509, (500 MHz, CDCl3) d: 1.22—1.28 (2H, m, alkyl H), 1.42—1.47 (1H, m,
1489, 1476, 1447, 1385, 1328, 1290, 1249, 1177, 1130, 1109, 1072, 1022,
alkyl H), 1.60—1.64 (1H, m, alkyl H), 2.11 (3H, s, COMe), 2.15—2.18 (1H,
990, 899, 832, 765, 739, 691; H-NMR (600 MHz, CDCl3) d: 3.71 (3H, s, m, alkyl H), 2.47—2.50 (1H, m, alkyl H), 3.73 (1H, d, Jϭ14 Hz, SCH2),
Me), 4.18 (2H, s, CH), 6.69 (2H, d, Jϭ8 Hz, ArH), 6.96 (2H, d, Jϭ8 Hz, 3.79 (1H, s, OMe), 3.87 (1H, d, Jϭ14 Hz, SCH2), 5.23 (1H, t, Jϭ4 Hz,
1
ArH), 7.22—7.28 (8H, m, ArH), 7.37—7.40 (1H, m, ArH), 7.47—7.48 (2H, olefinic H), 6.79 (2H, d, Jϭ9 Hz, ArH), 6.85 (2H, d, Jϭ9 Hz, ArH), 7.21—
m, ArH), 7.56 (2H, d, Jϭ7 Hz, ArH), 7.74 (2H, d, Jϭ7 Hz, ArH); 13C-NMR
(150 MHz, CDCl3) d: 21.9 (t), 51.1 (q), 113.8 (dϫ2), 123.6 (s), 125.0 (s),
7.23 (3H, m, ArH), 7.29—7.31 (2H, m, ArH); 13C-NMR (125 MHz, CDCl3)
d: 18.4 (t), 22.0 (t), 25.9 (q), 27.1 (t), 30.4 (t), 55.2 (q), 63.5 (s), 100.4 (d),
126.2 (dϫ2), 127.9 (d), 128.3 (dϫ2), 128.3 (d), 128.4 (dϫ2), 129.1 (dϫ2), 114.0 (dϫ2), 118.1 (s), 124.0 (s), 127.0 (d), 129.0 (dϫ2), 129.7 (dϫ2),
129.2 (s), 129.5 (s), 129.8 (dϫ2), 130.1 (dϫ2), 131.5 (d), 133.3 (d), 134.9 131.0 (dϫ2), 134.7 (s), 150.6 (s), 155.4 (s), 159.0 (s), 205.5 (s); MS m/z:
(dϫ2), 137.2 (s), 147.6 (s), 151.3 (s), 158.7 (s), 193.5 (s); MS m/z: 419 392 (Mϩ), 349 (MϩϪCOMe). High resolution mass Calcd for C24H24O3S:
(MϩϪCOPh), 367 (MϩϪSePh). Anal. Calcd for C31H24O3Se: C, 71.13; H, 392.1446, Found m/z: 392.1381.
4.62. Found: C, 69.82; H, 4.72.
3-(p-Methoxyphenyl)-2-(phenylsulfanylmethyl)-4,5,6,7-tetrahydrobenzo-
3-Benzoyl-4-(benzodioxol-5-yl)-2-phenyl-5-(phenylselanylmethyl)furan furan (5p): A yellow oil, IR (KBr, cmϪ1) n: 2932, 1760, 1607, 1511, 1440,
(4f): A yellow oil, IR (KBr, cmϪ1) n: 3058, 2898, 1712, 1661, 1596, 1579,
1560, 1503, 1490, 1447, 1359, 1339, 1321, 1239, 1176, 1129, 1072, 1039,
999, 935, 904, 887, 810, 766, 739, 718, 692, 625; 1H-NMR (600 MHz,
CDCl3) d: 4.17 (2H, s, CH2Se), 5.85 (2H, s, OCH2O), 6.47 (1H, d, Jϭ1 Hz,
ArH), 6.50 (1H, dd, Jϭ1, 8 Hz, ArH), 6.60 (1H, d, Jϭ9 Hz, ArH), 7.21—
7.29 (8H, m, ArH), 7.39—7.41 (1H, m, ArH), 7.46—7.47 (2H, m, ArH),
7.55—7.56 (2H, m, ArH), 7.72—7.74 (2H, m, ArH); 13C-NMR (150 MHz,
1289, 1250, 1177, 1034, 987, 837, 741, 419; 1H-NMR (600 MHz, CDCl3) d:
1.70—1.73 (2H, m, alkyl H), 1.83—1.85 (2H, m, alkyl H), 2.37 (2H, t,
Jϭ6 Hz, alkyl H), 2.60 (2H, t, Jϭ6 Hz, alkyl H), 3.82 (3H, s, Me), 4.17 (2H,
s, CH2), 6.90 (2H, d, Jϭ8 Hz, ArH), 7.18—7.19 (3H, m, ArH), 7.22—7.24
(2H, m, ArH), 7.32—7.33 (2H, m, ArH); 13C-NMR (600 MHz, CDCl3) d:
21.7 (t), 22.9 (t), 23.1 (t), 23.3 (t), 31.0 (t), 55.3 (t), 114.0 (dϫ2), 117.4 (s),
123.6 (s), 125.5 (s), 126.4 (d), 128.8 (dϫ2), 129.8 (dϫ2), 130.3 (dϫ2),
CDCl3) d: 21.8 (t), 100.9 (t), 108.2 (d), 109.4 (d), 121.7 (s), 122.7 (d), 125.0 136.1 (s), 143.5 (s), 150.4 (s), 158.5 (s); MS m/z: 350 (Mϩ). High resolution
(sϫ2), 126.2 (dϫ2), 127.9 (d), 128.3 (d), 128.4 (dϫ3), 129.0 (s), 129.1 mass Calcd for C22H22O2S: 350.1340, Found m/z 350.1329.
(dϫ2), 129.4 (s), 129.7 (dϫ3), 133.3 (d), 135.0 (dϫ2), 137.2 (s), 146.8 (s),
9-Acetyl-3-(benzodioxol-5-yl)-2-(phenylsulfanylmethyl)-4,5,6,9-tetrahy-
147.4 (s), 147.8 (s), 151.3 (s), 193.3 (s); MS m/z: 461 (MϩϪPh). Anal. drobenzofurane (6s): IR (KBr, cmϪ1) n: 2936, 1703, 1504, 1489, 1439,
1
Calcd for C31H22O4Se: C, 69.28; H, 4.13. Found: C, 69.43; H, 4.11.
1354, 1245, 1146, 1088, 1039, 984, 935, 891, 869, 813, 741, 691, 616; H-
3-Benzoyl-4-(4-fluorophenyl)-2-phenyl-5-(phenylselanylmethyl)furan
NMR (400 MHz, CDCl3) d: 1.21—1.29 (2H, m, alkyl H), 1.40—1.45 (1H,
(4g): mp 96 °C, IR (KBr, cmϪ1) n: 3057, 2924, 2359, 1658, 1596, 1579, m, alkyl H), 1.65—1.69 (1H, m, alkyl H), 2.04—2.20 (1H, m, CH), 2.11
1560, 1508, 1488, 1476, 1447, 1410, 1383, 1327, 1230, 1176, 1159, 1130,
(3H, s, Me), 2.48 (2H, dt, Jϭ3, 12 Hz, alkyl H), 3.72 (1H, d, Jϭ14 Hz, CH2),
3.84 (1H, d, Jϭ14 Hz, CH2), 5.24 (1H, t, Jϭ3 Hz, olefinic H), 5.94 (2H, s,
1
1096, 1072, 1021, 993, 899, 835, 807, 766, 739, 691; H-NMR (600 MHz,
CDCl3) d: 4.14 (2H, s, CH2Se), 6.81—6.84 (2H, m, ArH), 6.95—6.97 (2H, ArH), 6.36 (1H, d, Jϭ8 Hz, OCH2O), 6.69 (1H, d, Jϭ8 Hz, OCH2O), 7.22—
m, ArH), 7.20—7.30 (8H, m, ArH), 7.37—7.39 (1H, m, ArH), 7.47—7.54 7.26 (3H, m, ArH), 7.30—7.33 (2H, m, ArH); 13C-NMR (100 MHz, CDCl3)
(4H, m, ArH), 7.70—7.71 (2H, m, ArH); 13C-NMR (150 MHz, CDCl3) d: d: 18.4 (t), 22.0 (t), 26.0 (q), 27.1 (t), 30.5 (t), 63.5 (s), 100.5 (d), 101.1 (t),
21.7 (t), 115.2 (d), 115.3 (d), 121.6 (s), 124.3 (s), 126.3 (dϫ2), 128.0 (d),
128.3 (dϫ2), 128.4 (dϫ2), 128.5 (d), 128.8 (s), 129.1 (dϫ2), 129.3 (s),
108.4 (d), 108.9 (d), 118.1 (s), 122.3 (d), 125.3 (s), 127.1 (d), 128.9 (dϫ2),
131.3 (dϫ2), 134.5 (s), 147.1 (s), 147.7 (s), 151.0 (s), 155.3 (s), 205.4 (s);
129.7 (dϫ2), 130.6 (d), 130.7 (d), 133.4 (d), 135.1 (dϫ2), 137.1 (s), 148.0 MS m/z: 406 (Mϩ), 363 (MϩϪCOMe). High resolution mass Calcd for
(s), 151.7 (s), 161.1 (s), 162.7 (s), 193.1 (s); MS m/z: 512 (Mϩ), 355 C24H22O4S: 406.1239, Found m/z: 406.1132.
(MϩϪSePh). Anal. Calcd for C30H21O2FSe: C, 70.45; H, 4.14. Found: C,
70.17; H, 4.16.
9-Acetyl-3-(2-thienyl)-2-(phenylsulfanylmethyl)-4,5,6,9-tetrahydrobenzo-
furan (6r): IR (KBr, cmϪ1) n: 3422, 2932, 1712, 1635, 1582, 1480, 1439,
1355, 1300, 1247, 1147, 1087, 948, 848, 741, 691, 615; 1H-NMR (600 MHz,
3-Benzoyl-2-phenyl-5-(phenylselanylmethyl)-4-(2-thienyl)furan (4h): IR
(KBr, cmϪ1) n: 3057, 2923, 2852, 1661, 1596, 1579, 1561, 1490, 1476, CDCl3) d: 1.24—1.32 (1H, m, alkyl H), 1.45—1.53 (1H, m, alkyl H),
1447, 1384, 1348, 1316, 1231, 1175, 1129, 1071, 1020, 999, 943, 898, 849, 1.67—1.69 (1H, m, alkyl H), 2.06—2.10 (1H, m, alkyl H), 2.08 (3H, s, Me),
1
766, 735, 690; H-NMR (600 MHz, CDCl3) d: 4.27—4.30 (2H, m, CH2Se),
2.16—2.22 (1H, m, alkyl H), 2.72 (1H, dt, Jϭ3, 12 Hz, alkyl H), 3.90 (1H,
6.72 (1H, d, Jϭ4 Hz, ArH), 6.81 (1H, dd, Jϭ4, 5 Hz, ArH), 7.11—7.12 (1H, d, Jϭ14 Hz, CH2), 4.11 (1H, d, Jϭ14 Hz, CH2), 5.25 (1H, dd, Jϭ3, 5 Hz,
m, ArH), 7.20—7.29 (8H, m, ArH), 7.40—7.45 (3H, m, ArH), 7.59 (2H, d, olefinic H), 6.76 (1H, dd, Jϭ3, 1 Hz, ArH), 6.94—6.95 (1H, m, ArH),
Jϭ6 Hz, ArH), 7.77 (2H, d, Jϭ8 Hz, ArH); 13C-NMR (150 MHz, CDCl3) d: 7.19—7.26 (4H, m, ArH), 7.36—7.37 (2H, m, ArH); 13C-NMR (150 MHz,

1186
Vol. 58, No. 9
CDCl3) d: 18.3 (t), 21.8 (t), 25.8 (q), 27.1 (t), 30.6 (t), 63.1 (s), 101.0 (d),
112.6 (s), 125.0 (d), 126.0 (d), 127.1 (d), 127.3 (d), 128.9 (dϫ2), 131.1
(dϫ2), 132.8 (s), 134.5 (s), 151.8 (s), 154.8 (s), 204.8 (s); MS m/z: 368
(Mϩ), 325 (MϩϪCOMe). High resolution mass Calcd for C21H20O2S2:
368.0905, Found m/z: 368.0904.
9) Marshall J. A., Wallace E. M., Coan P. S., J. Org. Chem., 60, 796—797
(1995).
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Soc., 123, 3393—3394 (2001).
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Chem., 69, 3408—3412 (2004).
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1994, 493—494 (1994).
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dron, 59, 4661—4671 (2003).
5-Acetyl-4-(p-methoxyphenyl)-3-(phenylsulfanyl)-2-oxa-
bicyclo[3,3,0]octa-3,8-diene (6q): IR (KBr, cmϪ1) n: 2933, 1706, 1680,
1
1608, 1514, 1440, 1355, 1291, 1251, 1180, 1035, 950, 834, 741, 691; H-
NMR (500 MHz, CDCl3) d: 1.94—2.02 (1H, m, alkyl H), 2.07 (3H, s,
COMe), 2.29—2.36 (1H, m, alkyl H), 2.52—2.58 (1H, m, alkyl H), 2.85
(1H, dd, Jϭ5, 11 Hz, CH), 3.79 (3H, s, OMe), 3.91 (1H, d, Jϭ14 Hz, CH2),
4.02 (1H, d, Jϭ14 Hz, CH2), 5.07—5.08 (1H, m, CH), 6.82 (2H, d, Jϭ8 Hz,
ArH), 7.00 (2H, d, Jϭ8 Hz, ArH), 7.20—7.27 (3H, m, ArH), 7.36—7.38
(2H, m, ArH); 13C-NMR (150 MHz, CDCl3) d: 25.4 (q), 31.1 (t), 31.6 (t),
36.0 (t), 55.2 (q), 73.2 (s), 101.4 (s), 114.3 (dϫ2), 120.3 (s), 124.4 (s), 127.1
(d), 128.5 (dϫ2), 129.0 (dϫ2), 131.0 (dϫ2), 134.8 (s), 153.7 (s), 158.9 (s),
160.5 (s), 205.2 (s); MS m/z: 378 (Mϩ), 335 (MϩϪCOMe). High resolution
mass Calcd for C23H22O3S: 378.1289, Found: 378.1274.
5-Acetyl-4-(2-thienyl)-3-(phenylsulfanyl)-2-oxabicyclo[3,3,0]octa-3,8-
diene (6v): IR (KBr, cmϪ1) n: 2931, 1709, 1680, 1583, 1480, 1439, 1355,
1312, 1243, 1193, 1098, 1044, 943, 844, 744, 692; 1H-NMR (600 MHz,
CDCl3) d: 2.03—2.08 (1H, m, alkyl H), 2.04 (3H, s, Me), 2.34—2.38 (1H,
m, alkyl H), 2.57—2.62 (1H, m, alkyl H), 2.96 (1H, dd, Jϭ5, 11 Hz, alkyl
H), 4.05 (1H, d, Jϭ14 Hz, CH2), 4.20 (1H, d, Jϭ14 Hz, CH2), 5.10—5.11
(1H, m, ArH), 6.78 (1H, t, Jϭ3 Hz, ArH), 6.95 (1H, dd, Jϭ3, 5 Hz, ArH),
7.21—7.28 (4H, m, ArH), 7.46 (2H, d, Jϭ8 Hz, ArH); 13C-NMR (150 MHz,
CDCl3) d: 25.3 (q), 31.2 (t), 31.9 (t), 36.2 (t), 73.0 (s), 102.3 (d), 115.6 (s),
124.9 (d), 125.5 (d), 127.3 (d), 127.4 (d), 129.0 (dϫ2), 131.4 (dϫ2), 133.6
(s), 134.5 (s), 154.1 (s), 159.9 (s), 204.6 (s); MS m/z: 354 (Mϩ), 311
(MϩϪCOMe). High resolution mass Calcd for C20H18O2S2: 354.0748,
Found m/z 354.0730.
Conversion of 9-Acetyl-3-(2-thienyl)-2-(phenylsulfanylmethyl)-4,5,6,7-
tetrahydrobenzofuran (6r) to 3-(2-Thienyl)-2-(phenylsulfanylmethyl)-
4,5,6,7-tetrahydrobenzofuran (7r) 1,8-Diazabicyclo[5.4.0]undec-7-ene
(50 mg, 0.33 mmol) was added to a DMF (0.50 ml) solution of 6r (40 mg,
0.11 mmol) at room temperature. The reaction mixture was stirred for
10 min and then poured into water (50 ml). The organic layer was separated
and the aqueous layer was extracted with ether. The combined organic layer
was dried over MgSO4. The solvent was removed under reduced pressure.
The residue was purified by preparative TLC on silica gel eluting with
AcOEt–n-hexane (1 : 20) to give 7r (28 mg, 70%) as a yellow oil.
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Lett., 10, 4251—4254 (2008).
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(2000).
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Tetrahedron, 57, 3297—3300 (2001).
7r: A yellow oil, IR (KBr, cmϪ1) n: 3422, 2932, 1712, 1635, 1582, 1480,
1439, 1355, 1300, 1247, 1147, 1087, 948, 848, 741, 691, 615; 1H-NMR
(600 MHz, CDCl3) d: 1.24—1.32 (1H, m, alkyl H), 1.45—1.53 (1H, m,
alkyl H), 1.67—1.69 (1H, m, alkyl H), 2.06—2.10 (1H, m, alkyl H), 2.08
(3H, s, Me), 2.16—2.22 (1H, m, alkyl H), 2.72 (1H, dt, Jϭ3, 12 Hz, alkyl
H), 3.90 (1H, d, Jϭ14 Hz, CH2), 4.11 (1H, d, Jϭ14 Hz, CH2), 5.25 (1H, dd,
Jϭ3, 5 Hz, olefinic H), 6.76 (1H, dd, Jϭ3, 1 Hz, ArH), 6.94—6.95 (1H, m,
ArH), 7.19—7.26 (4H, m, ArH), 7.36—7.37 (2H, m, ArH); 13C-NMR
(150 MHz, CDCl3) d: 18.3 (t), 21.8 (t), 25.8 (q), 27.1 (t), 30.6 (t), 63.1 (s),
101.0 (d), 112.6 (s), 125.0 (d), 126.0 (d), 127.1 (d), 127.3 (d), 128.9 (dϫ2),
131.1 (dϫ2), 132.8 (s), 134.5 (s), 151.8 (s), 154.8 (s), 204.8 (s); MS m/z:
368 (Mϩ), 325 (MϩϪCOMe). High resolution mass Calcd for C21H20O2S2:
368.0905, Found m/z 368.0904.
Conversion of 6r to 7r by p-Toluenesulfonic Acid p-Toluenesulfonic
acid hydrate (44 mg, 0.23 mmol) was added a dioxane (0.50 ml) of 6r
(43 mg, 0.12 mmol) at room temperature. The mixture was refluxed for
10 min. The workup procedure gave 7r (24 mg, 62%).
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