Lewis acid-catalyzed propargylic etherification and sulfanylation from alcohols in MeNO2-H2O

Article abstract of DOI:10.1248/cpb.59.1133

Direct scandium- and lanthanum-catalyzed etherifications of propargyl alcohols 1 and 6 in MeNO₂-H₂O provided propargyl ethers 3, 4 and 7 in high yields. In addition, reactions of 1 and 6 with thiols exclusively yielded the corresponding propargyl sulfides.

Full text of DOI:10.1248/cpb.59.1133

September 2011
Regular Article
Chem. Pharm. Bull. 59(9) 1133—1140 (2011)
1133
Lewis Acid-Catalyzed Propargylic Etherification and Sulfanylation from
Alcohols in MeNO2–H2O
Katsuki OHTA, Eri KOKETSU, Yuya NAGASE, Nami TAKAHASHI, Hiroyasu WATANABE, and
Mitsuhiro YOSHIMATSU*
Department of Chemistry, Faculty of Education, Gifu University; 1–1 Yanagido, Gifu 501–1193, Japan.
Received May 9, 2011; accepted June 14, 2011; published online June 17, 2011
Direct scandium- and lanthanum-catalyzed etherifications of propargyl alcohols 1 and 6 in MeNO2–H2O
provided propargyl ethers 3, 4 and 7 in high yields. In addition, reactions of 1 and 6 with thiols exclusively
yielded the corresponding propargyl sulfides.
Key words C–O bond formation; C–S bond formation; propargyl alcohol
Ethers are one of the most fundamental structures of natu- Results and Discussion
ral products1—3) and carbohydrates4); thus, the development
First, we examined the reaction of 1a with n-butanol in
of general, straightforward synthetic methods for their prepa- MeNO2 under the previously reported propargylation condi-
ration has received much attention. Methods whereby only tions, which were described only as the synthetic procedure
H2O is produced as a byproduct, such as dehydrative etherifi- for the 4-oxahepta-1,6-diynes.40—43) Scandium-catalyzed
cation, are desirable yet challenging synthetic process. De- etherifications in nitromethane resulted in a complex mix-
hydrative etherifications generally employ two alternative ture; however, the addition of H2O drastically improved the
mechanistic pathways. In one case, alcohol is used as a pre- reaction and provided ether 3a in 84% yield (entries 1 and 2).
cursor for carbocations. Alternatively, the alcohol can func- Results of screening of other etherification conditions using
tion as a nucleophile (Chart 1). However, substitution of hy- 1a are shown in Table 1. Various metals, mainly lanthanoids,
droxyl group in an alcohol generally requires the prior acti- were found to be effective for etherifications in MeNO2–H2O.
vation of the hydroxyl group because of the poor leaving Next, we selected propargyl alcohols bearing other aromatic
ability of this group.5,6) An alcohol used as a precursor for substituents as starting materials and performed etherifica-
carbocations is usually activated by transforming it to the tions under the suitable condition using Sc(OTf)3/MeNO2–
corresponding acetate,7—17) carbonate,18,19) halide,20) phos- H2O at 30 °C. With the Sn(OTf)2 system, the product 2aa
phonate.21,22) Prior activation of an alcohol is also necessary was also obtained in the satisfactory yield, however, a small
if it has to be used as a nucleophile because of its low nu- amount of unknown compounds were contaminated. Results
cleophilicity. This is usually achieved by converting the of these comparisons are shown in Table 1.
hydroxyl group to a metal alkoxide.23—26) Various other use-
Using the same substrate, 3-p-methoxyphenylpropargyl al-
ful methods employing transition metals have been report- cohol 1a, etherification with 1° alcohols including methanol,
ed27—38); however, these methods have limited applicability. dodecanol and geraniol as nucleophiles produced products
To achieve one-pot etherification, the following four proc- 2ab, 2ac and 2af, respectively, in good yields (entries 1, 2
esses need to be performed: i) consider the alcohol as an
Table 1. Discovering Reaction Conditions for Lewis Acid-Catalyzed C–O
Bond Formation of 3-Sulfanyl Propargyl Alcohol 1a
electrophile and activate the hydroxyl group, ii) generate a
carbocation, iii) consider the alcohol as a nucleophile and
form an ether, and iv) control further reactions that lead to
fission of the newly formed C–O bond.
In this context, we previously devised a new method for
C–O bond formation with propargyl alcohols. This method
Producta)
(% yield)
Entry
Lewis acid
Sc(OTf)3
Condition
involves Lewis acid-catalyzed C–C bond formation and thia-
zole synthesis via a propargyl cation stabilized by a unique
structure.39) A more versatile propargylation using the alco-
hol directly as a carbocation precursor would be a powerful
tool leading to some useful compounds. In the present study,
we report a unique Lewis acid-catalyzed etherification using
both g-sulfur substituted and non-substituted propargyl alco-
hols in MeNO2–H2O.
1
2
3
4
5
6
7
8
9
10
11
12
13
14
MeNO2, 30 °C, 10 min
MeNO2–H2O, 30 °C, 20 min
MeNO2–H2O, 15 °C, 1 h
MeNO2, 30 °C, 10 min
MeNO2–H2O, 30 °C, 18 h
MeNO2, 30 °C, 10 min
MeNO2–H2O, 30 °C, 7 h
MeNO2, 30 °C, 20 min
MeNO2–H2O, 30 °C, 6 h
MeNO2–H2O, 30 °C, 30 min
MeNO2–H2O, 30 °C, 15 min
MeNO2–H2O, 30 °C, 50 min
MeNO2, 30 °C, 1 h
0
84
81
0
73
56
82
68
78
83
85
64
0
BF3–Et2O
SnCl4
TiCl4
Yb(OTf)3
La(OTf)3
Hf(OTf)4
TMSOTf
Sn(OTf)2
MeNO2–H2O, 30 °C, 1 h
85
a) The reaction was carried out with alcohol (10 eq) in the presence of 10 mol% of
Lewis acid.
Chart 1. Lewis Acid-Catalyzed Etherification of Alcohols
© 2011 Pharmaceutical Society of Japan
∗ To whom correspondence should be addressed. e-mail: yoshimae@gifu-u.ac.jp

1134
Vol. 59, No. 9
Table 2. Propargylic Etherifications of 1 and 3 with Some Alcohols
Alcohol 1
Reaction
time
Product
Entry
Y
R2
H
R3
R1
(% yield)a)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
1a (S)
p-MeOC6H4
Me
20 min
20 min
20 min
20 min
3 h
1 h
1 h
1 h
1 h
1.5 h
4 h
1.5 h
9 h
10 h
20 min
2ab (83)
2ac (59)
2ad (70)
2ae (75)
2af (71)
2ba (82)
2bb (75)
2bc (79)
2bd (82)
2be (74)
2ca (80)
2da (91)
2ea (78)
2eb (73)
2fa (78)
Me(CH2)11
Cyclopentyl
Cyclohexyl
Geranyl
Me
1b (S)
2-Thienyl
H
n-Bu
Cinnamyl
Cyclopentyl
Cyclohexyl
n-Bu
1c (S)
1d (S)
1e (S)
1-Naphthyl
2,4,6-Me3C6H2
p-FC6H4
H
H
H
H
H
n-Bu
n-Bu
Me
Allyl
1f (S)
16
17
18
19
20
21
22
23
24
H
Me
Cyclopentyl
Bn
10 min
1 h
3.5 h
2fb (84)
2fc (72)
1g (S)
1h (S)
1i (S)
n-Pent
Ph
(CH2)5
(CH2)4
(CH2)6
p-MeOC6H4
n-Pent
Ph
2ga (44)
2ha (41)
2ia (88)b)
2ja (58)b)
2ka (79)b)
4aa (80)
4ba (99)
Bu
3.5 h
Me(CH2)11
Me(CH2)11
Me(CH2)11
Me
10 min
10 min
10 min
10 min
10 min
1j (S)
1k (S)
3a (Se)
3b (Se)
H
H
Bn
25
26
3c (Se)
3d (Se)
1-Naphthyl
(CH2)5
H
Bn
Bn
3 h
1.5 h
4ca (99)
4da (99)
a) The reaction was carried out with alcohol (3—10 eq) in MeNO2–H2O (10 : 1) at 30 °C. b) The reactions of cycloalkanols gave a small amount of phenylsulfanylethynyl-
cycloalkenes 5.46)
and 5). In contrast, 2° alcohols such as cyclopentanol and cy- with both 1° and 2° alcohols in MeNO2–H2O might be pro-
clohexanol afforded 2ad and 2ae (entries 3 and 4). Surpris- ductive (Table 3). When alcohol 6a bearing an electron-do-
ingly, both 1° and 2° alcohols are also nucleophilic toward nating substituent (Arꢀp-MeOC6H4) was used, it took 12—
propargyl cations in MeNO2–H2O. Alcohols bearing other 24 h to complete the reaction because of the absence of the
aromatic substituents at the R1-position were examined with sulphur-accelerating component in the propargyl alcohols.
the 1° and 2° alcohols (entries 6—17). Alcohol 1d, bearing Therefore, we further optimized the reaction conditions for
the bulky aromatic substituent, 2,4,6-trimethylphenyl, also non-sulphur-substituted propargyl alcohols and found that
produced propargylic ether 2da in excellent yield (entry 12). the use of lanthanum triflate in MeNO2–H2O at room temper-
Di(n-pentyl)alcohol 1g and diphenyl derivative 1h produced ature was suitable. Using the optimized conditions, we per-
ether 2ga and 2ha in moderate yields (entries 18 and 19, formed reactions with n-dodecanol and allyl alcohol, as 1°
respectively). 1,3-Benzodioxol-5-yl derivative 1f provided alcohols, and isopropyl alcohol, as 2° alcohol (entries 2—4).
2fa—c (entries 15—17). Interestingly, phenylsulfanyl- Etherifications of the propargyl alcohols 6b (R1ꢀPh, R2ꢀH),
ethynylcycloalkanols, which were expected to undergo exclu- 6c (R1ꢀR2ꢀPh), and 6d (R1ꢀPh, R2ꢀn-Bu) proceeded in
sive b-elimination, gave ethers 2ia—2ka in good yields (en- high yields. Thus, we have found that lanthanum triflate-cat-
tries 20—22).44) Using similar conditions, the selenium alyzed propargylic etherifications in MeNO2–H2O represent a
analogs underwent etherification to produce 4aa—da (entries powerful tool for C–O bond formations.
23—26). 1-Aryl propargyl alcohols (R1ꢀAr, R2ꢀH) under-
Sulphur-substituted dipropargyl ethers were previously re-
went etherification to yield a wide variety of ethers 2a—f; ported to be good precursors for methoxide- and ethoxide-
however, reactions of the dialkyl derivatives were found to be mediated cyclizations giving the furan derivatives.45) There-
sensitive. Cycloalkanols (R1–R2ꢀ(CH2)n) provided ethers in fore, we investigated the sulfanylation of propargyl alcohol
high yields, while the dipentyl alcohol gave low yields of 1a with non-activated thiols, and the results of these investi-
products. On the other hand, most 1° and 2° alcohols, but not gations are shown in Table 4.
3° alcohols, were also found to be effective as electrophiles.
Compared to alcohols, reactions with thiols were com-
These successful results suggested the possibility that pleted more rapidly. The reaction of 1a with decanethiol gave
etherifications of non-sulfur-substituted propargyl alcohols propargyl decyl sulphide 8aa in 91% yield. We also per-

September 2011
1135
Table 3. Propargylic Etherifications of 6 with Some Alcohols
Alcohol 6
R3
(eq)
Reaction
time
Product 7
Entry
R2
H
R1
(% yield)a)
1
2
3
4
5
6
7
8
9
10
11
12
13
6a
p-MeOC6H4
Bn (3)
Me(CH2)11 (3)
Allyl (10)
i-Pr (10)
Bn (5)
Propargyl (2)
Me (5)
Allyl (10)
Propargyl (7)
Cyclopentyl (3)
Cyclohexyl (3)
Ph-propargyl (3)
Bn (3)
10 min
18 h
10 min
20 min
2 h
48 h
24 h
72 h
15 h
15 h
21 h
19 h
5 h
7aa (63)
7ab (79)
7ac (92)
7ad (64)
7ba (81)
7bb (75)
7bc (82)
7ca (96)
7cb (79)
7cc (73)
7cd (46)
7da (92)
7db (88)
6b
6c
Ph
Ph
H
Ph
6d
Ph
n-Bu
a) The reaction was carried out with alcohol (5—10 eq) in MeNO2–H2O (10 : 1) at 30 °C.
Table 4. C–S Bond Formation of Propargyl Alcohols with Some Thiols
Alcohol 1
Reaction
time
Product
Entry
R2
R3 (eq)
R1
(% yield)a)
1
2
3
4
5
6
7
8
9
1a
p-MeOC6H4
SPh
Me(CH2)9 (1.3)
2-Naphthyl (2)
2-Thienyl (2)
p-ClC6H4 (2)
Cyclohexyl (2)
Me(CH2)9 (2)
p-ClC6H4 (2)
2-Naphthyl (1.3)
2-Naphthyl (2)
Me(CH2)9 (2)
p-ClC6H4 (2)
2-Naphthyl (2)
Me(CH2)9 (3)
2-Naphthyl (1.5)
p-ClC6H4 (1.5)
Me(CH2)9 (2)
1 h
8aa (91)
8ab (85)
8ac (61)
8ad (99)
8ae (94)
8ba (95)
8bb (67)
8ca (65)
8ga (64)
8gb (82)
8gc (89)
9ba (—)
9ca (82)
9cb (72)
9cc (48)
9da (52)
15 min
15 min
20 min
30 min
15 min
15 min
15 min
20 min
15 min
30 min
12 h
1b
1c
2-Thienyl
SPh
1-Naphthyl
SPh
SPh
1g Benzodioxol-5-yl
10
11
12
13
14
15
16
6b
6c
Ph
Ph
H
Ph
30 min
20 min
12 h
6d
Ph
n-Bu
1 h
a) The reaction was carried out in MeNO2–H2O (10 : 1) at 30 °C.
formed the reaction with other thiols such as 2-thienyl, naph- able yields (entries 13—16). However, the reaction of 1-
thyl, p-chlorophenyl and cyclohexylthiol and obtained satis- phenylpropargyl alcohol resulted in complete recovery of the
factory results (entries 2—5, Table 4). A variety of propargyl starting alcohol (entry 12). Therefore, this protocol provided
alcohols bearing the substituents such as R1ꢀ2-thienyl, 1- a wide variety of sulphides directly from propargyl alcohols.
naphthyl and benzodioxol-5-yl produced some propargyl sul-
In summary, we developed a powerful and novel protocol
phides 8ba—8gc in moderate to high yields (entries 6—11). for dehydrative etherifications from propargyl alcohols using
Surprisingly, Lewis acid-catalyzed C–S bond formation with a variety of simple alcohols as nucleophiles and a combina-
thiols generally proceeded without further addition of thiols tion of commercially available Lewis acids–Bu4NHSO4 in
to the alkynyl group, and the desired propargyl sulphides MeNO2–H2O. Since the removable organosulfanyl functional
were obtained in good to high yields (entries 1—11). We ex- groups can be easily converted to other functional groups,
pected that this is due to the strong stabilizing effect of the these propargyl ethers and sulfides will become the leading
sulfanyl group on acetylene. On the other hand, propargyl al- compounds by some transformations. We also described the
cohols bearing no sulphur functional group at the terminal sulfanylation of propargyl alcohols with thiols. Further work,
acetylene afforded some of the desired sulphides in reason- aims at development of useful organic synthesis using sulfur-

1136
Vol. 59, No. 9
C21H22O2S: C, 74.52; H, 6.55. Found: C, 74.31; H, 6.53.
substituted propargyl ethers and sulfides, and the synthesis of
new catalysts used in conjunction with MeNO2–H2O, is in
progress. The results will be reported elsewhere.
1-Methoxy-4-[1-(cyclohexyloxy)-3-(phenylsulfanyl)-2-propyn-1-yl]-
benzene (2ae) Yellow powders, mp 46—49 °C, IR (KBr, cmꢁ1) n: 2932,
2857, 2178, 1713, 1610, 1583, 1511, 1478, 1442, 1361, 1304, 1249, 1221,
1173, 1074, 1034, 950, 892, 831, 772, 740, 688; 1H-NMR (600 MHz,
CDCl3) d: 1.20—1.30 (3H, m, CH2), 1.34—1.45 (2H, m, CH2), 1.53—1.55
(1H, m, CH2), 1.74—1.77 (2H, m, CH2), 1.96 (2H, br s, CH2), 3.67—3.70
(1H, m, CH), 3.80 (3H, s, OMe), 5.43 (1H, s, CH), 6.90 (2H, d, Jꢀ9 Hz,
ArH), 7.20 (1H, t, Jꢀ7 Hz, ArH), 7.29—7.31 (2H, m, ArH), 7.38—7.40
(2H, m, ArH), 7.46 (2H, d, Jꢀ8 Hz, ArH); 13C-NMR (150 MHz, CDCl3) d:
24.1 (t), 24.2 (t), 25.7 (t), 31.7 (t), 33.0 (t), 55.3 (q), 68.9 (d), 73.0 (s), 75.5
(d), 98.2 (s), 113.8 (dꢂ2), 126.2 (dꢂ2), 126.4 (d), 128.6 (dꢂ2), 129.1
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 Fourier Transform-Infrared (FT-
IR) 460PLUS infrared spectrometer and are expressed in reciprocal centime-
ters. Electron ionization (EI) mass spectra (MS) were obtained using a JEOL (dꢂ2), 131.5 (s), 132.7 (s), 159.5 (s); MS m/z: 352 (Mꢃ), 269 (Mꢃꢁcyclo-
MS-700 spectrometer with a direct-insertion probe at 70 eV. All high-resolu- hexyl), 253 (MꢃꢁOC6H11). Anal. Calcd for C22H24O2S: C, 74.96; H, 6.86.
tion mass spectra were obtained using a JMSD300 JMA2000 online system.
1-(Benzyloxy-2-propyn-1-yl)benzene (7e) (Registry No: 129758-80-1). 1-
(Methoxy-2-propyn-1-yl)benzene (7g) (Registry No: 50874-13-0).
Typical Procedure for the Synthesis of 1-Methoxy-4-[1-butoxy-3-
(phenylthio)-2-propyn-1-yl]benzene (3a), Typical Procedure Scandium
Found: C, 75.10; H, 6.64.
1-Methoxy-4-[1-(geranyloxy)-3-(phenylsulfanyl)-2-propyn-1-yl]ben-
zene (2af) A pale yellow oil, IR (KBr, cmꢁ1) n: 3435, 2928, 2177, 1611,
1
1584, 1511, 1478, 1442, 1304, 1249, 1173, 1033, 831, 740, 688; H-NMR
(600 MHz, CDCl3) d: 1.60 (3H, s, Me), 1.67 (6H, d, Jꢀ1 Hz, Mex2), 2.03—
2.06 (2H, m, CH2), 2.09—2.13 (2H, m, CH2), 3.80 (3H, s, OMe), 4.17 (2H,
triflate (55 mg, 0.11 mmol) was added to
a
mixture of 1a (0.60 g,
2.22 mmol), 1-butanol (0.82 g, 11.0 mmol), tetrabutylammonium hydrogen- d, Jꢀ7 Hz, CH2), 5.09 (1H, t, Jꢀ7 Hz, olefinic H), 5.36 (1H, s, OCH), 5.39
sulfate (75.3 mg, 0.22 mmol) in MeNO2 (6.0 ml)–H2O (0.6 ml) at 30 °C. The
reaction mixture was stirred for 10 min and 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 the
preparative TLC on silica gel eluting with AcOEt–n-hexane (1 : 50) to give
the title compound 2aa (0.52 g, 71%) as a yellow oil.
(1H, t, Jꢀ7 Hz, olefinic H), 6.90 (2H, d, Jꢀ9 Hz, ArH), 7.19—7.22 (1H, m,
ArH), 7.31 (2H, br t, Jꢀ8 Hz, ArH), 7.41 (2H, d, Jꢀ8 Hz, ArH), 7.45 (2H, d,
Jꢀ8 Hz, ArH); 13C-NMR (150 MHz, CDCl3) d: 16.5 (q), 17.7 (q), 25.7 (q),
26.3 (t), 39.6 (t), 55.3 (q), 64.5 (t), 70.7 (d), 73.9 (s), 97.3 (s), 113.9 (dꢂ2),
120.2 (d), 124.9 (d), 126.3 (dꢂ2), 126.5 (d), 128.8 (dꢂ2), 129.2 (dꢂ2),
130.8 (s), 131.7 (s), 132.6 (s), 141.3 (s), 159.7 (s); MS m/z: 406 (Mꢃ), 337
(MꢃꢁCH2CHꢀCMe2). Anal. Calcd for C26H30O2S: C, 76.81; H, 7.44.
Found: C, 76.37; H, 7.41.
1-Methoxy-4-[1-butoxy-3-(phenylthio)-2-propyn-1-yl]benzene
(2aa)
A yellow oil, IR (KBr, cmꢁ1) n: 2957, 2932, 2869, 2178, 1710, 1610, 1584,
2-[1-Methoxy-3-(phenylthio)-2-propyn-1-yl]thiophene (2ba)
A yel-
1511, 1478, 1442, 1304, 1250, 1173, 1084, 1034, 831, 740, 688, 585, 519;
low oil, IR (KBr, cmꢁ1) n: 3436, 2928, 2178, 1582, 1478, 1442, 1288, 1230,
1H-NMR (600 MHz, CDCl3) d: 0.91 (3H, t, Jꢀ7 Hz, Me), 1.36—1.43 (2H, 1079, 1023, 931, 740, 706; 1H-NMR (600 MHz, CDCl3) d: 3.46 (3H, s,
m, CH2), 1.59—1.64 (2H, m, CH2), 3.49—3.53 (1H, m, OCH2), 3.67—3.70 OMe), 5.58 (1H, s, OCH), 6.99 (1H, dd, Jꢀ4 and 5 Hz, ArH), 7.19 (1H, d,
(1H, m, OCH2), 3.80 (3H, s, OMe), 5.32 (1H, s, CH), 6.90 (2H, br d, Jꢀ4 Hz, ArH), 7.22—7.28 (1H, m, ArH), 7.33 (3H, br t, Jꢀ8 Hz, ArH), 7.44
Jꢀ9 Hz, ArH), 7.20—7.22 (1H, m, ArH), 7.30—7.33 (2H, m, ArH), 7.39— (2H, br d, Jꢀ7 Hz, ArH); 13C-NMR (100 MHz, CDCl3) d: 55.3 (q), 69.1 (d),
7.41 (2H, m, ArH), 7.45 (2H, brd, Jꢀ9 Hz, ArH); 13C-NMR (100 MHz,
CDCl3) d: 13.8 (q), 19.3 (t), 31.6 (t), 55.3 (q), 68.1 (t), 72.0 (d), 73.7 (s),
97.4 (s), 113.8 (dꢂ2), 126.2 (dꢂ2), 126.5 (d), 128.7 (dꢂ2), 129.2 (dꢂ2),
130.8 (s), 132.6 (s), 159.6 (s); MS m/z: 253 (MꢃꢁBu). Anal. Calcd for
C20H22O2S: C, 74.04; H, 6.46. Found: C, 73.95; H, 6.47.
74.7 (s), 95.4 (s), 126.4 (d), 126.5 (dꢂ2), 126.5 (d), 126.6 (d), 126.7 (d),
129.3 (dꢂ2), 132.1 (s), 141.4 (s); MS m/z: 245 (MꢃꢁMe), 229
(MꢃꢁOMe); high resolution mass Calcd for C14H12OS2: 260.0329, Found
m/z 260.0274.
2-[1-Butoxy-3-(phenylthio)-2-propyn-1-yl]thiophene (2bb) A yellow
1-Methoxy-4-[1-methoxy-3-(phenylthio)-2-propyn-1-yl]benzene (2ab)
oil, IR (KBr, cmꢁ1) n: 3425, 2957, 2929, 2870, 2352, 2178, 1732, 1583,
A yellow oil, IR (KBr, cmꢁ1) n: 3428, 2929, 2360, 1610, 1510, 1478, 1442, 1478, 1442, 1380, 1356, 1287, 1230, 1084, 1039, 1024, 999, 899, 855, 836,
1
1304, 1250, 1173, 1079, 1033, 831, 740, 688; H-NMR (600 MHz, CDCl3) 739, 703, 688, 1H-NMR (600 MHz, CDCl3) d: 0.91 (3H, t, Jꢀ7 Hz, Me),
d: 3.44 (3H, s, OMe), 3.81 (3H, s, OMe), 5.25 (1H, s, CH), 6.91 (2H, d, 1.37—1.43 (2H, m, CH2), 1.58—1.63 (2H, m, CH2), 3.55—3.59 (1H, m,
Jꢀ8 Hz, ArH), 7.20—7.24 (1H, m, ArH), 7.32 (2H, br t, Jꢀ8 Hz, ArH), 7.41 OCH2), 3.66—3.70 (1H, m, OCH2), 5.62 (1H, s, OCH), 6.95 (1H, dd, Jꢀ1
(2H, d, Jꢀ8 Hz, ArH), 7.44 (2H, d, Jꢀ8 Hz, ArH); 13C-NMR (100 MHz,
CDCl3) d: 55.3 (q), 55.7 (q), 73.5 (d), 74.4 (s), 96.7 (s), 113.9 (dꢂ2), 126.3
and 5 Hz, ArH), 7.16 (1H, d, Jꢀ3 Hz, ArH), 7.19—7.21 (1H, m, ArH),
7.28—7.32 (3H, m, ArH), 7.42—7.43 (2H, m, ArH); 13C-NMR (100 MHz,
(dꢂ2), 126.6 (d), 128.8 (dꢂ2), 129.2 (dꢂ2), 130.3 (s), 132.5 (s), 159.8 (s); CDCl3) d: 13.8 (q), 19.3 (t), 31.6 (t), 67.8 (tꢂd), 74.0 (s), 96.1 (s), 126.1 (d),
MS m/z: 269 (MꢃꢁMe), 253 (MꢃꢁMeO). Anal. Calcd for C17H16O2S: C,
71.80; H, 5.67. Found: C, 71.95; H, 5.58.
126.2 (d), 126.4 (dꢂ2), 126.5 (d), 126.6 (d), 129.2 (dꢂ2), 132.2 (s), 142.0
(s); MS m/z: 302 (Mꢃ), 245 (MꢃꢁBu), 229 (MꢃꢁBuO); high resolution
mass Calcd for C17H18OS2: 302.0799, Found m/z 302.0789.
1-Methoxy-4-[1-(dodecyloxy)-3-(phenylsulfanyl)-2-propyn-1-yl]ben-
zene (2ac) A yellow oil, IR (KBr, cmꢁ1) n: 2925, 2853, 2179, 1713, 1609,
2-[1-(Cinnamyloxy)-3-(phenylthio)-2-propyn-1-yl]thiophene (2bc)
A
1584, 1510, 1478, 1465, 1442, 1304, 1250, 1173, 1083, 1035, 832, 739, yellow oil, IR (KBr, cmꢁ1) n: 3060, 3026, 2924, 2852, 2177, 1582, 1478,
687, 582, 418, 409; 1H-NMR (600 MHz, CDCl3) d: 0.87 (3H, t, Jꢀ7 Hz, 1442, 1294, 1230, 1071, 967, 836, 740, 691; 1H-NMR (600 MHz, CDCl3) d:
Me), 1.24—1.37 (14H, m, CH2), 1.55—1.58 (6H, m, CH2), 3.64 (2H, t, 4.33—4.40 (2H, m, CH2), 5.74 (1H, s, OCH), 6.30—6.35 (1H, m, olefinic
Jꢀ7 Hz, CH2), 3.81 (3H, s, OMe), 5.65 (1H, s, CH), 6.92 (2H, d, Jꢀ8 Hz, H), 6.66 (1H, d, Jꢀ16 Hz, olefinic H), 6.99 (1H, dd, Jꢀ4 and 5 Hz, ArH),
ArH), 7.21 (1H, t, Jꢀ7 Hz, ArH), 7.32—7.34 (2H, m, ArH), 7.40 (2H, d,
7.17—7.25 (3H, m, ArH), 7.29—7.34 (5H, m, ArH), 7.38 (2H, d, Jꢀ8 Hz,
Jꢀ8 Hz, ArH), 7.45 (2H, d, Jꢀ9 Hz, ArH); 13C-NMR (150 MHz, CDCl3) d: ArH), 7.45 (2H, d, Jꢀ8 Hz, ArH); 13C-NMR (100 MHz, CDCl3) d: 66.9 (d),
14.1 (q), 22.7 (t), 26.2 (t), 29.3 (t), 29.4 (t), 29.6 (tꢂ3), 29.6 (tꢂ2), 31.9 (t), 68.5 (t), 74.8 (s), 95.8 (s), 125.1 (d), 126.4 (d), 126.5 (dꢂ2), 126.6 (dꢂ2),
55.3 (q), 68.4 (t), 72.0 (d), 73.8 (s), 97.5 (s), 113.9 (dꢂ2), 126.2 (dꢂ2), 126.6 (d), 126.7 (d), 127.8 (d), 128.5 (dꢂ2), 129.3 (dꢂ2), 132.1 (s), 133.4
126.5 (d), 128.7 (dꢂ2), 129.2 (dꢂ2), 130.9 (s), 132.7 (s), 159.7 (s); MS m/z: (dꢂ2), 136.5 (s), 141.7 (s); MS m/z: 362 (Mꢃ), 245 (Mꢃꢁcinnamyl), 229
438 (Mꢃ), 329 (MꢃꢁPhS), 253 (MꢃꢁOC12H25). High resolution mass
Calcd for C28H38O2S: 438.2592, Found: 438.2584.
(Mꢃꢁcinnamyloxy). Anal. Calcd for C22H18OS2: C, 72.89; H, 5.00. Found:
C, 72.56; H, 5.00.
1-Methoxy-4-[1-(cyclopentyloxy)-3-(phenylsulfanyl)-2-propyn-1-yl]-
2-[1-(Cyclopentyloxy)-3-(phenylthio)-2-propyn-1-yl]thiophene (2bd)
benzene (2ad) A pale yellow oil, IR (KBr, cmꢁ1) n: 2956, 2870, 2836, A yellow oil, IR (KBr, cmꢁ1) n: 2959, 2178, 1583, 1479, 1442, 1355, 1294,
2178, 1887, 1712, 1610, 1583, 1510, 1478, 1442, 1329, 1303, 1249, 1173, 1230, 1174, 1069, 1038, 1023, 972, 854, 738, 704, 687; 1H-NMR (600 MHz,
1
1079, 1025, 831, 771, 740, 688, 580, 421; H-NMR (600 MHz, CDCl3) d: CDCl3) d: 1.49—1.58 (2H, m, CH2), 1.75—1.85 (6H, m, CH2), 4.32—4.35
1.51—1.56 (2H, m, CH2), 1.72—1.84 (6H, m, CH2), 3.80 (3H, s, OMe),
(1H, m, CHO), 5.59 (1H, s, CH2), 6.96 (1H, t, Jꢀ4 Hz, ArH), 7.16 (1H, d,
4.30—4.31 (1H, m, CH), 5.32 (1H, s, CH), 6.90 (2H, d, Jꢀ9 Hz, ArH), Jꢀ3 Hz, ArH), 7.20—7.24 (1H, m, ArH), 7.29—7.33 (3H, m, ArH), 7.43
7.19—7.21 (1H, m, ArH), 7.29—7.32 (2H, m, ArH), 7.39—7.40 (2H, m, (2H, d, Jꢀ8 Hz, ArH); 13C-NMR (100 MHz, CDCl3) d: 23.5 (tꢂ2), 32.1 (t),
ArH), 7.44—7.45 (2H, m, ArH); 13C-NMR (150 MHz, CDCl3) d: 23.6 32.9 (t), 66.2 (d), 73.5 (s), 79.8 (d), 96.9 (s), 125.8 (d), 126.0 (d), 126.3
(tꢂ2), 32.0 (t), 32.8 (t), 55.3 (q), 70.1 (d), 73.2 (s), 79.5(d), 98.1 (s), 113.8
(dꢂ2), 126.5 (d), 126.6 (d), 129.2 (dꢂ2), 132.3 (s), 142.8 (s); MS m/z: 314
(dꢂ2), 126.2 (dꢂ2), 126.4 (d), 128.6 (dꢂ2), 129.2 (dꢂ2), 131.3 (s), 132.7 (Mꢃ), 245 (MꢃꢁC5H9), 229 (MꢃꢁC5H9O). Anal. Calcd for C18H18OS2: C,
(s), 159.6 (s); MS m/z: 269 (MꢃꢁC5H9), 253 (MꢃꢁC5H9O). Anal. Calcd for 68.75; H, 5.77. Found: C, 68.27; H, 5.77.

September 2011
1137
MS m/z: 267 (MꢃꢁOCH2CHꢀCH2). Anal. Calcd for C19H16O3S: C, 70.35;
H, 4.97. Found: C, 70.43; H, 5.07.
2-[1-(Cyclohexyloxy)-3-(phenylthio)-2-propyn-1-yl]thiophene (2be)
A yellow oil, IR (KBr, cmꢁ1) n: 3440, 2930, 2856, 2178, 1583, 1478, 1442,
1
1287, 1230, 1158, 1074, 1024, 739, 704, 688; H-NMR (600 MHz, CDCl3)
5-[1-Methoxy-3-(phenylsulfanyl)-2-propyn-1-yl]-1,3-benzodioxole
(2fb) A pale yellow oil, IR (KBr, cmꢁ1) n: 3430, 2926, 2179, 1582, 1503,
1488, 1442, 1246, 1102, 1082, 1039, 936, 864, 812, 740, 688; 1H-NMR
(600 MHz, CDCl3) d: 3.44 (3H, s, OMe), 5.20 (1H, s, OCH), 5.96 (2H, s,
OCH2O), 6.80 (1H, d, Jꢀ8 Hz, ArH), 6.99 (1H, dd, Jꢀ1, 8 Hz, ArH), 7.02
(1H, d, Jꢀ1 Hz, ArH), 7.21—7.23 (1H, m, ArH), 7.31—7.34 (2H, m, ArH),
7.41 (2H, d, Jꢀ8 Hz, ArH); 13C-NMR (150 MHz, CDCl3) d: 55.8 (q), 73.6
(d), 74.7 (s), 96.3 (s), 101.2 (t), 107.9 (d), 108.0 (d), 121.1 (d), 126.4 (dꢂ2),
126.6 (d), 129.2 (dꢂ2), 132.1 (s), 132.4 (s), 147.8 (s), 147.9 (s); MS m/z:
283 (MꢃꢁMe), 267 (MꢃꢁOMe). Anal. Calcd for C17H14O3S: C, 68.44; H,
4.73. Found: C, 67.96; H, 4.74.
d: 1.22—1.32 (3H, m, CH2), 1.38—1.47 (2H, m, CH2), 1.54 (1H, br s, CH2),
1.76 (2H, br d, Jꢀ10 Hz, CH2), 1.95 (2H, br s, CH2), 3.71—3.74 (1H, m,
OCH), 5.70 (1H, s, OCH), 6.96 (1H, dd, Jꢀ5 and 3 Hz, ArH), 7.17 (1H, d,
Jꢀ3 Hz, ArH), 7.22 (1H, q, Jꢀ8 Hz, ArH), 7.29 (1H, dd, Jꢀ4 and 5 Hz,
ArH), 7.32 (2H, t, Jꢀ8 Hz, ArH), 7.42 (2H, d, Jꢀ8 Hz, ArH); 13C-NMR
(100 MHz, CDCl3) d: 24.0 (t), 24.1 (t), 25.7 (t), 31.7 (t), 32.9 (t), 65.1 (d),
73.2 (s), 75.8 (d), 97.0 (s), 125.7 (d), 125.9 (d), 126.3 (dꢂ2), 126.5 (d),
126.6 (d), 129.2 (dꢂ2), 132.3 (s), 142.9 (s); MS m/z: 245 (Mꢃꢁcyclohexyl),
229 (Mꢃꢁcyclohexyloxy). Anal. Calcd for C19H20OS2: C, 69.47; H, 6.14.
Found: C, 69.17; H, 6.13.
1-[1-Butoxy-3-(phenylthio)-2-propyn-1-yl]naphthalene (2ca) A yel-
low oil, IR (KBr, cmꢁ1) n: 3059, 2957, 2869, 2176, 1582, 1510, 1478, 1442,
1300, 1256, 1165, 1083, 1045, 1024, 801, 780, 739, 687, 630, 586, 510,
424; 1H-NMR (600 MHz, CDCl3) d: 0.88 (3H, t, Jꢀ7 Hz, ArH), 1.36—1.42
(2H, m, CH2), 1.61—1.65 (2H, m, CH2), 3.57—3.61 (1H, m, OCH2), 3.76—
3.79 (1H, m, OCH2), 5.92 (1H, s, OCH), 7.15—7.18 (1H, m, ArH), 7.22—
7.24 (2H, m, ArH), 7.33—7.35 (2H, m, ArH), 7.43—7.45 (1H, m, ArH),
7.46—7.52 (1H, m, ArH), 7.53—7.56 (1H, m, ArH), 7.75 (1H, d, Jꢀ7 Hz,
ArH), 7.83 (1H, d, Jꢀ8 Hz, ArH), 7.87 (1H, d, Jꢀ8 Hz, ArH), 8.35 (1H,
br d, Jꢀ9 Hz, ArH); 13C-NMR (100 MHz, CDCl3) d: 13.8 (q), 19.4 (t), 31.8
(t), 68.5 (t), 71.4 (d), 74.6 (s), 97.2 (s), 124.5 (d), 125.1 (d), 125.8 (d), 125.9
(d), 126.2 (d), 126.2 (dꢂ2), 126.5 (d), 128.6 (d), 129.1 (dꢂ2), 129.3 (d),
130.8 (s), 132.6 (s), 133.9 (s), 134.1 (s); MS m/z: 346 (Mꢃ), 289 (MꢃꢁBu),
273 (MꢃꢁOBu). Anal. Calcd for C23H22OS: C, 79.73; H, 6.40. Found: C,
79.54; H, 6.37.
1,3,5-Trimethyl-2-[1-butoxy-3-(phenylthio)-2-propyn-1-yl]benzene
(2da) A yellow oil, IR (KBr, cmꢁ1) n: 2957, 2929, 2870, 2170, 1610,
1582, 1478, 1442, 1378, 1308, 1087, 1024, 851, 738, 687; 1H-NMR
(600 MHz, CDCl3) d: 0.90 (3H, t, Jꢀ7 Hz, Me), 1.36—1.42 (2H, m, CH2),
1.56—1.64 (2H, m, CH2), 2.25 (3H, s, Me), 2.46 (6H, s, Meꢂ2), 3.38—3.41
(1H, m, OCH2), 3.68—3.72 (1H, m, OCH2), 5.66 (1H, s, OCH), 6.84 (2H, s,
ArH), 7.17—7.20 (1H, m, ArH), 7.27—7.30 (2H, m, ArH), 7.35—7.36 (2H,
m, ArH); 13C-NMR (100 MHz, CDCl3) d: 13.8 (q), 19.4 (t), 20.4 (qꢂ2),
20.9 (q), 31.8 (t), 68.1 (d), 68.5 (t), 72.8 (s), 97.2 (s), 126.3 (dꢂ2), 126.4 (d),
129.1 (dꢂ2), 129.8 (dꢂ2), 132.0 (s), 132.9 (s), 136.7 (sꢂ2), 137.6 (s); MS
m/z: 281 (MꢃꢁBu), 265 (MꢃꢁBuO). Anal. Calcd for C22H26OS: C, 78.06;
H, 7.74. Found: C, 77.59; H, 7.55.
5-[1-Cyclopentyloxy-3-(phenylsulfanyl)-2-propyn-1-yl]-1,3-benzodi-
oxole (2fc) A pale yellow oil, IR (KBr, cmꢁ1) n: 2957, 1714, 1583, 1504,
1488, 1442, 1246, 1079, 1039, 933, 812, 740, 688; 1H-NMR (600 MHz,
CDCl3) d: 1.53—1.55 (2H, m, CH2), 1.71—1.85 (6H, m, CH2), 4.28—4.31
(1H, m, OCH), 5.26 (1H, s, OCH), 5.95 (2H, s, OCH2O), 6.78 (1H, d,
Jꢀ8 Hz, ArH), 6.98 (1H, dd, Jꢀ1, 8 Hz, ArH), 7.02 (1H, d, Jꢀ1 Hz, ArH),
7.19—7.24 (1H, m, ArH), 7.29—7.32 (2H, m, ArH), 7.39 (2H, dd, Jꢀ1,
9 Hz, ArH); 13C-NMR (150 MHz, CDCl3) d: 23.6 (tꢂ2), 32.0 (t), 32.8 (t),
70.3 (d), 73.4 (s), 79.6 (d), 97.7 (s), 101.1 (t), 107.9 (d), 108.0 (d), 120.9 (d),
126.3 (dꢂ2), 126.5 (d), 129.2 (dꢂ2), 132.6 (s), 133.1 (s), 147.6 (s), 147.8
(s); MS m/z: 352 (Mꢃ), 283 (MꢃꢁC5H9), 267 (MꢃꢁC5H9O). Anal. Calcd
for C21H20O3S: C, 71.57; H, 5.72. Found: C, 71.07; H, 5.93.
6-Benzyloxy-6-(plenylsulfanylethynyl)undecane (2ga) A colorless oil,
IR (KBr, cmꢁ1) n: 3063, 3031, 2954, 2862, 2164, 1942, 1868, 1799, 1716,
1583, 1496, 1478, 1455, 1442, 1378, 1360, 1309, 1245, 1217, 1139, 1086,
1026, 930, 737, 695, 688; 1H-NMR (600 MHz, CDCl3) d: 0.90 (6H, t,
Jꢀ7 Hz, Meꢂ2), 1.33 (8H, br s, CH2), 1.50—1.54 (5H, m, CH2), 1.82 (4H,
t, Jꢀ8 Hz, CH2), 4.64 (2H, s, CH2), 7.21 (1H, br t, Jꢀ7 Hz, ArH), 7.25 (1H,
br t, Jꢀ7 Hz, ArH), 7.30—7.33 (3H, m, ArH), 7.36 (2H, br d, Jꢀ7 Hz, ArH),
7.41 (2H, br d, Jꢀ7 Hz, ArH); 13C-NMR (150 MHz, CDCl3) d: 14.1 (qꢂ2),
22.6 (tꢂ2), 23.7 (tꢂ2), 32.1 (tꢂ2), 38.6 (tꢂ2), 66.2 (t), 72.3 (s), 78.0 (s),
100.6 (s), 126.0 (dꢂ2), 126.4 (d), 127.2 (d), 127.6 (dꢂ2), 128.2 (dꢂ2),
129.2 (dꢂ2), 133.0 (s), 139.2 (s); MS m/z: 394 (Mꢃ), 303 (MꢃꢁBn), 286
(MꢃꢁBnOH), 261 (MꢃꢁC2SPh). Anal. Calcd for C26H34OS: C, 79.14; H,
8.68. Found: C, 79.03; H, 8.68.
1-[1-Butoxy-1-phenyl-3-(phenylsulfanyl)-2-propyn-1-yl]benzene (2ha)
A pale yellow oil, IR (KBr, cmꢁ1) n: 3060, 3025, 2957, 2930, 2871, 2171,
1583, 1489, 1478, 1448, 1380, 1194, 1177, 1079, 1065, 1041, 1027, 968,
1-Fluoro-4-[1-butoxy-1-phenyl-3-(phenylthio)-2-propyn-1-yl]benzene
(2ea) A yellow oil, IR (KBr, cmꢁ1) n: 3062, 2958, 2932, 2871, 2179,
1731, 1604, 1583, 1508, 1478, 1442, 1412, 1381, 1296, 1226, 1156, 1086,
1
931, 902, 739, 699, 666, 651; H-NMR (600 MHz, CDCl3) d: 0.91 (3H, t,
Jꢀ7 Hz, Me), 1.41—1.48 (2H, m, CH2), 1.63—1.67 (2H, m, CH2), 3.53
(2H, t, Jꢀ7 Hz, OCH2), 7.18—7.21 (1H, m, ArH), 7.24—7.28 (4H, m,
ArH), 7.30—7.36 (6H, m, ArH), 7.57 (4H, d, Jꢀ8 Hz, ArH); 13C-NMR
(150 MHz, CDCl3) d: 13.9 (q), 19.5 (t), 32.0 (t), 64.6 (t), 76.0 (s), 81.0 (s),
99.1 (s), 126.2 (dꢂ2), 126.5 (d), 126.7 (dꢂ4), 127.6 (dꢂ2), 128.2 (dꢂ4),
129.2 (dꢂ2), 132.8 (s), 143.6 (sꢂ2); MS m/z: 372 (Mꢃ), 315 (MꢃꢁBu),
299 (MꢃꢁBuO). Anal. Calcd for C25H24OS: C, 80.61; H, 6.49. Found: C,
80.63; H, 6.71.
1
836, 787, 739, 687, 569, 509; H-NMR (600 MHz, CDCl3) d: 0.91 (3H, t,
Jꢀ7 Hz, Me), 1.36—1.44 (2H, m, CH2), 1.61—1.65 (2H, m, CH2), 3.47—
3.65 (1H, m, OCH2), 3.70—3.74 (1H, m, OCH2), 5.34 (1H, s, OCH), 7.04—
7.08 (2H, m, ArH), 7.20—7.24 (1H, m, ArH), 7.30—7.32 (2H, m, ArH),
7.38—7.40 (2H, m, ArH), 7.49—7.52 (2H, m, ArH); 13C-NMR (150 MHz,
CDCl3) d: 13.8 (q), 19.4 (t), 31.6 (t), 68.4 (t), 71.0 (d), 76.8 (s), 96.8 (s),
115.3 (d), 115.4 (d), 126.3 (dꢂ2), 126.6 (d), 129.0 (d), 129,1 (d), 129.2
(dꢂ2), 132.4 (s), 134.5 (s), 162.6 (d, Jꢀ247 Hz); MS m/z: 314 (Mꢃ), 257
(MꢃꢁBu); high resolution mass Calcd for C19H19FOS: 314.1140, Found m/z
314.1086.
1-(Dodecyloxy)-1-(phenylsulfanylethynyl)cyclohexane (2ia) A color-
less oil, IR (KBr, cmꢁ1) n: 2928, 2854, 1709, 1634, 1584, 1479, 1465, 1442,
1415, 1363, 1341, 1258, 1227, 1160, 1069, 1035, 1024, 965, 903, 738, 687;
1H-NMR (600 MHz, CDCl3) d: 0.88 (3H, t, Jꢀ7 Hz, Me), 1.23—1.30 (18H,
m, CH2), 1.54—1.74 (10H, m, CH2), 1.98—2.04 (2H, m, CH2), 3.62 (2H, t,
Jꢀ6 Hz, OCH2), 7.21 (1H, t, Jꢀ7 Hz, ArH), 7.32 (2H, t, Jꢀ7 Hz, ArH), 7.40
(2H, dd, Jꢀ1, 8 Hz, ArH); 13C-NMR (150 MHz, CDCl3) d: 14.1 (q), 22.6 (t),
23.2 (t), 25.1 (t), 25.7 (t), 29.3 (t), 29.4 (t), 29.6 (tꢂ2), 29.7 (tꢂ3), 31.9 (t),
32.7 (t), 39.8 (tꢂ2), 63.0 (t), 69.6 (s), 70.4 (s), 102.6 (s), 125.9 (dꢂ2), 126.4
(d), 129.2 (dꢂ2), 132.8 (s); MS m/z: 400 (Mꢃ), 215 (MꢃꢁOC12H25); high
resolution mass Calcd for C26H40OS: 400.2799, Found m/z 400.2783.
1-(Dodecyloxy)-1-(phenylsulfanylethynyl)cyclopentane (2ja) A pale
yellow oil, IR (KBr, cmꢁ1) n: 3076, 3062, 2956, 2925, 2871, 2853, 2363,
2170, 1703, 1584, 1478, 1467, 1441, 1378, 1314, 1210, 1181, 1075, 1024,
997, 945, 919, 738, 687; 1H-NMR (600 MHz, CDCl3) d: 0.88 (3H, t,
Jꢀ7 Hz, Me), 1.26—1.35 (18H, m, CH2), 1.53—1.58 (2H, m, CH2), 1.77—
1.80 (2H, m, CH2), 1.85—1.88 (2H, m, CH2), 2.02—2.07 (4H, m, CH2),
3.63 (2H, t, Jꢀ7 Hz, CH2), 7.21 (1H, t, Jꢀ7 Hz, ArH), 7.33 (2H, t, Jꢀ8 Hz,
ArH), 7.39—7.41 (2H, m, ArH); 13C-NMR (150 MHz, CDCl3) d: 14.1 (q),
22.6 (t), 23.5 (tꢂ2), 25.7 (t), 29.3 (t), 29.4 (t), 29.6 (tꢂ2, t), 29.6 (t), 31.9 (t),
32.7 (t), 42.5 (tꢂ2), 63.0 (t), 69.6 (s), 75.3 (s), 102.6 (s), 125.9 (dꢂ2), 126.4
(dꢂ2), 129.2 (d), 132.8 (s); MS m/z: 386 (Mꢃ), 277 (MꢃꢁSPh), 201
(MꢃꢁOC12H25). Anal. Calcd for C25H38OS: C, 77.66; H, 9.91. Found: C,
77.55; H, 9.90.
1-Fluoro-4-[1-methoxy-1-phenyl-3-(phenylthio)-2-propyn-1-yl]ben-
zene (2eb) A yellow oil, IR (KBr, cmꢁ1) n: 2931, 2179, 1604, 1583, 1508,
1478, 1327, 1226, 1184, 1157, 1082, 837, 789, 740, 688, 752; 1H-NMR
(600 MHz, CDCl3) d: 3.47 (3H, s, OMe), 5.28 (1H, s, OCH), 7.05—7.08
(2H, m, ArH), 7.21—7.24 (1H, m, ArH), 7.32 (2H, br t, Jꢀ7 Hz, ArH), 7.40
(2H, d, Jꢀ8 Hz, ArH), 7.49—7.50 (2H, m, ArH); 13C-NMR (150 MHz,
CDCl3) d: 56.0 (q), 73.2 (d), 75.2 (s), 96.1 (s), 115.4 (d), 115.5 (d), 126.4
(dꢂ2), 126.7 (d), 129.1 (d), 129.2 (d), 129.3 (dꢂ2), 132.3 (s), 134.1 (s),
162.8 (d, Jꢀ247 Hz); MS m/z: 272 (Mꢃ), 241 (MꢃꢁOMe); high resolution
mass Calcd for C16H13FOS: 272.0671, Found m/z 272.0601.
5-[1-Allyloxy-3-(phenylsulfanyl)-2-propyn-1-yl]-1,3-benzodioxole (2fa)
A pale yellow oil, IR (KBr, cmꢁ1) n: 3292, 2898, 2178, 1582, 1503, 1488,
1442, 1379, 1303, 1247, 1103, 1040, 937, 863, 813, 740, 687; 1H-NMR
(600 MHz, CDCl3) d: 4.10—4.13 (1H, m, OCH2), 4.19—4.22 (1H, m,
OCH2), 5.23 (1H, br d, Jꢀ11 Hz, olefinic H), 5.32 (1H, s, CHO), 5.35 (1H,
dd, Jꢀ2, 17 Hz, olefinic H), 5.92—5.98 (3H, m, olefinic H, OCH2O), 6.79
(1H, d, Jꢀ8 Hz, ArH), 6.99 (1H, dd, Jꢀ2, 8 Hz, ArH), 7.04 (1H, d, Jꢀ2 Hz,
ArH), 7.21—7.25 (1H, m, ArH), 7.32 (2H, t, Jꢀ8 Hz, ArH), 7.41 (2H, d,
Jꢀ8 Hz, ArH); 13C-NMR (150 MHz, CDCl3) d: 69.1 (t), 71.3 (d), 74.5 (s),
96.7 (s), 101.2 (t), 108.0 (d), 108.1 (d), 117.9 (t), 121.1 (d), 126.3 (dꢂ2),
126.6 (d), 129.2 (dꢂ2), 132.2 (s), 132.4 (s), 134.1 (d), 147.8 (s), 147.9 (s);

1138
1-(Dodecyloxy)-1-(phenylsulfanylethynyl)cycloheptane (2ka) A pale
Vol. 59, No. 9
oil, IR (KBr, cmꢁ1) n: 3452, 3309, 2925, 2854, 2360, 2112, 1714, 1610,
1512, 1465, 1360, 1304, 1250, 1173, 1084, 1037, 829, 775, 721, 657, 633,
584, 530; 1H-NMR (600 MHz, CDCl3) d: 0.88 (3H, t, Jꢀ7 Hz, Me), 1.25
(18H, br s, CH2), 1.58—1.63 (2H, m, CH2), 2.60 (1H, d, Jꢀ3 Hz, acetylenic
H), 3.44—3.48 (1H, m, OCH2), 3.60—3.64 (1H, m, OCH2), 3.80 (3H, s,
OMe), 5.09 (1H, d, Jꢀ2 Hz, OCH), 6.89 (2H, d, Jꢀ9 Hz, ArH), 7.43 (2H, d,
Jꢀ9 Hz, ArH); 13C-NMR (150 MHz, CDCl3) d: 14.1 (q), 22.7 (t), 26.1 (t),
29.3 (t), 29.4 (t), 29.5 (t), 29.6 (tꢂ2), 29.7 (tꢂ2), 31.9 (t), 55.3 (q), 68.4 (t),
70.8 (d), 75.0 (d), 82.2 (s), 113.8 (dꢂ2), 128.6 (dꢂ2), 130.7 (s), 159.7 (s);
MS m/z: 330 (Mꢃ); high resolution mass Calcd for C22H34O2: 330.2558,
Found m/z 330.2516.
1-Methoxy-4-(1-allyloxy-2-propyn-1-yl)benzene (7ac) A yellow oil,
IR (KBr, cmꢁ1) n: 3290, 3079, 3005, 2957, 2838, 2112, 1713, 1647, 1612,
1578, 1513, 1464, 1422, 1335, 1304, 1250, 1174, 830, 778, 658, 583, 542;
1H-NMR (600 MHz, CDCl3) d: 2.63 (1H, d, Jꢀ2 Hz, acetylenic H), 3.81
(3H, s, OMe), 4.08—4.10 (1H, m, OCH2), 4.15—4.16 (1H, m, OCH2), 5.16
(1H, d, Jꢀ3 Hz, OCH), 5.21 (1H, dd, Jꢀ1, 10 Hz, olefinic H), 5.32 (1H, dd,
Jꢀ1, 15 Hz, olefinic H), 5.91—5.97 (1H, m, olefinic H), 6.90 (2H, d,
Jꢀ9 Hz, ArH), 7.44 (2H, d, Jꢀ9 Hz, ArH); 13C-NMR (150 MHz, CDCl3) d:
55.3 (q), 69.0 (t), 69.9 (d), 75.3 (d), 81.8 (s), 113.9 (dꢂ2), 117.8 (t), 128.8
(dꢂ2), 130.4 (s), 134.2 (d), 159.8 (s); MS m/z: 202 (Mꢃ); high resolution
mass Calcd for C13H14O2: 202.0994, Found m/z 202.0944.
1-Methoxy-4-(1-isopropyloxy-2-propyn-1-yl)benzene (7ad) A yellow
oil, IR (KBr, cmꢁ1) n: 3289, 2972, 2933, 2837, 2359, 2112, 1713, 1613,
1586, 1513, 1465, 1420, 1373, 1334, 1304, 1249, 1173, 1122, 1037, 969,
914, 819, 914, 819, 771, 655, 586, 540; 1H-NMR (600 MHz, CDCl3) d: 1.20
(3H, d, Jꢀ7 Hz, Me), 1.23 (3H, d, Jꢀ7 Hz, Me), 2.57 (1H, d, Jꢀ2 Hz,
acetylenic H), 3.80 (3H, s, OMe), 3.91—3.99 (1H, m, OCH), 5.14 (1H, d,
Jꢀ1 Hz, OCH), 6.89 (2H, d, Jꢀ8 Hz, ArH), 7.42 (2H, d, Jꢀ8 Hz, ArH); 13C-
NMR (150 MHz, CDCl3) d: 21.7 (q), 22.7 (q), 55.3 (q), 68.2 (d), 69.5 (d),
74.4 (d), 82.9 (s), 113.9 (dꢂ2), 128.6 (dꢂ2), 131.3 (s), 159.6 (s); MS m/z:
204 (Mꢃ); high resolution mass Calcd for C13H16O2: 204.1150, Found m/z
204.1080.
yellow oil, IR (KBr, cmꢁ1) n: 2926, 2854, 2364, 2174, 1938, 1706, 1584,
1479, 1461, 1442, 1378, 1350, 1200, 1123, 1024, 957, 909, 846, 738, 723,
687, 667; 1H-NMR (600 MHz, CDCl3) d: 0.88 (3H, t, Jꢀ6 Hz, Me), 1.30
(18H, br s, CH2), 1.53—1.62 (8H, m, CH2), 1.69 (2H, br s, CH2), 1.90—1.94
(2H, m, CH2), 2.04—2.13 (2H, m, CH2), 3.62 (2H, t, Jꢀ7 Hz, CH2), 7.21
(1H, t, Jꢀ7 Hz, ArH), 7.32 (2H, t, Jꢀ8 Hz, ArH), 7.41 (2H, d, Jꢀ8 Hz,
ArH); 13C-NMR (150 MHz, CDCl3) d: 14.1 (q), 22.2 (tꢂ2), 22.6 (t), 25.7
(t), 28.0 (tꢂ2), 29.3 (t), 29.4 (t), 29.6 (tꢂ2), 29.6 (tꢂ2), 31.9 (t), 32.7 (t),
42.9 (tꢂ2), 63.0 (t), 69.6 (s), 72.7 (s), 103.7 (s), 125.9 (dꢂ2), 126.3 (d),
129.1 (dꢂ2), 132.9 (s); MS m/z: 414 (Mꢃ), 305 (MꢃꢁSPh), 229
(MꢃꢁOC12H25). Anal. Calcd for C27H42OS: C, 78.20; H, 10.21. Found: C,
78.24; H, 10.14.
1-Methoxy-4-[3-(phenylselanyl)-1-methoxy-2-propyn-1-yl]benzene
(4aa) A pale yellow oil, IR (KBr, cmꢁ1) n: 2933, 2836, 2168, 1890, 1712,
1675, 1602, 1577, 1510, 1476, 1439, 1359, 1304, 1250, 1173, 1081, 1022,
832, 737, 688, 580; 1H-NMR (600 MHz, CDCl3) d: 3.43 (3H, s, OMe), 3.80
(3H, s, OMe), 5.24 (1H, s, CH), 6.91 (2H, d, Jꢀ9 Hz, ArH), 7.24—7.26
(1H, m, ArH), 7.28—7.31 (2H, m, ArH), 7.44 (2H, d, Jꢀ9 Hz, ArH), 7.51—
7.52 (2H, m, ArH); 13C-NMR (150 MHz, CDCl3) d: 55.3 (q), 55.7 (q), 67.8
(s), 73.6 (d), 101.5 (s), 113.9 (dꢂ2), 127.1 (d), 128.5 (s), 128.8 (dꢂ2), 129.1
(dꢂ2), 129.5 (dꢂ2), 130.4 (s), 159.8 (s); MS m/z: 332 (Mꢃ), 301
(MꢃꢁOMe), 175 (MꢃꢁPhSe), 151 (MꢃꢁC2SePh). Anal. Calcd for
C17H16O2Se: C, 61.63; H, 4.87. Found: C, 61.33; H, 4.89.
1-[1-Benzyloxy-3-(phenylselanyl)-2-propyn-1-yl]benzodioxole (4ba)
A pale yellow oil, IR (KBr, cmꢁ1) n: 3060, 3030, 2892, 2169, 1952, 1865,
1608, 1577, 1502, 1487, 1441, 1373, 1303, 1247, 1208, 1123, 1100, 1084,
1065, 1039, 999, 935, 864, 811, 784, 736, 698, 688, 666; 1H-NMR
(600 MHz, CDCl3) d: 4.64 (1H, d, Jꢀ16 Hz, CH2), 4.71 (1H, d, Jꢀ16 Hz,
CH2), 5.30 (1H, s, CH), 5.93 (2H, s, OCH2O), 6.77 (1H, d, Jꢀ8 Hz, ArH),
6.98 (1H, dd, Jꢀ1, 8 Hz, ArH), 7.04 (1H, d, Jꢀ1 Hz, ArH), 7.21—7.30 (4H,
m, ArH), 7.32—7.37 (4H, m, ArH), 7.51 (2H, d, Jꢀ7 Hz, ArH); 13C-NMR
(150 MHz, CDCl3) d: 68.1 (s), 69.9 (t), 71.1 (d), 101.1 (t), 101.3 (s), 108.0
(d), 108.1 (d), 121.2 (d), 127.2 (d), 127.7 (d), 128.1 (dꢂ2), 128.3 (s), 128.4
(dꢂ2), 129.1 (dꢂ2), 129.5 (dꢂ2), 132.3 (s), 137.5 (s), 147.7 (s), 147.8 (s);
MS m/z: 422 (Mꢃ), 315 (MꢃꢁOCH2Ph), 265 (MꢃꢁPhSe). Anal. Calcd for
C23H18O3Se: C, 65.60; H, 4.31. Found: C, 65.24; H, 4.29.
1-(1-Propargyloxy-2-propyn-1-yl)benzene (7bb)46,47)
1-Allyloxy-3-phenyl-2-propyn-1-ylbenzene (7ca)
A yellow oil, IR
(KBr, cmꢁ1) n: 3066, 3032, 2923, 2858, 2225, 1716, 1601, 1493, 1450,
1277, 1180, 1061, 926, 756, 694, 532; 1H-NMR (600 MHz, CDCl3) d:
4.16—4.19 (1H, m, OCH2), 4.24—4.26 (1H, m, OCH2), 5.23 (1H, dd, Jꢀ1,
10 Hz, olefinic H), 5.35 (1H, dd, Jꢀ1, 14 Hz, olefinic H), 5.44 (1H, s, OCH),
5.96—6.02 (1H, m, olefinic H), 7.29—7.31 (3H, m, ArH), 7.32—7.33 (1H,
m, ArH), 7.34—7.39 (2H, m, ArH), 7.47—7.48 (2H, m, ArH), 7.59 (2H, d,
Jꢀ7 Hz, ArH); 13C-NMR (150 MHz, CDCl3) d: 69.2 (t), 71.1 (d), 86.9 (s),
87.5 (s), 117.7 (t), 122.5 (s), 127.5 (dꢂ2), 128.2 (dꢂ2), 128.4 (d), 128.5
(dꢂ3), 131.8 (dꢂ2), 134.3 (d), 138.7 (s); MS m/z: 248 (Mꢃ), 191 (Mꢃꢁ
allyloxy); high resolution mass Calcd for C18H16O: 248.1201, Found m/z
248.1161.
2-[Benzyloxy-3-(phenylselanyl)-2-propyn-1-yl]naphthalene (4ca)
A
pale yellow oil, IR (KBr, cmꢁ1) n: 3060, 2924, 2856, 2169, 1948, 1875,
1598, 1577, 1509, 1476, 1454, 1440, 1395, 1379, 1359, 1302, 1258, 1233,
1210, 1166, 1083, 1065, 1050, 1021, 999, 932, 905, 802, 780, 735, 698,
687, 666; 1H-NMR (600 MHz, CDCl3) d: 4.76 (2H, s, CH2), 5.99 (1H, s,
CH), 7.18—7.23 (3H, m, ArH), 7.24—7.40 (5H, m, ArH), 7.43—7.52 (5H,
m, ArH), 7.76 (1H, d, Jꢀ7 Hz, ArH), 7.80—7.87 (2H, m, ArH), 8.28—8.29
(1H, m, ArH); 13C-NMR (150 MHz, CDCl3) d: 68.8 (s), 70.1 (t), 70.3 (d),
101.4 (s), 124.5 (d), 125.1 (d), 125.8 (d), 126.2 (d), 126.2 (d), 126.9 (d),
127.1 (d), 127.8 (d), 128.3 (dꢂ2), 128.4 (dꢂ2), 128.5 (s), 128.6 (d), 129.1
(dꢂ2), 129.5 (dꢂ2), 130.8 (s), 133.6 (s), 134.1 (s), 137.5 (s); MS m/z: 428
(Mꢃ), 321 (MꢃꢁOCH2Ph), 271 (MꢃꢁSePh). Anal. Calcd for C26H20Se: C,
73.07; H, 4.72. Found: C, 72.97; H, 4.86.
1-(3-Phenyl-1-propargyloxyprop-2-yn-1-yl)benzene (7cb)46,47) A yel-
low oil, IR (KBr, cmꢁ1) n: 3294, 3062, 3033, 2903, 2854, 2360, 2224, 2117,
1640, 1599, 1574, 1491, 1454, 1443, 1330, 1311, 1193, 1177, 1062, 1028,
984, 938, 918, 900, 844, 758, 726, 692, 640, 591, 556, 528; 1H-NMR
(600 MHz, CDCl3) d: 2.48 (1H, t, Jꢀ2 Hz, acetylenic H), 4.31 (1H, dd, Jꢀ2,
14 Hz, OCH2), 4.44 (1H, dd, Jꢀ2, 14 Hz, OCH2), 5.64 (1H, s, OCH), 7.29—
7.31 (4H, m, ArH), 7.34—7.40 (2H, m, ArH), 7.47—7.48 (2H, m, ArH),
7.59 (2H, d, Jꢀ7 Hz, ArH); 13C-NMR (150 MHz, CDCl3) d: 55.4 (t), 70.5
(d), 75.0 (d), 79.3 (s), 85.9 (s), 88.0 (s), 122.3 (s), 127.7 (dꢂ2), 128.2
(dꢂ2), 128.5 (dꢂ2), 128.6 (dꢂ2), 131.8 (dꢂ2), 137.9 (s); MS m/z: 245
(Mꢃꢁ1), 191 (MꢃꢁOCH2CCH). Anal. Calcd for C18H14O: C, 87.78; H,
5.73. Found: C, 87.56; H, 5.88.
1-Cyclopentyloxy-3-phenylprop-2-yn-1-ylbenzene (7cc) White pow-
ders, mp 90—91 °C, IR (KBr, cmꢁ1) n: 3062, 3032, 2958, 2871, 2224, 1715,
1599, 1491, 1451, 1369, 1306, 1278, 1175, 1053, 1004, 990, 915, 757, 723,
692, 640, 527; 1H-NMR (600 MHz, CDCl3) d: 1.51—1.56 (2H, m, CH2),
1.72—1.87 (6H, m, CH2), 4.35—4.37 (1H, m, OCH), 5.38 (1H, s, OCH),
7.29—7.32 (4H, m, ArH), 7.36—7.38 (2H, m, ArH), 7.46—7.48 (2H, m,
ArH), 7.56—7.58 (2H, m, ArH); 13C-NMR (150 MHz, CDCl3) d: 23.6
(tꢂ2), 32.0 (t), 32.9 (t), 70.1 (d), 79.7 (d), 86.7 (s), 88.0 (s), 122.8 (s), 127.4
(dꢂ2), 128.1 (d), 128.2 (dꢂ2), 128.3 (d), 128.4 (dꢂ2), 131.8 (dꢂ2), 139.5
(s); MS m/z: 276 (Mꢃ); high resolution mass Calcd for C20H20O: 276.1514,
Found m/z 276.1501.
1-Benzyloxy-1-[3-(phenylselanyl)-1-propyn-1-yl]cyclohexane (4da)
A
pale yellow oil, IR (KBr, cmꢁ1) n: 3061, 3031, 2934, 2856, 2359, 2341,
2162, 1946, 1864, 1803, 1714, 1577, 1496, 1451, 1441, 1379, 1339, 1286,
1256, 1203, 1149, 1087, 1066, 1022, 999, 967, 937, 905, 853, 734, 696,
1
687, 667; H-NMR (600 MHz, CDCl3) d: 1.32—1.36 (1H, m, CH2), 1.53—
1.62 (4H, m, CH2), 1.70—1.79 (4H, m, CH2), 2.04 (2H, t, Jꢀ7 Hz, CH),
4.69 (2H, s, CH2), 7.22—7.33 (5H, m, ArH), 7.37 (2H, d, Jꢀ7 Hz, ArH),
7.50—7.52 (2H, m, ArH); 13C-NMR (150 MHz, CDCl3) d: 22.8 (t), 25.4
(tꢂ2), 37.3 (tꢂ2), 65.2 (s), 65.7 (t), 75.2 (s), 105.6 (s), 126.9 (d), 127.3 (d),
127.7 (dꢂ2), 128.2 (dꢂ2), 128.7 (dꢂ2), 128.9 (s), 129.5 (dꢂ2), 139.1 (s);
MS m/z: 370 (Mꢃ), 263 (MꢃꢁOCH2Ph), 213 (MꢃꢁPhSe). Anal. Calcd for
C21H22OSe: C, 68.29; H, 6.00. Found: C, 68.54; H, 6.10.
1-Methoxy-4-(1-benzyloxy-2-propyn-1-yl)benzene (7aa) A yellow oil,
IR (KBr, cmꢁ1) n: 3287, 3033, 2933, 2838, 2360, 2112, 1611, 1512, 1455,
1421, 1389, 1305, 1250, 1174, 1060, 1036, 930, 831, 749, 699, 650, 589,
556; 1H-NMR (600 MHz, CDCl3) d: 2.64 (1H, d, Jꢀ3 Hz, acetylenic H),
3.74 (3H, s, OMe), 4.60 (1H, d, Jꢀ12 Hz, OCH2), 4.67 (1H, d, Jꢀ12 Hz,
OCH2), 5.14 (1H, d, Jꢀ2 Hz, OCH), 6.87 (2H, d, Jꢀ8 Hz, ArH), 7.24—7.27
(1H, m, ArH), 7.30—7.36 (4H, m, ArH), 7.43 (2H, d, Jꢀ8 Hz, ArH); 13C-
NMR (150 MHz, CDCl3) d: 55.1 (q), 69.7 (t), 75.6 (d), 81.6 (s), 113.8
(dꢂ2), 127.7 (d), 128.0 (dꢂ2), 128.3 (dꢂ2), 128.7 (dꢂ2), 130.2 (s), 137.5
(s), 159.7 (s); MS m/z: 252 (Mꢃ), 221 (MꢃꢁOMe). Anal. Calcd for
C17H16O2: C, 80.09; H, 6.39. Found: C, 79.75; H, 6.52.
1-Cyclohexyloxy-3-phenylprop-2-yn-1-ylbenzene (7 cd) A yellow oil,
IR (KBr, cmꢁ1) n: 3062, 3031, 2931, 2856, 2220, 1949, 1716, 1599, 1491,
1451, 1375, 1328, 1303, 1278, 1189, 1156, 1132, 1068, 1028, 980, 945,
914, 847, 756, 723, 693, 652, 610, 565, 528; 1H-NMR (600 MHz, CDCl3) d:
1.26—1.60 (6H, m, CH2), 1.75—1.78 (2H, m, CH2), 1.99—2.01 (2H, m,
1-Methoxy-4-(1-dodecyloxy-2-propyn-1-yl)benzene (7ab)
A yellow

September 2011
1139
CH2), 3.71—3.76 (1H, m, OCH), 5.49 (1H, s, OCH), 7.28—7.30 (4H, m, (4H, d, Jꢀ7 Hz, ArH); 13C-NMR (150 MHz, CDCl3) d: 44.4 (d), 55.3 (q),
ArH), 7.35—7.38 (2H, m, ArH), 7.45—7.47 (2H, m, ArH), 7.58—7.60 (2H, 73.1 (s), 96.2 (s), 113.9 (dꢂ2), 126.3 (dꢂ2), 126.5 (d), 128.9 (dꢂ2), 129.1
m, ArH); 13C-NMR (150 MHz, CDCl3) d: 24.1 (t), 24.2 (t), 25.8 (t), 31.8 (t),
(d), 129.2 (dꢂ3), 131.7 (s), 132.4 (s), 134.7 (s), 135.5 (dꢂ2), 159.4 (s); MS
33.0 (t), 69.0 (d), 75.8 (d), 86.5 (s), 88.2 (s), 122.8 (s), 127.3 (dꢂ2), 128.1 m/z: 396 (Mꢃ), 287 (MꢃꢁSPh), 253 (MꢃꢁC6H4Cl). Anal. Calcd for
(d), 128.2 (dꢂ2), 128.3 (d), 128.4 (dꢂ2), 131.7 (dꢂ2), 139.7 (s); MS m/z: C22H17ClOS2: C, 66.57; H, 4.32. Found: C, 66.47; H, 4.32.
290 (Mꢃ), 207 (MꢃꢁC6H5), 191 (MꢃꢁC6H5O); high resolution mass Calcd
for C21H22O: 290.1670, Found m/z 290.1711.
1-Methoxy-4-[1-(cyclohexylsulfanyl)-3-(phenylsulfanyl)-2-propyn-1-
yl]benzene (8ae) A yellow oil, IR (KBr, cmꢁ1) n: 2928, 2851, 2359, 2185,
1608, 1583, 1509, 1478, 1461, 1441, 1325, 1303, 1248, 1203, 1173, 1110,
1068, 1034, 999, 887, 834, 739, 688, 564, 529; 1H-NMR (600 MHz, CDCl3)
1-Phenylpropargyloxy-2-heptyn-1-ylbenzene (7da) A yellow oil, IR
(KBr, cmꢁ1) n: 3064, 3033, 2957, 2932, 2871, 2861, 2360, 2235, 1599,
1
1491, 1454, 1380, 1356, 1303, 1132, 1058, 1029, 914, 757, 694; H-NMR d: 1.21—1.46 (5H, m, CH2), 1.56—1.59 (1H, m, CH2), 1.72—1.75 (2H, m,
(600 MHz, CDCl3) d: 0.92 (3H, t, Jꢀ7 Hz, Me), 1.41—1.47 (2H, m, CH2), CH2), 1.90—1.92 (1H, m, CH2), 2.04—2.05 (1H, m, CH2), 2.93—2.97 (1H,
1.51—1.57 (2H, m, CH2), 2.30 (2H, dt, Jꢀ2, 7 Hz, CH2), 4.45 (1H, d, m, CH2), 3.78 (3H, s, OMe), 5.03 (1H, s, CHO), 6.86 (2H, d, Jꢀ8 Hz, ArH),
Jꢀ16 Hz, OCH2), 4.57 (1H, d, Jꢀ16 Hz, OCH2), 5.47 (1H, s, OCH), 7.28— 7.19—7.22 (1H, m, ArH), 7.30—7.33 (2H, m, ArH), 7.42—7.44 (4H, m,
7.38 (6H, m, ArH), 7.45—7.50 (2H, m, ArH), 7.56 (2H, d, Jꢀ8 Hz, ArH); ArH); 13C-NMR (150 MHz, CDCl3) d: 25.75 (t), 25.80 (t), 25.97 (t), 32.95
13C-NMR (150 MHz, CDCl3) d: 13.5 (q), 18.5 (t), 21.9 (t), 30.6 (t), 55.9 (t),
(t), 33.61 (t), 38.09 (d), 44.24 (d), 55.26 (q), 71.10 (s), 97.26 (s), 113.98
70.4 (d), 84.9 (s), 86.4 (s), 89.1 (s), 122.6 (s), 127.7 (dꢂ2), 128.2 (dꢂ2), (dꢂ2), 126.14 (dꢂ2), 126.39 (d), 128.94 (dꢂ2), 129.16 (dꢂ2), 130.10 (s),
128.3 (dꢂ2), 128.4 (dꢂ2), 131.7 (dꢂ2), 138.6 (s); MS m/z: 301 (Mꢃꢁ1), 132.97 (s), 159.10 (s); MS m/z: 368 (Mꢃ). Anal. Calcd for C22H24OS2: C,
245 (MꢃꢁBu). Anal. Calcd for C22H22O: C, 87.38; H, 7.33. Found: C, 71.70; H, 6.56. Found: C, 71.64; H, 6.57.
87.03; H, 7.41.
2-[1-(1-Decylsulfanyl)-3-(phenylsulfanyl)prop-2-ynyl]thiophene (8ba)
1-(Benzyloxy)-2-heptyn-1-ylbenzene (7db) A yellow oil, IR (KBr,
A brown oil, IR (KBr, cmꢁ1) n: 3429, 3066, 2924, 2854, 2360, 2183, 1712,
cmꢁ1) n: 3063, 3032, 2957, 2932, 2862, 2274, 2224, 1715, 1604, 1495, 1674, 1581, 1469, 1362, 1273, 1227, 1173, 1080, 1026, 845, 737, 698, 490;
1454, 1381, 1328, 1303, 1272, 1203, 1176, 1132, 1085, 1061, 1028, 1001,
1H-NMR (600 MHz, CDCl3) d: 0.88 (3H, t, Jꢀ7 Hz, Me), 1.23—1.34 (14H,
940, 914, 735, 697, 641, 602, 548; 1H-NMR (600 MHz, CDCl3) d: 0.91 (3H, br s, CH2), 1.55—1.63 (2H, m, CH2), 2.60—2.65 (1H, m, CH2), 2.74—2.78
t, Jꢀ7 Hz, Me), 1.40—1.46 (2H, m, CH2), 1.51—1.56 (2H, m, CH2), 2.28
(2H, t, Jꢀ7 Hz, CH2), 4.62 (1H, d, Jꢀ11 Hz, OCH2), 4.68 (1H, d, Jꢀ11 Hz,
(1H, m, CH2), 5.23 (1H, s, CH), 6.91—6.92 (1H, m, ArH), 7.13 (1H, d,
Jꢀ1 Hz, ArH), 7.19—7.23 (3H, m, ArH), 7.31 (1H, t, Jꢀ8 Hz, ArH), 7.43
OCH2), 5.20 (1H, br s, OCH), 7.24-7.37 (8H, m, ArH), 7.51 (2H, d, Jꢀ8 Hz, (2H, d, Jꢀ8 Hz, ArH); 13C-NMR (125 MHz, CDCl3) d: 14.1 (q), 22.6 (t),
ArH); 13C-NMR (150 MHz, CDCl3) d: 13.5 (q), 18.5 (t), 21.9 (t), 30.7 (t),
69.0 (t), 70.6 (d), 77.2 (s), 88.6 (s), 127.4 (dꢂ2), 127.6 (d), 128.0 (dꢂ2),
128.1 (d), 128.3 (dꢂ2), 137.9 (s), 139.2 (s); MS m/z 278 (Mꢃ), 221
(MꢃꢁBu); high resolution mass Calcd for C20H22O: 278.1670, Found m/z
278.1676.
28.9 (t), 29.0 (t), 29.1 (t), 29.3 (t), 29.4 (t), 29.5 (t), 31.6 (t), 31.8 (t), 35.4
(d), 71.4 (s), 96.0 (s), 125.5 (d), 126.1 (d), 126.2 (dꢂ2), 126.5 (dꢂ2), 129.2
(dꢂ2), 132.6 (s), 142.3 (s); MS m/z: 402 (Mꢃ), 293 (MꢃꢁSPh). Anal. Calcd
for C23H30S2: C, 68.60; H, 7.51. Found: C, 68.29; H, 7.43.
2-[1-(p-Chlorophenyl)-3-(phenylsulfanyl)prop-2-ynyl]thiophene (8bb)
1-Methoxy-4-[1-(4-decanesulfanyl)-3-(phenylsulfanyl)-2-propyn-1-yl]-
A brown oil, IR (KBr, cmꢁ1) n: 3073, 3060, 2923, 2852, 2182, 1657, 1581,
benzene (8aa) A brown oil, IR (KBr, cmꢁ1) n: 3061, 2925, 2853, 2187, 1573, 1475, 1441, 1389, 1265, 1230, 1173, 1093, 1024, 1013, 852, 822,
1
1609, 1583, 1509, 1478, 1464, 1441, 1377, 1303, 1249, 1110, 1034, 900, 739, 703, 688, 500; H-NMR (600 MHz, CDCl3) d: 5.45 (1H, s, CH), 6.88
834, 738, 687, 564, 528; 1H-NMR (600 MHz, CDCl3) d: 0.88 (3H, t, (1H, dd, Jꢀ3, 6 Hz, ArH), 6.69 (1H, d, Jꢀ3 Hz, ArH), 7.20—7.24 (4H, m,
Jꢀ7 Hz, Me), 1.24 (14H, br s, CH2), 1.57—1.61 (2H, m, CH2), 2.56—2.60 ArH), 7.24—7.33 (4H, m, ArH), 7.33—7.35 (2H, m, ArH); 13C-NMR
(1H, m, CH2), 2.71—2.76 (1H, m, CH2), 3.79 (3H, s, OMe), 4.96 (1H, s, (150 MHz, CDCl3) d: 40.3 (d), 73.3 (s), 95.2 (s), 125.9 (d), 126.4 (dꢂ2),
CHS), 6.87 (2H, d, Jꢀ8 Hz, ArH), 7.19—7.21 (1H, m, ArH), 7.30—7.33 126.6 (d), 126.7 (d), 126.8 (d), 128.9 (dꢂ2), 129.2 (dꢂ2), 130.9 (s), 132.1
(2H, m, ArH), 7.42—7.44 (4H, m, ArH); 13C-NMR (600 MHz, CDCl3) d:
14.08 (q), 22.64 (t), 28.94 (t), 29.08 (t), 29.17 (t), 29.28 (t), 29.47 (t), 29.52
(s), 135.2 (s), 135.9 (dꢂ2), 140.9 (s); MS m/z: 372 (Mꢃ), 263 (MꢃꢁSPh),
229 (MꢃꢁC6H4SCl). Anal. Calcd for C19H13S3Cl: C, 61.19; H, 3.51. Found:
(t), 31.86 (tꢂ2), 39.47 (d), 55.27 (q), 71.31 (s), 96.93 (s), 113.95 (dꢂ2), C, 60.85; H, 3.61.
126.13 (dꢂ2), 126.42 (d), 128.94 (dꢂ2), 129.18 (dꢂ2), 130.09 (s), 132.96
1-[1-(2-Naphthylsulfanyl)-3-(phenylsulfanyl)prop-2-ynyl]naphthalene
(s), 159.15 (s); MS m/z: 426 (Mꢃ). Anal. Calcd for C26H34OS2: C, 73.19; H, (8ca) Yellow crystals, mp 100—105 °C, IR (KBr cmꢁ1) n: 3445, 3054,
8.03. Found: C, 72.93; H, 7.97.
1-Methoxy-4-[1-(2-naphthylsulfanyl)-3-(phenylsulfanyl)-2-propyn-1-
1625, 1582, 1510, 1500, 1478, 1441, 1395, 1132, 1072, 1023, 944, 857,
1
814, 800, 777, 740, 687, 476; H-NMR (600 MHz, CDCl3) d: 6.01 (1H, s,
yl]benzene (8ab) Brown powers, mp 85—87 °C, IR (KBr, cmꢁ1) n: 3452, CH), 7.04—7.08 (3H, m, ArH), 7.20 (2H, d, Jꢀ8 Hz, ArH), 7.32 (1H, t,
3054, 2929, 2853, 1711, 1608, 1583, 1509, 1478, 1441, 1304, 1250, 1174,
Jꢀ8 Hz, ArH), 7.41—7.51 (4H, m, ArH), 7.57 (1H, t, Jꢀ8 Hz, ArH), 7.63—
1
1069, 1032, 834, 814, 740, 689, 472; H-NMR (600 MHz, CDCl3) d: 3.72 7.70 (3H, m, ArH), 7.77 (2H, d, Jꢀ8 Hz, ArH), 7.86 (1H, d, Jꢀ8 Hz, ArH),
(3H, s, OMe), 5.34 (1H, s, CH), 6.81 (2H, d, Jꢀ8 Hz, ArH), 7.01—7.06
(3H, m, ArH), 7.15 (2H, d, Jꢀ8 Hz, ArH), 7.36—7.48 (5H, m, ArH), 7.67—
7.76 (3H, m, ArH), 7.93 (1H, br s, ArH); 13C-NMR (150 MHz, CDCl3) d:
7.94 (1H, s, ArH), 8.32 (1H, d, Jꢀ8 Hz, ArH); 13C-NMR (150 MHz, CDCl3)
d: 42.2 (d), 73.1 (s), 96.7 (s), 123.4 (d), 125.1 (d), 125.9 (d), 126.1 (dx3),
126.3 (d), 126.4 (dꢂ2), 126.5 (d), 126.8 (d), 127.6 (d), 127.8 (d), 128.2 (d),
44.2 (d), 55.2 (q), 72.6 (s), 96.7 (s), 133.9 (dꢂ2) 126.2 (dꢂ2), 126.3 (d), 129.0 (d), 129.0 (dꢂ2), 129.1 (s), 130.7 (d), 131.0 (s), 132.3 (s), 132.4 (s),
126.4 (d), 126.5 (d), 127.6 (d), 127.7 (d), 128.2 (d), 129.0 (dꢂ2), 129.2 132.8 (s), 133.2 (d), 133.5 (s), 134.0 (s); MS m/z: 432 (Mꢃ), 323
(dꢂ2), 130.5 (d), 131.1 (s), 132.4 (s), 132.7 (s), 132.9 (d), 133.5 (s), 134.2 (MꢃꢁSPh), 273 (MꢃꢁC10H7S). Anal. Calcd for C29H20S2: C, 80.52; H,
(s), 159.3 (s); MS m/z: 412 (Mꢃ), 303 (MꢃꢁSPh), 253 (MꢃꢁC10H7S). Anal.
Calcd for C26H20OS2: C, 75.69; H, 4.89. Found: C, 75.42; H, 4.93.
4-[3-(Phenylsulfanyl)-1-(2-thienylsulfanyl)prop-2-ynyl]-1-methoxy-
4.66. Found: C, 80.43; H, 4.64.
5-[1-(2-Naphthylsulfanyl)-3-(phenylsulfanyl)prop-2-ynyl]-1,3-benzodi-
oxole (8ga) Pale orange crystals, mp 105—106 °C, IR (KBr, cmꢁ1) n:
benzene (8ac) A brown oil, IR (KBr, cmꢁ1) n: 2835, 2186, 1608, 1583, 3651, 3054, 2894, 2777, 1582, 1501, 1487, 1442, 1364, 1249, 1132, 1102,
1
1509, 1478, 1441, 1400, 1304, 1249, 1217, 1173, 1112, 1086, 1033, 833, 1039, 941, 927, 858, 814, 781, 740, 688, 477; H-NMR (600 MHz, CDCl3)
740, 708, 688, 467; 1H-NMR (600 MHz, CDCl3) d: 3.79 (3H, s, OMe), 5.10 d: 5.29 (1H, s, CH), 5.29 (2H, s, OCH2O), 6.70 (1H, d, Jꢀ8 Hz, ArH), 6.88
(1H, s, CH), 6.84 (2H, d, Jꢀ7 Hz, ArH), 6.95 (1H, dd, Jꢀ3, 5 Hz, ArH),
7.05—7.06 (1H, dd, Jꢀ1, 3 Hz, ArH), 7.21 (1H, t, Jꢀ7 Hz, ArH), 7.29—
7.32 (4H, m, ArH), 7.35—7.39 (3H, m, ArH); 13C-NMR (150 MHz, CDCl3)
(1H, dt, Jꢀ1, 8 Hz, ArH), 7.02—7.09 (4H, m, ArH), 7.15—7.16 (2H, m,
ArH), 7.43—7.49 (3H, m, ArH), 7.50—7.73 (2H, m, ArH), 7.78 (1H, d,
Jꢀ8 Hz, ArH), 7.95 (1H, br s, ArH); 13C-NMR (150 MHz, CDCl3) d: 44.7
d: 47.2 (d), 55.3 (q), 73.5 (s), 96.3 (s), 113.9 (dꢂ2), 126.3 (dꢂ2), 126.5 (d), (d), 72.9 (s), 96.3 (s), 101,1 (t), 108.0 (d), 108.5 (d), 121.6 (d), 126.1 (dꢂ2),
127.5 (d), 129.1 (s), 129.2 (dꢂ2), 129.2 (dꢂ2), 131.0 (s), 131.5 (d), 132.6 126.3 (d), 126.4 (d), 126.5 (d), 127.6 (d), 127.7 (d), 128.3 (d), 129.0 (dꢂ2),
(s), 136.7 (d), 159.4 (s); MS m/z: 368 (Mꢃ), 291 (MꢃꢁPh), 253 130.5 (d), 130.9 (s), 131.0 (s), 132.3 (s), 132.8 (s), 133.0 (d), 133.4 (s),
(MꢃꢁC4H3S2); high resolution mass Calcd for C20H16OS3: 368.0364, Found 147.4 (s), 147.8 (s); MS m/z: 426 (Mꢃ), 317 (MꢃꢁSPh), 267
m/z 368.0352.
(MꢃꢁC10H7S); high resolution mass Calcd for C26H18O2S2: 426.0748.
Found: 426.0748.
1-Methoxy-4-[1-(4-chlorophenylsulfanyl)-3-(phenylsulfanyl)-2-
propyn-1-yl]benzene (8ad) White powders, mp 67—68 °C, IR (KBr,
5-[1-(1-Decylsulfanyl)-3-(phenylsulfanyl)prop-2-ynyl]-1,3-benzodi-
cmꢁ1) n: 2955, 2928, 2836, 2186, 1734, 1608, 1583, 1509, 1475, 1441, oxole (8gb) A yellow oil, IR (KBr, cmꢁ1) n: 3060, 2922, 2852, 2190,
1
1388, 1325, 1304, 1250, 1174, 1111, 1093, 1033, 822, 739, 688, 662; H- 1859, 1729, 1610, 1583, 1503, 1488, 1442, 1365, 1247, 1181, 1156, 1123,
1
NMR (600 MHz, CDCl3) d: 3.79 (3H, s, OMe), 5.20 (1H, s, CH), 6.84 (2H, 1101, 1040, 941, 862, 815, 783, 738, 687; H-NMR (600 MHz, CDCl3) d:
d, Jꢀ7 Hz, ArH), 7.20—7.23 (3H, m, ArH), 7.26—7.29 (4H, m, ArH), 7.32 0.88 (3H, t, Jꢀ8 Hz, Me), 1.24—1.36 (14H, br s, CH2), 1.56—1.64 (2H, m,

1140
Vol. 59, No. 9
CH2), 2.56—2.61 (1H, m, CH2), 2.71—2.75 (1H, m, CH2), 4.91 (1H, s, CH),
5.95 (2H, s, CH2), 6.76 (1H, d, Jꢀ8 Hz, ArH), 6.96 (1H, dd, Jꢀ2, 8 Hz,
ArH), 7.03 (1H, d, Jꢀ2 Hz, ArH), 7.20—7.23 (1H, m, ArH), 7.31—7.34
(2H, m, ArH), 7.42 (2H, d, Jꢀ8 Hz, ArH); 13C-NMR (150 MHz, CDCl3) d:
14.1 (q), 22.6 (t), 28.9 (t), 29.0 (t), 29.1 (t), 29.2 (t), 29.4 (t), 29.5 (t), 31.8
(tꢂ2), 39.8 (d), 71.6 (s), 96.6 (s), 101.1 (t), 107.9 (d), 108.3 (d), 121.1 (d),
126.1 (dꢂ2), 126.4 (d), 129.1 (dꢂ2), 131.9 (s), 132.8 (s), 147.2 (s), 147.8
(s); MS m/z: 440 (Mꢃ); high resolution mass Calcd for C26H32O2S2:
440.1843, Found m/z 440.1783.
5-[1-(p-Chlorophenyl)-3-(phenylsulfanyl)prop-2-ynyl]-1,3-benzodi-
oxole (8gc) Orange crystals, mp 58 °C, IR (KBr, cmꢁ1) n: 3434, 3060,
2893, 2777, 1609, 1581, 1502, 1487, 1476, 1442, 1389, 1365, 1249, 1181,
1093, 1039, 939, 928, 861, 816, 781, 740, 688; 1H-NMR (600 MHz, CDCl3)
d: 5.14 (1H, s, CH), 5.93 (2H, s, CH2), 6.70 (1H, d, Jꢀ8 Hz, ArH), 6.82
(1H, d, Jꢀ8 Hz, ArH), 6.96 (1H, br s, ArH), 7.19—7.28 (7H, m, ArH), 7.33
(2H, d, Jꢀ7 Hz, ArH); 13C-NMR (150 MHz, CDCl3) d: 44.9 (d), 73.4 (s),
95.8 (s), 101.3 (t), 108.0 (d), 108.4 (d), 121.6 (d), 126.3 (dꢂ2), 126.6 (d),
128.9 (dꢂ2), 129.2 (dꢂ2), 130.8 (s), 131.6 (s), 132.3 (s), 134.8 (s), 135.5
(dꢂ2), 147.5 (s), 147.8 (s); MS m/z: 410 (Mꢃ), 301 (MꢃꢁSPh), 267
(MꢃꢁC6H4SCl). Anal. Calcd for C22H15O2S2Cl: C, 64.30; H, 3.68. Found:
C, 64.69; H, 3.81.
1-[1ꢀ-(Decylsulfanyl)-3ꢀ-phenylprop-2-ynyl]benzene (9ca) A pale yel-
low oil, IR (KBr, cmꢁ1) n: 3081, 3061, 3030, 2953, 2925, 2853, 1599, 1491,
1454, 1377, 1298, 1277, 1070, 1029, 913, 825, 756, 692, 618; 1H-NMR
(600 MHz, CDCl3) d: 0.88 (3H, t, Jꢀ7 Hz, Me), 1.24—1.38 (14H, br s,
CH2), 1.57—1.68 (2H, m, CH2), 2.60—2.64 (1H, m, CH2), 2.77—2.81 (1H,
m, CH2), 4.99 (1H, s, CH), 7.27—7.35 (6H, m, ArH), 7.47—7.49 (2H, m,
ArH), 7.57 (2H, d, Jꢀ8 Hz, ArH); 13C-NMR (150 MHz, CDCl3) d: 14.1 (q),
22.7 (t), 29.0 (t), 29.1 (t), 29.2 (t), 29.3 (t), 29.5 (tꢂ2), 31.8 (t), 31.9 (t), 39.3
(d), 85.7 (s), 87.4 (s), 123.0 (s), 127.6 (d), 127.9 (dꢂ2), 128.2 (dꢂ3), 128.5
(dꢂ2), 131.7 (dꢂ2), 138.6 (s); MS m/z: 364 (Mꢃ), 223 (MꢃꢁC10H21), 191
(MꢃꢁC10H21S). Anal. Calcd for C25H32S: C, 82.36; H, 8.85. Found: C,
82.24; H, 8.81.
Trost B. M., Fleming I., Pergamon Press, New York, 1991, pp. 22—28.
5) Keinan E., Sahai M., Poth Z., Nudelman A., Herzig J., J. Org. Chem.,
50, 3558—3566 (1985).
6) Trost B. M., Tenaglia A., Tetrahedron Lett., 29, 2927—2930 (1988).
7) Takahashi K., Miyake A., Hata G., Bull. Chem. Soc. Jpn., 45, 230—
236 (1972).
8) Stanton S. A., Felman S. W., Parkhurst C. S., Godleski S. A., J. Am.
Chem. Soc., 105, 1964—1969 (1983).
9) Mahwald R., Schick H., Angew. Chem. Int. Ed. Engl., 30, 593—594
(1991).
10) Chen Z., Jiang Q., Zhu G., Xiao D., Cao P., Guo C., Zhang X., J. Org.
Chem., 62, 4521—4523 (1997).
11) van der Deen H., van Oeveren A., Kellogg R. M., Feringa B. L., Tetra-
hedron Lett., 40, 1755—1758 (1999).
12) Bartels A., Mahrwald R., Quint S., Tetrahedron Lett., 40, 5989—5990
(1999).
13) Mahrwald R., Quint S., Tetrahedron, 56, 7463—7468 (2000).
14) Hattori G., Matsuzawa H., Miyake Y., Nishibayashi Y., Angew. Chem.
Int. Ed., 47, 3781—3783 (2008).
15) Müller T. J. J., Netz A., Tetrahedron Lett., 40, 3145—3148 (1999).
16) Stork G., Poirier J. M., J. Am. Chem. Soc., 105, 1073—1074 (1983).
17) Mahrwald R., Quint S., Scholtis S., Tetrahedron, 58, 9847—9851
(2002).
18) Lakhmiri R., Lhoste P., Sinou D., Tetrahedron Lett., 30, 4669—4672
(1989).
19) Thorey C., Wilken J., Hénin F., Martens J., Mehler T., Muzart J., Tetra-
hedron Lett., 36, 5527—5530 (1995).
20) Bhatt R. K., Shin D.-S., Falck J. R., Mioskowski C., Tetrahedron Lett.,
33, 4885—4888 (1992).
21) Imada Y., Yuasa M., Nakamura I., Murahashi S., J. Org. Chem., 59,
2282—2284 (1994).
22) Hamada Y., Seto N., Takayanagi Y., Nakano T., Hara O., Tetrahedron
Lett., 40, 7791—7794 (1999).
23) Trost B. M., McEachern E. J., Toste F. D., J. Am. Chem. Soc., 120,
12702—12703 (1998).
[1-(2-Naphthylsulfanyl)-3-phenylprop-2-ynyl]benzene (9cb)
A pale
yellow oil, IR (KBr, cmꢁ1) n: 3512, 3055, 1598, 1490, 1454, 1132, 1028,
858, 814, 756, 694, 634, 529, 477, 448, 433, 422, 410; 1H-NMR (600 MHz,
CDCl3) d: 5.29 (1H, s, CH), 7.20—7.26 (6H, m, ArH), 7.32 (2H, s, ArH),
7.40 (2H, d, Jꢀ4 Hz, ArH), 7.45 (2H, d, Jꢀ7 Hz, ArH), 7.50—7.51 (1H, m,
ArH), 7.68 (2H, br s, ArH), 7.73 (1H, d, Jꢀ5 Hz, ArH), 7.95 (1H, s, ArH);
13C-NMR (150 MHz, CDCl3) d: 44.3 (d), 87.0 (s), 87.4 (s), 122.7 (s), 126.3
(d), 126.5 (d), 127.6 (d), 127.7 (d), 127.8 (d), 128.0 (dꢂ3), 128.1 (dꢂ2),
128.2 (d), 128.4 (dꢂ2), 130.7 (s), 131.1 (d), 131.5 (dꢂ2), 132.8 (s), 133.4
(s), 133.7 (d), 137.9 (s); MS m/z: 350 (Mꢃ), 273 (MꢃꢁPh), 191
(MꢃꢁC10H7S); high resolution mass Calcd for C25H18S: 350.1129, Found
m/z 350.1138.
1-[1ꢀ-(p-Chlorophenylsulfanyl)-3ꢀ-phenylprop-2-ynyl]benzene (9cc)
A pale yellow oil, IR (KBr, cmꢁ1) n: 3060, 3031, 1713, 1598, 1573, 1490,
1475, 1454, 1442, 1388, 1093, 1013, 915, 828, 817, 757, 693, 666, 621,
530, 499; 1H-NMR (600 MHz, CDCl3) d: 5.19 (1H, s, CH), 7.23 (2H, d,
Jꢀ8 Hz, ArH), 7.27—7.33 (6H, m, ArH), 7.35—7.39 (4H, m, ArH), 7.41
(2H, d, Jꢀ8 Hz, ArH); 13C-NMR (150 MHz, CDCl3) d: 44.3 (d), 86.9 (s),
87.2 (s), 122.7 (s), 127.9 (d), 128.0 (dꢂ2), 128.3 (dꢂ2), 128.4 (d), 128.5
(dꢂ2), 128.8 (dꢂ2), 131.5 (s), 131.6 (dꢂ2), 134.9 (s), 136.0 (dꢂ2), 137.7
(s); MS m/z: 334 (Mꢃ), 191 (MꢃꢁC6H4SCl). Anal. Calcd for C21H15ClS: C,
75.32; H, 4.52. Found: C, 75.11; H, 4.61.
1-(Decylsulfanyl)hept-2-ynylbenzene (9da) A yellow oil, IR (KBr,
cmꢁ1) n: 3428, 3029, 2956, 2926, 2854, 2359, 1694, 1600, 1494, 1465,
1455, 1378, 1260, 1073, 1030, 914, 758, 698, 616, 411; 1H-NMR (600 MHz,
CDCl3) d: 0.88 (3H, t, Jꢀ8 Hz, Me), 0.92 (3H, t, Jꢀ8 Hz, Me), 1.25 (14H,
br s, CH2), 1.42—1.47 (2H, m, CH2), 1.52—1.67 (4H, m, CH2), 2.29 (2H,
dt, Jꢀ2, 8 Hz, CH2), 2.51—2.56 (1H, m, CH2), 2.67—2.71 (1H, m, CH2),
4.75 (1H, s, CH), 7.22—7.25 (1H, m, ArH), 7.30—7.35 (2H, m, ArH), 7.48
(2H, d, Jꢀ8 Hz, ArH); 13C-NMR (150 MHz, CDCl3) d: 13.5 (q), 14.0 (q),
18.6 (t), 21.9 (t), 22.6 (t), 28.9 (t), 29.0 (t), 29.1 (t), 29.2 (t), 29.4 (t), 29.5 (t),
30.8 (t), 31.6 (t), 31.8 (t), 39.0 (d), 77.8 (s), 86.2 (s), 127.3 (d), 127.7 (dꢂ2),
128.3 (dꢂ2), 139.2 (s); MS m/z: 344 (Mꢃ), 171 (MꢃꢁC10H21S); high reso-
lution mass Calcd for C23H36S: 344.2537, Found m/z 344.2284.
24) Evans P. A., Leahy D. K., J. Am. Chem. Soc., 122, 5012—5013 (2000).
25) Evans P. A., Leahy D. K., J. Am. Chem. Soc., 124, 7882—7883 (2002).
26) Kim H., Lee C., Org. Lett., 4, 4369—4371 (2002).
27) Ru: Inada Y., Nishibayashi Y., Hidai M., Uemura S., J. Am. Chem.
Soc., 124, 15172—15173 (2002).
28) Ru: Nishibayashi Y., Milton M. D., Inada Y., Yoshikawa M., Wakiji I.,
Hidai M., Uemura S., Chemistry, 11, 1433—1451 (2005).
29) Nishibayashi Y., Wakiji I., Hidai M., J. Am. Chem. Soc., 122, 11019—
11020 (2000).
30) Bi: Qin H., Yamagiwa N., Matsunaga S., Shibasaki M., Angew. Chem.
Int. Ed., 46, 409—413 (2007).
31) Bi: Zhan Z.-P., Yang W.-Z., Yang R.-F., Yu J. L., Li J.-P., Liu H.-J.,
Chem. Commun. (Cambridge), 3352—3354 (2006).
32) Co: Nicholas K. M., Acc. Chem. Res., 20, 207—214 (1987).
33) Co: Teobald B. J., Tetrahedron, 58, 4133—4170 (2002).
34) Co: Brummond K. M., Kent J. L., Tetrahedron, 56, 3263—3283
(2000).
35) Re: Sherry B. D., Radosevich A. T., Toste F. D., J. Am. Chem. Soc.,
125, 6076—6077 (2003).
36) V: Maeda Y., Kakiuchi N., Matsumura S., Nishimura T., Kawamura T.,
Uemura S., J. Org. Chem., 67, 6718—6724 (2002).
37) Au: Georgy M., Boucard V., Campagne J.-M., J. Am. Chem. Soc., 127,
14180—14181 (2005).
38) Fe: Zhan Z.-P., Yu J.-L., Liu H.-J., Cui Y.-Y., Yang R.-F., Yang W.-Z.,
Li J.-P., J. Org. Chem., 71, 8298—8301 (2006).
39) Müller T. J. J., Eur. J. Org. Chem., 2021—2033 (2001).
40) Yoshimatsu M., Otani T., Matsuda S., Yamamoto T., Sawa A., Org.
Lett., 10, 4251—4254 (2008).
41) Yoshimatsu M., Yamamoto T., Sawa A., Kato T., Tanabe G., Muraoka
O., Org. Lett., 11, 2952—2955 (2009).
42) Ohta K., Kobayashi T., Tanabe G., Muraoka O., Yoshimatsu M., Chem.
Pharm. Bull., 58, 1180—1186 (2010).
43) Yoshimatsu M., Matsui M., Yamamoto T., Sawa A., Tetrahedron, 66,
7975—7987 (2010).
44) Yoshimatsu M., Naito M., Kawahigashi M., Shimizu H., Kataoka T., J.
Org. Chem., 60, 4798—4802 (1995).
References
1) Suzuki T., Hirama M., Tetrahedron Lett., 31, 4747—4750 (1990).
2) Suzuki T., Sato O., Hirama M., Yamamoto Y., Murata M., Yasumoto
T., Harada N., Tetrahedron Lett., 32, 4505—4508 (1991).
3) Jiang L., Burke S. D., Org. Lett., 4, 3411—3414 (2002).
4) Mitsunobu O., “Comprehensive Organic Synthesis,” Vol. 6, ed. by
45) Yoshimatsu M., Watanabe H., Koketsu E., Org. Lett., 12, 4192—4194
(2010).
46) Bustelo E., Dixneuf P. H., Adv. Synth. Catal., 349, 933—942 (2007).
47) Srihari P., Reddy J. S. S., Bhunia D. C., Mandal S. S., Yadav J. S.,
Synth. Commun., 38, 1448—1455 (2008).