Bronsted acid catalyzed intramolecular hydroarylation for the synthesis of cycloalkenyl selenides and tellurides

Article abstract of DOI:10.1002/ejoc.201201763

Trifluoromethanesulfonic acid catalyzed intramolecular hydroarylation of alkynyl selenides and tellurides is developed for the preparation of cycloalkenyl selenide and telluride derivatives through a selective 6- and 7-endo mode. The cycloalkenyl selenides and tellurides can be easily converted into a wide range of other valuable functionalities, including cyclic olefins, allylic alcohols, enynes, 1,3-dienes, and α,β-unsaturated aldehydes. Trifluoromethanesulfonic acid catalyzed intramolecular hydroarylation of alkynyl selenides and tellurides is developed for the preparation of cycloalkenyl selenide and telluride derivatives through a selective 6- and 7-endo mode. The cycloalkenyl selenides and tellurides can be easily converted into a variety of valuable functionalities, including cyclic olefins, allylic alcohols, enynes, 1,3-dienes, and α,β-unsaturated aldehydes. Copyright

Full text of DOI:10.1002/ejoc.201201763

Job/Unit: O21763
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Date: 12-03-13 12:48:54
Pages: 12
FULL PAPER
DOI: 10.1002/ejoc.201201763
Brønsted Acid Catalyzed Intramolecular Hydroarylation for the Synthesis of
Cycloalkenyl Selenides and Tellurides
Dahan Eom,[a] Sangjune Park,[a] Youngchul Park,[a] Kooyeon Lee,[b] Gilbert Hong,[c] and
Phil Ho Lee*[a]
Keywords: Synthetic methods / Hydroarylation / Brønsted acids / Alkenes / Selenium / Tellurium
Trifluoromethanesulfonic acid catalyzed intramolecular hy-
droarylation of alkynyl selenides and tellurides is developed
for the preparation of cycloalkenyl selenide and telluride de-
alkenyl selenides and tellurides can be easily converted into
a wide range of other valuable functionalities, including cy-
clic olefins, allylic alcohols, enynes, 1,3-dienes, and α,β-un-
rivatives through a selective 6- and 7-endo mode. The cyclo- saturated aldehydes.
Recently, we have been interested in intramolecular
Introduction
hydroarylation reactions with arenes having functionalized
alkynes.[10] In this regard, we envisioned that if an alkynyl
substrate containing a selenide or telluride at the sp-hy-
bridized carbon atom was activation by an appropriate
Brønsted acid catalyst, then the π system of the aryl group
could initiate intramolecular attack on the activated alkyne
to give cycloalkenyl selenides and tellurides. We report
herein a synthetic method to cycloalkenyl selenides and tel-
lurides from alkynyl selenides and tellurides through cata-
lytic intramolecular hydroarylation in the presence of a
Brønsted acid catalyst (Scheme 1).
Organochalcogenium chemistry has received consider-
able attention for its highly useful synthetic applications.[1]
Furthermore, organoselenium[2] and organotellurium[3]
compounds have become attractive synthetic targets be-
cause of their chemo-, regio-, and stereoselective reactions
and because of their biological activities.[4] These com-
pounds can usually be used in the presence of a variety
of functional groups (FGs), which thus avoid protection–
deprotection strategies.[5] Specifically, functionalized alkenyl
selenides[6] and tellurides[7] have great potential in organic
synthesis, as they are valuable intermediates for the selective
preparation of several organic compounds. Accordingly, the
development of synthetic methods for these compounds has
been a significant goal in organic synthesis. Synthetic
methods for alkenyl selenides and tellurides are based on
three general approaches, namely, hydroselenation of
alkynes,[8a–8j] Wittig olefination,[8k] and direct nucleophilic
substitution of alkenyl halides.[8l–8s] However, these meth-
ods have been mainly applied to the preparation of linear
alkenyl selenides and tellurides, whereas little attention has
been paid to cycloalkenyl selenides and tellurides.[9] Thus,
considering the importance of cycloalkenyl selenides and
tellurides, a milder and more convenient methodology is
highly required.
Scheme 1. Preparation of cycloalkenyl selenides and tellurides
through Brønsted acid catalyzed hydroarylation.
Results and Discussion
First, a variety of alkynyl selenides 2 were prepared in
good to excellent yields by treatment of propargyl ethers
and amines 1 derived from phenol and N-phenyl sulfon-
amides with phenyl selenyl bromide in the presence of cop-
per iodide in DMF at room temperature (Scheme 2).[11]
Alkynyl tellurides 3 were prepared in good yields by reac-
tion of propargyl ethers and amines 1 with phenyl ditellur-
ide in the presence of copper iodide and potassium carbon-
ate in DMSO at room temperature (Scheme 3).[11] In ad-
dition, treatment of a terminal alkyne with n-butyl ditellur-
ide in the presence of InCl3 and Cs2CO3 in DMSO afforded
[a] Department of Chemistry, Kangwon National University,
Chuncheon 200-701, Republic of Korea
Fax: +82-33-253-7582
E-mail: phlee@kangwon.ac.kr
Homepage: http://indium.kangwon.ac.kr
[b] Department of Bio-Health Technology, Kangwon National
University,
Republic of Korea
[c] Korean Minjok Leadership Academy,
Republic of Korea
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201201763.
Eur. J. Org. Chem. 0000, 0–0
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D. Eom, S. Park, Y. Park, K. Lee, G. Hong, P. H. Lee
FULL PAPER
Scheme 3. Preparation of alkynyl tellurides.
which was isolated in 9% yield (Table 1, entry 6). To con-
duct the hydroarylation reaction of 2a more efficiently, we
examined Brønsted acids such bis(trifluoromethanesulf-
onyl)imide (Tf2NH) and trifluoromethanesulfonic acid
(TfOH) and a variety of solvents. Treatment of 2a with
Tf2NH (5 mol-%) in DCE at 25 °C for 20 min provided 4a
in 77% yield (Table 1, entry 7). The best result was obtained
with TfOH (5 mol-%) in DCE, which produced 4a with
98% conversion (92% isolated yield) at 25 °C after 5 min
(Table 1, entry 8). The use of 3 mol-% of TfOH gave 4a with
88% conversion (82% isolated yield; Table 1, entry 9). In
addition, reaction of 2a with TfOH (5 mol-%) in CH2Cl2
furnished 4a in 79% yield (Table 1, entry 10). Toluene, ni-
tromethane, and 1,4-dioxane were inferior to DCE (Table 1,
entries 11–13).
Table 1. Reaction optimization.
Scheme 2. Preparation of alkynyl selenides.
corresponding alkynyl butyl telluride 3e in 58% yield
[Equation (1)].[11] 4-Phenyl-1-butyne (1b) was treated with
n-butyllithium followed by the telluride and n-butyl brom-
ide to produce 3f in 93% yield [Equation (2)].[12]
Entry
Catalyst
Solvent
t [h]
Conversion
yield [%][a]
1
2
3
4
5
6
7
8
HCl
DCE
DCE
DCE
DCE
DCE
DCE
DCE
DCE
6
6
6
6
6
0
0
0
0
0
CH3CO2H
CF3CO2H
CH3SO3H
pTsOH
H2SO4
Tf2NH
TfOH
TfOH
TfOH
TfOH
TfOH
2
57 (9)[b]
77
0.3
0.1
0.2
0.5
6
1
12
98 (92)[c]
88 (82)[c,d]
79
9
DCE
10
11
12
13
CH2Cl2
toluene
CH3NO2
dioxane
71 (4)[b]
70 (6)[b]
12
To determine the most effective catalyst for the intramo-
lecular hydroarylation reaction, an initial study was carried
out with alkynyl selenide 2a (Table 1). When the reaction
was carried out with 5 mol-% of hydrochloric acid, acetic
acid, trifluoroacetic acid, methanesulfonic acid, or p-tolu-
enesulfonic acid in dichloroethane (DCE) at 25 °C, the reac-
tion did not proceed (Table 1, entries 1–5). However, sub-
jecting 2a to sulfuric acid (5 mol-%) in DCE at 25 °C for 2 h
TfOH
1
[a] Determined by analysis of the crude mixture by H NMR spec-
troscopy with dodecane as an internal standard. [b] Isolated yield
of 1-tosyl-2,3-dihydroquinolin-4-(1H)-one is given in parentheses.
[c] Isolated yield of 4a is given in parentheses. [d] 3 mol-% of the
catalyst was used.
To demonstrate the efficiency and scope of the present
produced hydroarylated product 4a with 57% conversion method, we applied this catalytic system to a wide range
together with 1-tosyl-2,3-dihyhydroquinolin-4-(1H)-one, of alkynyl selenides 2, and the results are summarized in
2
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Catalytic Intramolecular Hydroarylation
Scheme 4. Treatment of 2b with TfOH (5 mol-%) gave hy- dition, hydroarylation of 2k possessing an electron-with-
droarylated product 4b selectively in 91% yield after 5 min drawing nitrile group on the aromatic ring required a higher
without contamination of α-tetralone. Under the optimized reaction temperature (80 °C), but under these conditions, it
reaction conditions, diethyl malonate tethered alkynyl sele- afforded 4j in 85% yield after 30 min. This result indicated
nide 2c having an electron-donating methoxy group that the nitrile group was tolerated under the present condi-
smoothly cyclized to produce 4c in 82% yield after 10 min tions. When 2l was exposed to the optimized reaction con-
through a selective 6-endo mode. Exposure of oxygen-teth- ditions, cycloheptenyl selenide 4k was obtained in 83%
ered 2d and 2e to TfOH (5 mol-%) in DCE at 25 °C for yield after 2 h through an exclusive 7-endo mode. N-Tosyl-
10 min provided cyclohexenyl selenides 4d and 4e in 87 and amine-linked alkynyl selenide 2m was compatible with the
90% yield, respectively. Reaction of alkynyl selenide 2f pre- reaction conditions, although a higher reaction temperature
pared from 1-naphthol with the TfOH catalyst afforded hy- (80 °C) was required and a lower product yield (57%) was
droarylated product 4f in 80% yield, although a higher re- obtained.
action temperature was required (80 °C). Next, twofold in-
When 2h was employed as the substrate, there could
tramolecular hydroarylation was briefly examined. When theoretically be two possible products from two different
bis(alkynyl selenide) 2g was subjected to TfOH (5 mol-%) cyclization paths of the corresponding alkynyl selenide, and
in DCE at 80 °C for 60 min, 4g having a phenylselenyl thus, 5- and 7-methyl cyclic vinyl selenides 4m were ob-
group on the sp2 benzylic carbon atom was isolated in 62% tained in 91% yield [5-Me/7-Me = 1:1.3, Equation (3)].
yield in one reaction vessel. Intramolecular hydroarylation
of 2i having a 2-isopropyl group proceeded to afford 4h in
93% at 80 °C after 30 min as a result of steric effects. Reac-
tion of 2j with TfOH provided 4i in 89% after 40 min
through a 6-endo mode, even in the presence of an electron-
withdrawing bromide group on the aromatic ring. In ad-
On the basis of the catalytic hydroarylation of alkynyl
selenides, we next turned our attention to the hydroaryl-
ation of alkynyl tellurides (Scheme 5). Treatment of alkynyl
n-butyl telluride 3f with TfOH (20-mol-%) provided hy-
droarylated product 5a selectively in 76% yield in DCE at
25 °C after 60 min without contamination of α-tetralone.
Alkynyl phenyl telluride 3a is more reactive than 3f, which
results in the formation of desired cyclohexenyl telluride 5b
in 88% yield with TfOH (5 mol-%). When oxygen-tethered
alkynyl phenyl tellurides 3b and 3c were subjected to the
optimized reaction conditions, cycloalkenyl tellurides 5c
and 5d were selectively obtained in 90 and 73% yield,
respectively through a 6-endo mode. The hydroarylation re-
action with N-tosylamine-tethered alkynyl n-butyl telluride
Scheme 4. Preparation of cycloalkenyl selenides through TfOH-cat-
alyzed hydroarylation. Isolated yields are given.
Scheme 5. Preparation of cycloalkenyl tellurides through TfOH-
catalyzed hydroarylation.
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D. Eom, S. Park, Y. Park, K. Lee, G. Hong, P. H. Lee
FULL PAPER
3e proceeded smoothly to provide corresponding cyclohex-
enyl telluride 5e in 72% yield, although higher amounts of
TfOH (20 mol-%) were needed. Under the optimum reac-
tion conditions, N-tosylamine-linked 3d underwent clean
intramolecular hydroarylation to give cycloalkenyl telluride
5f in 80% yield.
Next, we examined the synthetic usefulness of both cy-
cloalkenyl selenides and tellurides because little attention
has been paid to the application of cycloalkenyl selenides
and tellurides. The Ni-catalyzed coupling reaction of 4b
with phenylmagnesium bromide in THF was tested first,
and this reaction produced corresponding cyclic styrene de-
rivative 6a in 71% yield [Equation (4), dppp = 1,3-bis(di-
phenylphosphanyl)propane].[13]
Although the mechanism of the present reaction has not
been fully established at the present stage, a possible reac-
tion pathway is shown in Scheme 6. Protonation of alkynyl
selenides 2 or tellurides 3 might provide vinyl cationic inter-
mediate 10 generated in situ from 7 as a result of π-electron
delocalization between the heteroatom and the conjugated
alkyne. When Brønsted acid catalyzed intramolecular hy-
droarylation was carried out on substrates without chalco-
genide moieties under the same reaction conditions, the cy-
clized products were not produced, and this indicates that
delocalization is important for a successful reaction. Intra-
molecular hydroarylation through the addition of an aro-
matic C–H bond across a π bond might give intermediate
12. Subsequent deprotonation of 12 affords cycloalkenyl
selenides 4 or tellurides 5 with the release of a proton back
into the catalytic cycle. Exclusive formation of 4 or 5
through a 6- or 7-endo mode rules out intermediate vinyl
cation 8 in the catalytic cycle.
The reaction of 5a with n-butyllithium followed by butyr-
aldehyde and benzaldehyde led to addition products 6b and
6c in 90 and 87% yield, respectively [Equation (5)].[14]
Moreover, Sonogashira coupling of 5a with 1-hexyne under
basic conditions furnished enyne 6d in 75% yield [Equa-
tion (6)].[15] Homocoupling of 5a proceeded smoothly in the
presence of Pd(OAc)2 and AgOAc in acetonitrile to afford
1,3-diene 6e in 62% yield [Equation (7)].[16]
Treatment of 5b with n-butyllithium in THF followed by
DMF produced formylated product 6f in 63% yield [Equa-
tion (8)].[14]
Scheme 6. Plausible reaction mechanism.
Likewise, 5f having an N-tosylamine group was con-
verted into 1,3-diene 6g through a Heck reaction [Equa-
tion (9)].[17] Finally, lithium–telluride exchange followed by
addition to butyraldehyde led to allylic alcohol 6h in 67%
yield [Equation (10)].[14]
Conclusions
In summary, we have developed an efficient synthetic
method for cycloalkenyl selenides and tellurides from alk-
4
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Catalytic Intramolecular Hydroarylation
9.0 Hz, 2 H), 4.29–4.21 (m, 4 H), 3.80 (s, 3 H), 3.43 (s, 2 H), 1.25
(t, J = 7.2 Hz, 6 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 170.0,
159.5, 129.8, 129.7, 129.2, 128.2, 127.2, 114.4, 113.9, 99.9, 62.5,
ynyl selenides and tellurides through a TfOH-catalyzed in-
tramolecular hydroarylation reaction in a selective 6- and
7-endo mode. This method provides a variety of 1,2-dihy-
dronaphthalenes, 2H-chromenes, and 1,2-dihydroquinolines
having a phenylselenyl, phenyltelluryl, and butyltelluryl
group on the sp2 benzylic carbon atom. The cycloalkenyl
selenides and tellurides can be easily converted into an ar-
ray of other valuable functionalities such as cyclic olefins,
allylic alcohols, enynes, 1,3-dienes, and α,β-unsaturated al-
dehydes.
62.4, 62.1, 55.6, 28.8, 14.4 ppm. IR (film): ν = 2980, 2837, 1732,
˜
1515, 1235, 1182, 1028, 737 cm–1. HRMS (EI): calcd. for
C23H24O5Se 460.0789; found 460.0788.
(3-Phenoxyprop-1-ynyl)(phenyl)selane (2d): Yield 98% (844 mg); Rf
1
= 0.3 (EtOAc/hexane, 1:50); pale yellow oil. H NMR (400 MHz,
CDCl3): δ = 7.49–7.47 (m, 2 H), 7.33–7.25 (m, 5 H), 7.01–6.99 (m,
3 H), 4.90 (s, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 158.0,
129.9, 129.89, 129.8, 128.5, 127.7, 121.9, 115.5, 99.1, 68.8,
57.3 ppm. IR (film): ν = 3060, 2913, 2175, 1597, 1495, 1212, 1043,
˜
753, 735 cm–1. HRMS (EI): calcd. for C15H12OSe 288.0053; found
288.0051.
Experimental Section
General Methods: A variety of chemical reagents were commer-
cially purchased and used without further purification. CH2Cl2 and
DCE were freshly distilled from calcium hydride. All reaction mix-
tures were stirred magnetically and were monitored by thin-layer
chromatography by using silica gel precoated glass plates, which
were visualized with UV light and then developed by using a solu-
tion of p-anisaldehyde. Flash column chromatography was carried
out by using silica gel (230–400 mesh). 1H NMR and 13C NMR
spectra were measured with 400 MHz NMR spectrometer. Chemi-
cal shifts are reported in ppm relative to the internal standard tet-
ramethylsilane. 13C NMR are reported in ppm downfield from tet-
ramethylsilane and relative to the signal of CDCl3 (δ = 77.00 ppm,
t). Mass spectrometry was performed with a GC–HRMS spectrom-
eter (KBSI) under electron impact (EI) ionization technique (mag-
netic sector–electric sector double focusing mass analyzer). IR
spectra were recorded with an FTIR spectrometer as a thin film
pressed between two sodium chloride plates. Melting points were
determined in open capillary tubes.
[3-(4-Methoxyphenoxy)prop-1-ynyl](phenyl)selane (2e): Yield 88 %
(838 mg); Rf = 0.2 (EtOAc/hexane, 1:40); yellow oil. 1H NMR
(400 MHz, CDCl3): δ = 7.48–7.46 (m, 2 H), 7.29–7.26 (m, 3 H),
6.95 (d, J = 9.1 Hz, 2 H), 6.85 (d, J = 9.1 Hz, 2 H), 4.85 (s, 2 H),
3.78 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 154.9, 152.1,
129.9, 129.7, 128.5, 127.7, 116.8, 115.0, 99.4, 68.6, 58.3, 56.1 ppm.
IR (film): ν = 3057, 2950, 2832, 2174, 1506, 1477, 1242, 1206, 1041,
˜
736 cm–1. HRMS (EI): calcd. for C16H14O2Se 318.0159; found
318.0161.
[3-(Naphthalen-1-yloxy)prop-1-ynyl](phenyl)selane (2f): Yield 79%
(799 mg); Rf = 0.3 (EtOAc/hexane, 1:70); yellow oil. 1H NMR
(400 MHz, CDCl3): δ = 8.29 (d, J = 9.6 Hz, 1 H), 7.82–7.79 (m, 1
H), 7.52–7.46 (m, 5 H), 7.38 (t, J = 7.9 Hz, 1 H), 7.30–7.23 (m, 3
H), 6.97 (d, J = 7.6 Hz, 1 H), 5.10 (s, 2 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 153.8, 135.0, 129.9, 129.8, 128.5, 127.9,
127.7, 126.9, 126.2, 126.0, 125.8, 122.5, 121.6, 106.2, 99.1, 69.0,
57.7 ppm. IR (film): ν = 3053, 2175, 1578, 1401, 1268, 1096,
˜
770 cm–1. HRMS (EI): calcd. for C19H14OSe 338.0210; found
338.0211.
4-Methyl-N-phenyl-N-[3-(phenylselanyl)prop-2-ynyl]benzenesulfon-
amide (2a):[11a] A mixture of anhydrous CuI (1.14 g, 6 mmol), phen-
ylselenyl bromide (850 mg, 3.6 mmol), and 4-methyl-N-phenyl-N-
(prop-2-ynyl)benzenesulfonamide (855 mg, 3 mmol) in DMF
(6 mL) under a nitrogen atmosphere was stirred at 25 °C for 4 h.
The mixture was then quenched with water. The aqueous layer was
extracted with ethyl ether (2ϫ 15 mL), and the combined organic
layer was washed with NH4Cl, dried, filtered, and concentrated
under reduced pressure. The crude product was purified by silica
gel flash chromatography (EtOAc/hexane, 1:15) to give 2a (88%,
1.16 g). Rf = 0.2 (EtOAc/hexane, 1:15); yellow oil. 1H NMR
(400 MHz, CDCl3): δ = 7.52 (d, J = 8.3 Hz, 2 H), 7.31–7.24 (m, 10
H), 7.15 (d, J = 8.3 Hz, 2 H), 4.66 (s, 2 H), 2.35 (s, 3 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 144.1, 140.1, 135.9, 129.9, 129.7,
129.5, 129.46, 128.8, 128.5, 128.47, 128.4, 127.6, 98.3, 66.6, 43.1,
2,3-Bis[3-(phenylselanyl)prop-2-ynyloxy]naphthalene (2g): Yield
77% (1.26 g); Rf = 0.3 (EtOAc/hexane, 1:10); white solid; m.p. 80–
84 °C. 1H NMR (400 MHz, CDCl3): δ = 7.73–7.59 (m, 2 H), 7.49–
7.33 (m, 6 H), 7.33–7.29 (m, 2 H), 7.23–7.09 (m, 6 H), 5.05 (s, 4
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 147.5, 129.6, 129.4,
129.3, 128.2, 127.3, 126.7, 124.7, 109.4, 98.6, 69.6, 57.7 ppm. IR
(film): ν = 3056, 2924, 2175, 1478, 1247, 1162, 1111, 1021,
˜
735 cm–1. HRMS (EI): calcd. for C28H20O2Se2 547.9794; found
547.9790.
4-Methyl-N-[3-(phenylselanyl)prop-2-ynyl]-N-m-tolylbenzenesulfon-
amide (2h): Yield 78% (1.06 g); Rf = 0.4 (EtOAc/hexane, 1:7); yel-
1
low oil. H NMR (400 MHz, CDCl3): δ = 7.54 (d, J = 8.24 Hz, 2
H), 7.30–7.27 (m, 2 H), 7.26–7.22 (m, 3 H), 7.20–7.14 (m, 2 H),
7.01 (d, J = 7.6 Hz, 1 H), 4.65 (s, 2 H), 2.36 (s, 3 H), 2.29 (s, 3
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 143.6, 139.6, 139.0,
135.7, 129.5, 129.3, 129.2, 129.0, 128.9, 128.7, 128.1, 127.2, 125.1
22.0 ppm. IR (film): ν = 3060, 1596, 1493, 1351, 1164, 1092, 661,
˜
573 cm–1. HRMS (EI): calcd. for C22H19NO2SSe 441.0302; found
441.0305.
98.0, 66.0, 42.8, 21.6, 21.3 ppm. IR (film): ν = 3057, 2921, 1477,
˜
Phenyl(4-phenylbut-1-ynyl)selane (2b): Yield 91% (778.7 mg); Rf =
0.3 (hexane); yellow oil. 1H NMR (400 MHz, CDCl3): δ = 7.35–
7.32 (m, 2 H), 7.24–7.19 (m, 2 H), 7.17–7.11 (m, 5 H), 2.82 (t, J =
7.4 Hz, 2 H), 2.67 (t, J = 7.4 Hz, 2 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 140.8, 129.8, 129.5, 129.1, 129.0, 128.9, 127.2, 126.8,
1350, 1164, 1092, 693, 660 cm–1. HRMS (EI): calcd. for
C23H21NO2SSe 455.0458; found 455.0458.
N-(2-Isopropylphenyl)-4-methyl-N-[3-(phenylselanyl)prop-2-ynyl]-
benzenesulfonamide (2i): Yield 80% (1.16 g); Rf = 0.2 (EtOAc/hex-
104.1, 59.1, 35.5, 23.1 ppm. IR (film): ν = 3060, 3027, 2925, 1577,
˜
1
ane, 1:15); yellow oil. H NMR (400 MHz, CDCl3): δ = 7.65 (d, J
1476, 1439, 1021, 734, 698 cm–1. HRMS (EI): calcd. for C16H14Se
286.0261; found 286.0262.
= 6.8 Hz, 2 H), 7.40 (dd, J = 7.9, 1.6 Hz, 1 H), 7.33 (t, J = 7.5 Hz,
1 H), 7.28–7.21 (m, 7 H), 7.01 (t, J = 7.6 Hz, 1 H), 6.73 (d, J =
8.0 Hz, 1 H), 4.77 (d, J = 17.8 Hz, 1 H), 4.43 (d, J = 18.0 Hz, 1
H), 3.60–3.57 (m, 1 H), 2.41 (s, 3 H), 1.27 (d, J = 6.8 Hz, 3 H),
1.18 (d, J = 6.8 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ =
Diethyl 2-(4-Methoxyphenyl)-2-[3-(phenylselanyl)prop-2-ynyl]-
malonate (2c): Yield 78% (1.07 g); Rf = 0.3 (EtOAc/hexane, 1:10);
pale yellow oil. 1H NMR (400 MHz, CDCl3): δ = 7.43 (d, J =
9.0 Hz, 2 H), 7.37–7.32 (m, 2 H), 7.25–7.20 (m, 3 H), 6.87 (d, J = 150.3, 143.7, 136.5, 136.0, 129.5, 129.4, 129.2, 129.1, 128.4, 128.3,
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
5

Job/Unit: O21763
/KAP1
Date: 12-03-13 12:48:54
Pages: 12
D. Eom, S. Park, Y. Park, K. Lee, G. Hong, P. H. Lee
FULL PAPER
128.0, 127.4, 127.2, 125.8, 97.6, 66.1, 43.5, 27.7, 24.8, 23.5,
3 H), 7.02–6.99 (m, 2 H), 6.99–76.96 (m, 1 H), 4.95 (s, 2 H) ppm.
21.6 ppm. IR (film): ν = 2964, 1489, 1477, 1350, 1163, 1092,
13C NMR (100 MHz, CDCl3): δ = 157.6, 135.5, 129.8, 129.5, 128.1,
˜
659 cm–1. HRMS (EI): calcd. for C25H25NO2SSe 483.0771; found 121.5, 115.1, 112.4, 109.9, 57.1, 46.7 ppm. IR (film): ν = 3289,
˜
483.0771.
3064, 1598, 1495, 1214, 1038, 754, 689 cm–1. HRMS (EI): calcd.
for C15H12OTe 337.9950; found 337.9950.
N-(4-Bromophenyl)-4-methyl-N-[3-(phenylselanyl)prop-2-ynyl]-
benzenesulfonamide (2j): Yield 84% (1.31 g); Rf = 0.2 (EtOAc/hex-
ane, 1:15); white solid; m.p. 90–94 °C. 1H NMR (400 MHz,
CDCl3): δ = 7.51 (d, J = 8.3 Hz, 2 H), 7.42 (d, J = 8.8 Hz, 2 H),
7.27 (s, 5 H), 7.17 (d, J = 8.2 Hz, 2 H), 7.13 (d, J = 8.8 Hz, 2 H),
4.63 (s, 2 H), 2.37 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ
= 144.3, 139.0, 135.5, 132.6, 130.3, 129.9, 129.8, 129.7, 128.4, 128.2,
[3-(4-tert-Butylphenoxy)prop-1-ynyl](phenyl)tellane (3c): Yield 65%
(255 mg); Rf = 0.5 (EtOAc/hexane, 1:20); yellow oil. 1H NMR
(400 MHz, CDCl3): δ = 7.68–7.65 (m, 2 H), 7.32–7.21 (m, 5 H),
6.92 (d, J = 8.9 Hz, 2 H), 4.93 (s, 2 H), 1.30 (s, 9 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 155.4, 144.2, 135.5, 129.7, 128.1,
126.2, 114.5, 114.3, 110.2, 57.3, 46.4, 34.1, 31.5 ppm. IR (film): ν˜
127.8, 122.4, 97.6, 67.2, 42.9, 22.0 ppm. IR (film): ν = 3065, 2923, = 3054, 2961, 1608, 1511, 1222, 1184, 1033, 828, 731 cm–1. HRMS
˜
2849, 2361, 1345, 1161, 740, 668 cm–1. HRMS (EI): calcd. for
C22H18BrNO2SSe 518.9407; found 518.9409.
(EI): calcd. for C19H20OTe 394.0576; found 394.0579.
4-Methyl-N-phenyl-N-[3-(phenyltellanyl)prop-2-ynyl]benzenesulfon-
amide (3d): Yield 76% (372 mg); Rf = 0.1 (EtOAc/hexane, 1:20);
N-(4-Cyanophenyl)-4-methyl-N-[3-(phenylselanyl)prop-2-ynyl]-
benzenesulfonamide (2k): Yield 68% (949.5 mg); Rf = 0.3 (EtOAc/
1
brown oil. H NMR (400 MHz, CDCl3): δ = 7.54–7.50 (m, 2 H),
1
7.49–7.45 (m, 2 H), 7.31–7.23 (m, 6 H), 7.23–7.18 (m, 2 H), 7.17–
7.13 (m, 2 H), 4.74 (s, 2 H), 2.36 (s, 3 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 143.6, 139.7, 135.6, 135.3, 129.7, 129.2,
129.0, 128.4, 128.2, 128.1, 128.0, 112.2, 109.0, 44.4, 43.0, 21.6 ppm.
hexane, 1:5); yellow oil. H NMR (400 MHz, CDCl3): δ = 7.57 (d,
J = 8.6 Hz, 2 H), 7.49 (d, J = 8.3 Hz, 2 H), 7.44 (d, J = 8.7 Hz, 2
H), 7.31–7.27 (m, 5 H), 7.16 (d, J = 8.2 Hz, 2 H), 4.69 (s, 2 H),
2.36 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 144.4, 143.9,
134.8, 132.9, 129.6, 129.5, 129.53, 127.9, 127.6, 127.5, 127.4, 118.2,
IR (film): ν = 3285, 1596, 1492, 1350, 1163, 1092, 695, 660,
˜
572 cm–1. HRMS (EI): calcd. for C22H19NO2STe 491.0199; found
491.0200.
111.0, 96.6, 67.7, 42.0, 21.6 ppm. IR (film): ν = 3058, 2924, 2359,
˜
2336, 1598, 1501, 1356, 1162, 591 cm–1. HRMS (EI): calcd. for
C23H18N2O2SSe 466.0254; found 466.0252.
Synthesis of N-[3-(Butyltellanyl)prop-2-ynyl]-4-methyl-N-phenyl-
benzenesulfonamide (3e):[11c] A mixture of anhydrous InCl3
(22.12 mg, 0.1 mmol), Cs2CO3 (325.82 mg, 1 mmol), dibutyl di-
telluride (184.7 mg, 0.5 mmol), and 4-methyl-N-phenyl-N-(prop-2-
ynyl)benzenesulfonamide (285 mg, 1 mmol) in DMSO (3 mL) un-
der a nitrogen atmosphere was stirred at 80 °C for 12 h. The mix-
ture was then quenched with water. The aqueous layer was ex-
tracted with ethyl ether (2ϫ 15 mL), and the combined organic
layer was washed with brine, dried, filtered, and concentrated under
reduced pressure. The crude product was purified by silica gel flash
chromatography (EtOAc/hexane, 1:15) to give 3e (58%, 272.1 mg).
Rf = 0.3 (EtOAc/hexane, 1:15); yellow oil. 1H NMR (400 MHz,
CDCl3): δ = 7.54 (d, J = 8.3 Hz, 2 H), 7.30–7.27 (m, 3 H), 7.26–
7.22 (m, 4 H), 4.67 (s, 2 H), 2.64 (t, J = 7.5 Hz, 2 H), 2.41 (s, 3 H),
1.69 (quint., J = 7.5 Hz, 2 H), 1.33 (sext., J = 7.5 Hz, 2 H), 0.89
(t, J = 7.4 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 143.5,
139.8, 135.7, 129.2, 128.9, 128.4, 128.2, 128.0, 105.8, 43.0, 41.3,
Phenyl(5-phenylpent-1-ynyl)selane (2l): Yield 90% (808 mg); Rf =
0.2 (hexane); yellow oil. 1H NMR (400 MHz, CDCl3): δ = 7.53 (d,
J = 7.60 Hz, 2 H), 7.33–7.26 (m, 4 H), 7.26–7.22 (m, 1 H), 7.22–
7.15 (m, 3 H), 2.76 (t, J = 7.56 Hz, 2 H), 2.46 (t, J = 7.00 Hz, 2
H), 1.91 (quint., J = 7.28 Hz, 2 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 141.5, 129.4, 129.3, 128.7, 128.6, 128.4, 126.8, 126.0,
104.1, 58.2, 34.8, 30.3, 20.0 ppm. IR (film): ν = 3025, 2941, 1577,
˜
1476, 1439, 1021, 734, 699 cm–1. HRMS (EI): calcd. for C17H16Se
300.0417; found 300.0413.
N-Benzyl-4-methyl-N-[3-(phenylselanyl)prop-2-ynyl]benzenesulfon-
amide (2m): Yield 81% (1.1 g); Rf = 0.4 (EtOAc/hexane, 1:15); pale
1
yellow oil. H NMR (400 MHz, CDCl3): δ = 7.77 (d, J = 8.3 Hz,
2 H), 7.35–7.28 (m, 10 H), 7.21 (d, J = 7.9 Hz, 2 H), 4.35 (s, 2 H),
4.16 (s, 2 H), 2.35 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ
= 144.1, 136.1, 135.3, 129.95, 129.9, 129.5, 129.2, 129.1, 128.5,
128.4, 128.2, 127.7, 96.4, 66.5, 50.6, 37.7, 21.9 ppm. IR (film): ν =
˜
33.7, 24.7, 21.6, 13.4, 9.3 ppm. IR (film): ν = 2957, 2927, 1492,
˜
3061, 3032, 2920, 1598, 1573, 1480, 1162, 736 cm–1. HRMS (EI):
calcd. for C23H21NO2SSe 455.0458; found 455.0458.
1351, 1163, 1092, 853, 659, 571 cm–1. HRMS (EI): calcd. for
C20H23NO2STe 471.0512; found 471.0514.
Synthesis of Phenyl(4-phenylbut-1-ynyl)tellane (3a):[11b] A mixture
of anhydrous CuI (19.5 mg, 0.1 mmol), K2CO3 (276.4 mg,
2.0 mmol), diphenyl ditelluride (204.7 mg, 0.5 mmol), and 4-
phenyl-1-butyne (260 mg, 2 mmol) in DMSO (5 mL) under a nitro-
gen atmosphere was stirred at 30 °C for 48 h. The mixture was then
quenched with water. The aqueous layer was extracted with ethyl
ether (2ϫ 15 mL), and the combined organic layer was washed
with NH4Cl, dried, filtered, and concentrated under reduced pres-
sure. The crude product was purified by silica gel flash chromatog-
raphy (hexane) to give 3a (76%, 254.0 mg). Rf = 0.2 (hexane); col-
Synthesis of Butyl(4-phenylbut-1-ynyl)tellane (3f):[12] n-BuLi (1.6 m
in hexane, 1.88 mL, 3 mmol) was added dropwise to a solution of
4-phenyl-1-butyne (390.6 mg, 3 mmol) in THF (5 mL) at 0 °C un-
der a nitrogen atmosphere. After 5 min of stirring at 0 °C, elemen-
tal tellurium (383 mg, 3 mmol) was added, and the mixture was
heated at reflux until the tellurium disappeared (30 min). The heat
source was removed, and n-butyl bromide (411 mg, 3 mmol) was
added. The mixture was stirred for 40 min at 30 °C, then diluted
with diethyl ether (60 mL) and washed with brine; the organic layer
was dried with MgSO4. The crude product was purified by silica
gel flash chromatography (hexane) to give 3f (93%, 874.0 mg). Rf
= 0.3 (hexane); colorless oil. 1H NMR (400 MHz, CDCl3): δ =
7.31–7.27 (m, 2 H), 7.22–7.21 (m, 3 H), 2.86–2.83 (m, 2 H), 2.80–
2.74 (m, 4 H), 1.81 (quint., J = 7.5 Hz, 2 H), 1.40 (sext., J = 7.5 Hz,
2 H), 0.93 (t, J = 7.4 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3):
δ = 140.6, 128.5, 128.4, 126.3, 111.6, 35.5, 33.7, 32.6, 24.7, 23.2,
1
orless oil. H NMR (400 MHz, CDCl3): δ = 7.60 (d, J = 7.9 Hz, 2
H), 7.31–7.19 (m, 8 H), 2.91–2.83 (m, 4 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 141.3, 135.7, 130.4, 129.3, 129.2, 128.5,
127.1, 115.8, 113.7, 36.3, 35.5, 23.4 ppm. IR (film): ν = 3059, 3026,
˜
1574, 1474, 1435, 1017, 997, 731, 698 cm–1. HRMS (EI): calcd. for
C16H14Te 336.0158; found 336.0155.
(3-Phenoxyprop-1-ynyl)(phenyl)tellane (3b): Yield 81% (272 mg); Rf 13.4, 9.0 ppm. IR (film): ν = 2955, 2926, 2869, 1496, 1454, 1182,
˜
= 0.3 (EtOAc/hexane, 1:40); yellow oil. 1H NMR (400 MHz,
1077, 747, 698 cm–1. HRMS (EI): calcd. for C14H18Te 316.0471,
CDCl3): δ = 7.68–7.62 (m, 2 H), 7.32–7.27 (m, 2 H), 7.27–7.20 (m, found 316.0472.
6
www.eurjoc.org
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 0000, 0–0

Job/Unit: O21763
/KAP1
Date: 12-03-13 12:48:54
Pages: 12
Catalytic Intramolecular Hydroarylation
Synthesis of 4-(Phenylselanyl)-1-tosyl-1,2-dihydroquinoline (4a): To
a solution of 2a (220.2 mg, 0.5 mmol) in CH2Cl2 (5 mL) was added
TfOH (3.8 mg, 0.025 mmol, 5 mol-%) at room temperature. The
mixture was stirred at room temperature for 5 min. The solvent was
removed under reduced pressure. The crude product was purified
by silica gel flash chromatography (EtOAc/hexane, 1:15) to give 4a
(92%, 202.6 mg). Rf = 0.2 (EtOAc/hexane, 1:15); white solid; m.p.
103–107 °C. 1H NMR (400 MHz, CDCl3): δ = 7.73 (d, J = 8.0 Hz,
1 H), 7.36–7.28 (m, 4 H), 7.26–7.13 (m, 6 H), 7.09 (d, J = 7.0 Hz,
2 H), 5.66 (t, J = 4.5 Hz, 1 H), 4.41 (d, J = 4.5 Hz, 2 H), 2.39 (s,
3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 144.1, 136.8, 135.6,
133.4, 130.2, 129.8, 129.75, 129.2, 128.3, 128.2, 128.0, 127.8, 127.5,
124.8, 124.7, 122.6, 121.1, 117.9, 67.1 ppm. IR (film): ν = 3055,
˜
1673, 1625, 1437, 1385, 1361, 1097, 1021, 737, 688 cm–1. HRMS
(EI): calcd. for C19H14OSe 338.0210; found 338.0208.
4,9-Bis(phenylselanyl)-2,11-dihydrobenzo[f]pyrano[3,2-h]chromene
(4g): Yield 62% (169.3 mg); Rf = 0.3 (EtOAc/hexane, 1:10); yellow
1
solid; m.p. 43–47 °C. H NMR (400 MHz, CDCl3): δ = 8.41–8.39
(m, 2 H), 7.63–7.61 (m, 4 H), 7.44–7.42 (m, 2 H), 7.34–7.30 (m, 6
H), 5.68 (t, J = 5.1 Hz, 2 H), 4.57 (t, J = 5.1 Hz, 4 H) ppm. 13C
NMR (100 MHz, CDCl3): δ = 145.1, 136.5, 130.4, 130.2, 129.5,
128.7, 127.1, 126.2, 125.1, 122.4, 122.2, 66.5 ppm. IR (film): ν =
˜
3056, 2924, 2849, 1475, 1437, 1302, 1241, 1118, 1021, 999, 737,
689 cm–1. HRMS (EI): calcd. for C28H20O2Se2 547.9794; found
547.9798.
127.3, 127.0, 47.0, 22.0 ppm. IR (film): ν = 3059, 2848, 1599, 1476,
˜
1354, 1165, 1090, 814, 763, 684 cm–1. HRMS (EI): calcd. for
C22H19NO2SSe 441.0302; found 441.0305.
8-Isopropyl-4-(phenylselanyl)-1-tosyl-1,2-dihydroquinoline (4h):
Yield 93% (224.3 mg); Rf = 0.2 (EtOAc/hexane, 1:15); white solid;
m.p. 150–155 °C. H NMR (400 MHz, CDCl3): δ = 7.39–7.36 (m,
(3,4-Dihydronaphthalen-1-yl)(phenyl)selane (4b): Yield 91 %
(129.8 mg); Rf = 0.4 (hexane); yellow oil. 1H NMR (400 MHz,
CDCl3): δ = 7.59–7.54 (m, 1 H), 7.41–7.38 (m, 2 H), 7.24–7.15 (m,
3 H), 7.14–7.08 (m, 3 H), 6.59 (t, J = 4.7 Hz, 1 H), 2.84 (t, J =
8.0 Hz, 2 H), 2.44–2.39 (m, 2 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 138.8, 136.6, 134.5, 131.9, 131.3, 129.6, 128.8, 128.1,
1
1 H), 7.28 (d, J = 8.3 Hz, 2 H), 7.26–7.21 (m, 7 H), 7.16 (d, J =
8.2 Hz, 2 H), 5.44 (dd, J = 5.9, 2.5 Hz, 1 H), 4.64 (dd, J = 18.1,
6.0 Hz, 1 H), 3.97–3.89 (m, 2 H), 2.44 (s, 3 H), 1.44 (d, J = 6.9 Hz,
3 H), 1.10 (d, J = 6.9 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3):
δ = 149.0, 144.1, 136.6, 133.7, 132.5, 132.0, 129.8, 129.75, 129.4,
129.3, 129.28, 128.5, 128.3, 128.2, 127.8, 124.0, 47.8, 29.0, 26.4,
127.9, 127.3, 127.2, 126.9, 28.3, 25.7 ppm. IR (film): ν = 3059,
˜
2933, 2827, 1577, 1476, 1437, 1069, 1021, 761, 732, 689 cm–1
HRMS (EI): calcd. for C16H14Se 286.0261; found 286.0262.
.
22.2, 22.1 ppm. IR (film): ν = 3058, 2959, 2869, 1577, 1475, 1438,
˜
1353, 1164, 1090, 815, 738, 676 cm–1. HRMS (EI): calcd. for
C25H25NO2SSe 483.0771; found 483.0773.
Diethyl 6-Methoxy-4-(phenylselanyl)naphthalene-1,1(2H)-dicarb-
oxylate (4c): Yield 82% (188.3 mg); Rf = 0.3 (EtOAc/hexane, 1:10);
colorless oil. 1H NMR (400 MHz, CDCl3): δ = 7.34–7.30 (m, 2 H),
7.25 (s, 1 H), 7.20–7.15 (m, 3 H), 7.10 (d, J = 8.5 Hz, 1 H), 6.76
(dd, J = 8.5, 2.7 Hz, 1 H), 6.62 (t, J = 4.7 Hz, 1 H), 4.28–4.19 (m,
4 H), 3.69 (s, 3 H), 3.12 (d, J = 4.7 Hz, 2 H), 1.25 (t, J = 7.1 Hz,
6 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 170.9, 159.5, 135.4,
134.4, 131.1, 130.9, 129.1, 128.6, 128.4, 126.6, 124.7, 113.6, 113.3,
6-Bromo-4-(phenylselanyl)-1-tosyl-1,2-dihydroquinoline (4i): Yield
89% (231.0 mg); Rf = 0.2 (EtOAc/hexane, 1:15); white solid; m.p.
104–106 °C. 1H NMR (400 MHz, CDCl3): δ = 7.60 (d, J = 8.6 Hz,
1 H), 7.51 (d, J = 2.2 Hz, 1 H), 7.41 (dd, J = 8.6, 2.3 Hz, 1 H),
7.34 (d, J = 8.3 Hz, 2 H), 7.29–7.23 (m, 1 H), 7.23–7.16 (m, 4 H),
7.12–7.09 (m, 2 H), 5.66 (t, J = 4.5 Hz, 1 H), 4.39 (d, J = 4.5 Hz,
2 H), 2.41 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 144.3,
136.6, 134.6, 133.7, 132.0, 131.9, 130.0, 129.9, 129.8, 129.0, 128.5,
62.0, 58.4, 55.2, 32.7, 14.0 ppm. IR (film): ν = 2980, 2905, 1731,
˜
1478, 1234, 1178, 1049, 1025, 737 cm–1. HRMS (EI): calcd. for
C23H24O5Se 460.0789; found 460.0786.
128.4, 127.7, 127.4, 120.8, 46.9, 22.1 ppm. IR (film): ν = 3059,
˜
2922, 1597, 1577, 1468, 1355, 1164, 1088, 816, 737, 688, 661 cm–1.
HRMS (EI): calcd. for C22H18BrNO2SSe 518.9407; found
518.9409.
4-(Phenylselanyl)-2H-chromene (4d): Yield 87% (125.0 mg); Rf =
0.3 (EtOAc/hexane, 1:50); yellow oil. 1H NMR (400 MHz, CDCl3):
δ = 7.50–7.47 (m, 2 H), 7.38 (dd, J = 7.7, 1.5 Hz, 1 H), 7.28–7.25
(m, 3 H), 7.12 (td, J = 7.7, 1.5 Hz, 1 H), 6.85 (td, J = 7.6, 1.0 Hz,
1 H), 6.80 (dd, J = 8.0, 1.0 Hz, 1 H), 6.00 (t, J = 3.8 Hz, 1 H), 4.78
(d, J = 3.8 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 154.5,
133.1, 131.9, 130.3, 129.8, 129.6, 127.8, 127.6, 127.2, 123.3, 122.0,
4-(Phenylselanyl)-1-tosyl-1,2-dihydroquinoline-6-carbonitrile (4j):
Yield 85% (197.8 mg); Rf = 0.3 (EtOAc/hexane, 1:15); white solid;
m.p. 136–139 °C. 1H NMR (400 MHz, CDCl3): δ = 7.84 (d, J =
8.4 Hz, 1 H), 7.68 (d, J = 1.8 Hz, 1 H), 7.55 (dd, J = 8.3, 1.8 Hz,
1 H), 7.39 (d, J = 8.3 Hz, 2 H), 7.29–7.26 (m, 1 H), 7.23–7.19 (m,
4 H), 7.10–7.07 (m, 2 H), 5.90 (t, J = 4.5 Hz, 1 H), 4.48 (d, J =
4.5 Hz, 2 H), 2.43 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ
= 144.8, 139.7, 136.6, 133.2, 132.5, 131.1, 130.7, 130.6, 130.1, 129.9,
128.4, 128.38, 127.6, 127.4, 126.9, 118.6, 110.5, 46.7, 22.1 ppm. IR
116.4, 66.7 ppm. IR (film): ν = 3057, 2924, 1687, 1609, 1476, 1465,
˜
1219, 1020, 758, 737, 688 cm–1. HRMS (EI): calcd. for C15H12OSe
288.0053; found 288.0050.
6-Methoxy-4-(phenylselanyl)-2H-chromene (4e): Yield 90 %
(142.7 mg); Rf = 0.2 (EtOAc/hexane, 1:50); yellow oil. 1H NMR
(400 MHz, CDCl3): δ = 7.50–7.47 (m, 2 H), 7.28–7.24 (m, 3 H),
6.97 (d, J = 2.9 Hz, 1 H), 6.75 (d, J = 8.7 Hz, 1 H), 6.68 (dd, J =
8.7, 2.9 Hz, 1 H), 6.10 (t, J = 4.0 Hz, 1 H), 4.71 (d, J = 4.0 Hz, 2
H), 3.66 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 154.6,
148.4, 133.0, 129.8, 128.8, 127.8, 127.0, 124.1, 117.0, 115.7, 112.5,
(film): ν = 3059, 2925, 2229, 1599, 1477, 1359, 1167, 738, 672,
˜
591 cm–1. HRMS (EI): calcd. for C23H18N2O2SSe 466.0254; found
466.0251.
(6,7-Dihydro-5H-benzo[7]annulen-9-yl)(phenyl)selane (4k): Yield
83 % (124.2 mg); Rf = 0.3 (hexane); pale yellow oil. 1H NMR
(400 MHz, CDCl3): δ = 7.63 (d, J = 7.5 Hz, 1 H), 7.41–7.39 (m, 2
H), 7.19–7.11 (m, 6 H), 6.60 (t, J = 7.3 Hz, 1 H), 2.63 (t, J =
7.0 Hz, 2 H), 2.16 (quint., J = 7.1 Hz, 2 H), 1.91 (q, J = 7.3 Hz, 2
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 142.2, 140.5, 137.3,
133.3, 132.8, 132.1, 129.9, 129.8, 129.6, 128.3, 127.7, 127.0, 35.6,
66.7, 56.1 ppm. IR (film): ν = 2937, 1651, 1485, 1281, 1205, 1037,
˜
737, 689 cm–1. HRMS (EI): calcd. for C16H14O2Se 318.0159; found
318.0161.
4-(Phenylselanyl)-2H-benzo[h]chromene (4f): Yield 80% (134.9 mg);
Rf = 0.4 (EtOAc/hexane, 1:70); yellow oil. 1H NMR (400 MHz,
CDCl3): δ = 8.17–8.15 (m, 1 H), 7.72–7.68 (m, 1 H), 7.54 (d, J =
8.5 Hz, 1 H), 7.50–7.47 (m, 2 H), 7.45–7.41 (m, 2 H), 7.32 (d, J =
8.5 Hz, 1 H), 7.27–7.22 (m, 3 H), 6.06 (t, J = 4.0 Hz, 1 H), 4.95 (d,
J = 4.0 Hz, 2 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 150.4,
135.0, 132.8, 130.1, 129.8, 128.0, 127.7, 127.6, 127.2, 126.0, 125.9,
32.9, 26.8 ppm. IR (film): ν = 3058, 3014, 2930, 2854, 1577, 1476,
˜
1446, 1069, 1022, 906 cm–1. HRMS (EI): calcd. for C17H16Se
300.0417; found 300.0416.
5-(Phenylselanyl)-2-tosyl-2,3-dihydro-1H-benzo[c]azepine (4l): Yield
57% (129.5 mg); Rf = 0.3 (EtOAc/hexane, 1:10); colorless oil. 1H
Eur. J. Org. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Date: 12-03-13 12:48:54
Pages: 12
D. Eom, S. Park, Y. Park, K. Lee, G. Hong, P. H. Lee
FULL PAPER
NMR (400 MHz, CDCl3): δ = 7.68 (d, J = 8.3 Hz, 2 H), 7.63 (d,
J = 7.9 Hz, 1 H), 7.33–7.19 (m, 10 H), 5.87 (t, J = 7.3 Hz, 1 H),
1.19 (s, 9 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 151.4, 144.4,
138.2, 134.0, 129.6, 128.0, 127.7, 126.6, 123.7, 115.5, 113.7, 113.5,
4.16 (s, 2 H), 3.57 (d, J = 7.3 Hz, 2 H), 2.44 (s, 3 H) ppm. 13C 67.0, 31.6, 31.4 ppm. IR (film): ν = 3053, 2962, 2903, 2866, 1487,
˜
NMR (100 MHz, CDCl3): δ = 143.4, 139.2, 138.8, 135.9, 134.6,
133.4, 130.0, 129.7, 129.3, 128.9, 128.7, 128.5, 128.2, 127.5, 124.9,
1230, 1017, 826, 730, 690 cm–1. HRMS (EI): calcd. for C19H20OTe
394.0576; found 394.0578.
49.7, 44.5, 21.6 ppm. IR (film): ν = 3058, 2847, 1600, 1476, 1354,
˜
4-(Butyltellanyl)-1-tosyl-1,2-dihydroquinoline (5e): Yield 72 %
(168.8 mg); Rf = 0.3 (EtOAc/hexane, 1:15); pale yellow oil. 1H
NMR (400 MHz, CDCl3): δ = 7.69–7.67 (m, 1 H), 7.35–7.22 (m, 5
H), 7.09 (d, J = 8.0 Hz, 2 H), 6.08 (t, J = 4.4 Hz, 1 H), 4.41 (d, J
= 4.4 Hz, 2 H), 2.41 (t, J = 7.6 Hz, 2 H), 2.35 (s, 3 H), 1.59 (quint.,
J = 7.6 Hz, 2 H), 1.31 (sext., J = 7.5 Hz, 2 H), 0.89 (t, J = 7.4 Hz,
3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 143.5, 136.2, 134.7,
134.5, 132.1, 130.2, 129.2, 128.6, 127.4, 127.3, 127.1, 111.6, 47.1,
1165, 1090, 815, 738, 676 cm– 1 . HRMS (EI): calcd. for
C23H21NO2SSe 455.0458; found 455.0457.
7-Methyl-4-(phenylselanyl)-1-tosyl-1,2-dihydroquinoline (major) and
5-Methyl-4-(phenylselanyl)-1-tosyl-1,2-dihydroquinoline (minor)
(4m): Yield 91% (206.7 mg); Rf = 0.2 (EtOAc/hexane, 1:15); color-
less oil. 1H NMR (400 MHz, CDCl3, major): δ = 7.56 (s, 1 H), 7.34
(d, J = 8.3, 2 H), 7.24–7.14 (m, 6 H), 7.10–7.07 (m, 2 H), 6.99 (dd,
J = 7.9, 0.8, 1 H), 5.59 (t, J = 4.5, 1 H), 4.40 (d, J = 4.5, 2 H), 2.41
33.3, 25.0, 21.6, 13.4, 7.9 ppm. IR (film): ν = 2926, 1596, 1449,
˜
1
1165, 1090, 813, 762, 683, 575 cm–1. HRMS (EI): calcd. for
C20H23NO2STe 471.0512; found 471.0512.
(s, 3 H), 2.40 (s, 3 H) ppm. H NMR (400 MHz, CDCl3, minor): δ
= 7.68 (d, J = 8.0 Hz, 1 H), 7.39 (d, J = 8.3 Hz, 2 H), 7.29–7.28
(m, 1 H), 7.25–7.17 (m, 4 H), 7.14 (d, J = 8.3 Hz, 2 H), 7.10–7.04
(m, 2 H), 5.46 (t, J = 5.2 Hz, 1 H), 4.16 (d, J = 5.2 Hz, 2 H), 2.53
(s, 3 H), 2.41 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3, major):
δ = 143.6, 139.1, 136.4, 135.0, 134.5, 132.8, 129.3, 129.28, 127.7,
127.6, 127.5, 127.4, 127.2, 126.7, 126.4, 46.6, 21.6, 21.5 ppm. 13C
NMR (100 MHz, CDCl3, minor): δ = 143.4, 137.5, 137.0, 135.8,
130.4, 129.6, 129.4, 129.2, 128.9, 128.3, 128.2, 128.1, 127.9, 127.8,
4-(Phenyltellanyl)-1-tosyl-1,2-dihydroquinoline (5f): Yield 80%
(195.6 mg); Rf = 0.2 (EtOAc/hexane, 1:15); yellow oil. 1H NMR
(400 MHz, CDCl3): δ = 7.67 (dd, J = 7.9, 0.8 Hz, 1 H), 7.44 (dd,
J = 7.9, 1.1 Hz, 2 H), 7.33–7.26 (m, 4 H), 7.24–7.16 (m, 4 H), 7.12
(d, J = 8.1 Hz, 2 H), 5.90 (t, J = 4.5 Hz, 1 H), 4.38 (d, J = 4.5 Hz,
2 H), 2.40 (s, 3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 143.7,
138.0, 136.1, 135.4, 134.7, 131.9, 129.6, 129.4, 129.3, 128.8, 128.2,
124.6, 46.0, 23.1, 21.7 ppm. IR (film): ν = 3057, 1596, 1352, 1162,
˜
127.4, 127.38, 127.2, 113.6, 113.2, 47.4, 21.7 ppm. IR (film): ν =
˜
1089, 1009, 814, 739, 683 cm– 1 . HRMS (EI): calcd. for
C23H21NO2SSe 455.0458; found 455.0458 (major), 455.0457
(minor).
3060, 2922, 1596, 1474, 1353, 1165, 1090, 734, 683 cm–1. HRMS
(EI): calcd. for C22H19NO2STe 491.0199; found 491.0201.
Synthesis of 4-Phenyl-1,2-dihydronaphthalene (6a):[13] To a solution
of cycloalkenyl selenide (0.3 mmol) and NiCl2[dppp] (5 mol-%) in
THF (2 mL) was added the Grignard reagent (1.0 m in THF,
2.5 equiv.) at room temperature. The mixture was stirred at 70 °C
for 1 h and then quenched with water. The aqueous layer was ex-
tracted with ethyl ether (2ϫ 15 mL), and the combined organic
layer was washed with brine, dried, filtered, and concentrated under
reduced pressure. The crude product was purified by silica gel flash
chromatography (hexane) to give 6a (71%, 44.0 mg). Rf = 0.5 (hex-
ane); colorless oil. 1H NMR (400 MHz, CDCl3): δ = 7.39–7.30 (m,
5 H), 7.20–7.18 (m, 1 H), 7.15 (td, J = 7.2, 1.4 Hz, 1 H), 7.10 (td,
J = 7.2, 1.7 Hz, 1 H), 7.01–6.99 (m, 1 H), 6.08 (t, J = 4.7 Hz, 1
H), 2.85 (t, J = 7.9 Hz, 2 H), 2.42–2.37 (m, 2 H) ppm. 13C NMR
(100 MHz, CDCl3): δ = 140.8, 139.9, 136.8, 135.1, 128.8, 128.3,
127.7, 127.6, 127.1, 127.0, 126.2, 125.5, 28.3, 23.6 ppm. IR (film):
Butyl(3,4-Dihydronaphthalen-1-yl)tellane (5a): Yield 76 %
(119.2 mg); Rf = 0.5 (hexane); colorless oil. 1H NMR (400 MHz,
CDCl3): δ = 7.51 (dd, J = 7.6, 0.8 Hz, 1 H), 7.20 (td, J = 7.6,
1.3 Hz, 1 H), 7.13 (td, J = 7.3, 1.3 Hz, 1 H), 7.05 (dd, J = 7.3,
0.8 Hz, 1 H), 6.75 (t, J = 4.7 Hz, 1 H), 2.80–2.72 (m, 4 H), 2.39–
2.34 (m, 2 H), 1.73 (quint., J = 7.5 Hz, 2 H), 1.37 (sext., J = 7.5 Hz,
2 H), 0.88 (t, J = 7.4 Hz, 3 H) ppm. 13C NMR (100 MHz, CDCl3):
δ = 142.1, 136.2, 135.7, 130.3, 127.6, 127.4, 126.9, 113.8, 33.6, 28.2,
26.2, 25.1, 13.5, 7.3 ppm. IR (film): ν = 2954, 2927, 1476, 1448,
˜
1424, 1159, 1043, 949, 757, 729 cm–1. HRMS (EI): calcd. for
C14H18Te 316.0471; found 316.0472.
(3,4-Dihydronaphthalen-1-yl)(phenyl)tellane (5b): Yield 88 %
(146.9 mg); Rf = 0.3 (hexane); colorless oil. 1H NMR (400 MHz,
CDCl3): δ = 7.63 (d, J = 6.9 Hz, 2 H), 7.49–7.46 (m, 1 H), 7.23–
7.11 (m, 5 H), 7.10–7.06 (m, 1 H), 6.84 (t, J = 4.6 Hz, 1 H), 2.82
(t, J = 8.0 Hz, 2 H), 2.44–2.38 (m, 2 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 145.6, 137.5, 136.6, 136.57, 131.0, 130.2, 128.4, 128.39,
ν = 2933, 2829, 1663, 1492, 1443, 771, 757, 739 cm–1. HRMS (EI):
˜
calcd. for C16H14 206.1096; found 206.1097.
Synthesis of 1-(3,4-Dihydronaphthalen-1-yl)butan-1-ol (6b):[14] To a
solution of cycloalkenyl telluride (0.3 mmol) in THF (1.5 mL) at
–78 °C under a nitrogen atmosphere was dropwise added a solution
of n-BuLi (1.6 m in hexanes, 1.1 equiv.). After 20 min of stirring at
this temperature, the electrophile (1.5 equiv.) was added. The mix-
ture was stirred for 1 h at –78 °C and then diluted with ethyl acetate
(2ϫ 15 mL) and washed with water (2ϫ 10 mL). The organic layer
was separated, dried with MgSO4, filtered, and concentrated under
reduced pressure. The crude product was purified by silica gel flash
chromatography (EtOAc/hexane, 1:10) to give 6b (90%, 55.0 mg).
128.2, 127.8, 117.2, 115.5, 28.2, 26.6 ppm. IR (film): ν = 3061,
˜
2931, 2880, 2825, 1574, 1474, 1434, 1017, 758, 728, 689 cm–1
HRMS (EI): calcd. for C16H14Te 336.0158; found 336.0155.
.
4-(Phenyltellanyl)-2H-chromene (5c): Yield 90% (151.1 mg); Rf =
0.3 (EtOAc/hexane, 1:40); pale yellow oil. 1H NMR (400 MHz,
CDCl3): δ = 7.72–7.70 (m, 2 H), 7.29–7.21 (m, 4 H), 7.12 (td, J =
7.7, 1.5 Hz, 1 H), 6.87 (td, J = 7.5, 1.2 Hz, 1 H), 6.77 (dd, J = 8.0,
1.1 Hz, 1 H), 6.27 (t, J = 3.9 Hz, 1 H), 4.78 (d, J = 3.9 Hz, 2
H) ppm. 13C NMR (100 MHz, CDCl3): δ = 153.5, 138.0, 134.0,
130.1, 129.9, 129.6, 128.1, 124.6, 121.8, 116.1, 113.3, 112.9,
1
Rf = 0.3 (EtOAc/hexane, 1:10); colorless oil. H NMR (400 MHz,
67.0 ppm. IR (film): ν = 3053, 2924, 1599, 1478, 1226, 1060, 755,
˜
CDCl3): δ = 7.41 (d, J = 7.4 Hz, 1 H), 7.21–7.13 (m, 3 H), 6.14
(td, J = 4.6, 0.8 Hz, 1 H), 4.68 (s, 1 H), 2.72 (t, J = 8.0 Hz, 2 H),
2.30–2.24 (m, 2 H), 1.81–1.72 (m, 2 H), 1.70–1.61 (m, 1 H), 1.55–
735, 690 cm–1. HRMS (EI): calcd. for C15H12OTe 337.9950; found
337.9948.
6-tert-Butyl-4-(phenyltellanyl)-2H-chromene (5d): Yield 73 % 1.35 (m, 2 H), 0.93 (t, J = 7.4 Hz), 3 H ppm. 13C NMR (100 MHz,
(143.0 mg); Rf = 0.5 (EtOAc/hexane, 1:15); yellow oil. 1H NMR
CDCl3): δ = 139.5, 136.9, 133.4, 127.8, 126.8, 126.3, 124.7, 123.0,
(400 MHz, CDCl3): δ = 7.72–7.70 (m, 2 H), 7.26–7.23 (m, 2 H), 71.9, 38.5, 28.4, 22.8, 19.3, 14.0 ppm. IR (film): ν = 3361, 2956,
˜
7.20–7.16 (m, 2 H), 7.11 (dd, J = 8.4, 2.4 Hz, 1 H), 6.69 (d, J =
8.4 Hz, 1 H), 6.31 (t, J = 3.9 Hz, 1 H), 4.72 (d, J = 3.9 Hz, 2 H),
2932, 2871, 1449, 768, 737, 425 cm–1. HRMS (EI): calcd. for
C14H18O: 202.1358; found 202.1360.
8
www.eurjoc.org
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Org. Chem. 0000, 0–0

Job/Unit: O21763
/KAP1
Date: 12-03-13 12:48:54
Pages: 12
Catalytic Intramolecular Hydroarylation
(3,4-Dihydronaphthalen-1-yl)(phenyl)methanol (6c):[18] Yield 87 %
yield (61.7 mg); Rf = 0.3 (EtOAc/hexane, 1:7); colorless oil. 1H
NMR (400 MHz, CDCl3): δ = 7.48–7.46 (m, 2 H), 7.39–7.31 (m, 3
H), 7.29–7.24 (m, 1 H), 7.15–7.11 (m, 3 H), 6.18–6.15 (m, 1 H),
5.78 (s, 1 H), 2.80 (t, J = 8.0 Hz, 2 H), 2.40–2.34 (m, 2 H), 2.16 (s,
1 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 142.3, 138.2, 136.6,
132.9, 128.3, 127.6, 127.3, 126.9, 126.7, 126.1, 125.8, 123.5, 73.9,
Synthesis of (E)-4-Styryl-1-tosyl-1,2-dihydroquinoline (6g):[17] To a
solution of PdCl2 (15 mol-%), AgOAc (4 equiv.), and Et3N
(4 equiv.) in MeOH (3 mL) at room temperature under a nitrogen
atmosphere was added cycloalkenyl telluride (0.3 mmol) and styr-
ene (4 equiv.). The mixture was stirred for 3 h at room temperature,
and the solid was filtered. The filtrate was poured into NH4Cl and
extracted with diethyl ether. The crude product was purified by
silica gel flash chromatography (EtOAc/hexane, 1:15) to give 6g
28.0, 22.9 ppm. IR (film): ν = 3408, 1600, 1349, 1163, 816, 761,
˜
684, 573 cm–1. HRMS (EI): calcd. for C17H16O 236.1201; found (80%, 93.0 mg). Rf = 0.2 (EtOAc/hexane, 1:15); colorless oil. 1H
236.1204.
NMR (400 MHz, CDCl3): δ = 7.76 (dd, J = 8.0, 1.0 Hz, 1 H), 7.38–
7.25 (m, 10 H), 7.03 (d, J = 8.0 Hz, 2 H), 6.50 (dd, J = 16.1, 1.0 Hz,
1 H), 6.36 (d, J = 16.1 Hz, 1 H), 5.67 (td, J = 4.5, 0.9 Hz, 1 H),
4.42 (d, J = 4.5 Hz, 2 H), 2.15 (s, 3 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 143.5, 136.9, 136.1, 135.8, 134.8, 131.4, 130.3, 129.1,
128.7, 128.3, 127.9, 127.88, 127.5, 126.8, 126.3, 124.6, 124.3, 120.7,
Synthesis of 4-(Hex-1-ynyl)-1,2-dihydronaphthalene (6d):[15] To a
solution of PdCl2 (20 mol-%) and CuI (20 mol-%) in MeOH (3 mL)
at room temperature under a nitrogen atmosphere was added cyclo-
alkenyl telluride (0.3 mmol), 1-hexyne (0.6 mmol), and Et3N
(0.3 mmol). The mixture was stirred for 12 h at room temperature,
treated with a saturated solution of NH4Cl (5 mL) and then ex-
tracted with ethyl acetate. The organic layer was washed with brine
and dried with MgSO4. The crude product was purified by silica
gel flash chromatography (hexane) to 6d (75%, 47.0 mg). Rf = 0.4
45.5, 21.4 ppm. IR (film): ν = 3028, 2922, 1598, 1485, 1450, 1350,
˜
1165, 1090, 738, 575 cm–1. HRMS (EI): calcd. for C24H21NO2S
387.1293; found 387.1297.
1-(1-Tosyl-1,2-dihydroquinolin-4-yl)butan-1-ol (6h): Yield 67 %
(71.9 mg); Rf = 0.2 (EtOAc/hexane, 1:4); colorless oil. 1H NMR
(400 MHz, CDCl3): δ = 7.69 (d, J = 7.9 Hz, 1 H), 7.25–7.23 (m, 10
H), 7.21 (d, J = 8.2 Hz, 2 H), 7.16 (d, J = 4.2 Hz, 1 H), 7.00 (d, J
= 8.0 Hz, 2 H), 5.64 (t, J = 4.0 Hz, 1 H), 4.46 (dd, J = 18.1, 4.8 Hz,
1 H), 4.25–4.20 (m, 2 H), 2.25 (s, 3 H), 1.33–1.23 (m, 1 H), 1.17–
1.06 (m, 2 H), 0.99–0.91 (m, 1 H), 0.77 (t, J = 7.4 Hz, 3 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 143.4, 138.9, 136.8, 135.3, 129.1,
129.06, 128.0, 127.7, 127.5, 126.7, 123.3, 119.3, 70.0, 45.1, 38.2,
1
(hexane); colorless oil. H NMR (400 MHz, CDCl3): δ = 7.57 (d,
J = 7.0 Hz, 1 H), 7.24–7.20 (m, 1 H), 7.15 (td, J = 7.3, 1.3 Hz, 1
H), 7.08 (d, J = 7.3 Hz, 1 H), 6.36 (t, J = 4.8 Hz, 1 H), 2.77 (t, J
= 8.0 Hz, 2 H), 2.42 (t, J = 7.0 Hz, 2 H), 2.37–2.31 (m, 2 H), 1.64–
1.56 (m, 2 H), 1.54–1.46 (m, 2 H), 0.95 (t, J = 7.3 Hz, 3 H) ppm.
13C NMR (100 MHz, CDCl3): δ = 135.2, 133.9, 133.3, 127.5, 127.3,
126.5, 125.1, 122.1, 91.2, 78.3, 31.1, 27.3, 23.6, 22.1, 19.2,
13.7 ppm. IR (film): ν = 2956, 2932, 2871, 1487, 1451, 1428, 1336,
˜
765, 736 cm–1. HRMS (EI): calcd. for C16H18 210.1409; found
210.1408.
21.4, 19.4, 14.0 ppm. IR (film): ν = 3470, 2958, 2871, 1345, 1164,
˜
1091, 762, 684, 579 cm–1. HRMS (EI): calcd. for C20H23NO3S
357.1399; found 357.1400.
Synthesis of 3,3Ј,4,4Ј-Tetrahydro-1,1Ј-binaphthyl (6e):[16] To a solu-
tion of Pd(OAc)2 (10 mol-%) and AgOAc (2 equiv.) in CH3CN
(5 mL) at room temperature under a nitrogen atmosphere was
added cycloalkenyl telluride (0.3 mmol). The mixture was stirred
for 4 h at room temperature, and the solid was filtered. The filtrate
was poured into brine and extracted with diethyl ether. The crude
product was purified by silica gel flash chromatography (hexane)
to give 6e (62%, 48.0 mg). Rf = 0.5 (hexane); white solid; m.p. 114–
116 °C. 1H NMR (400 MHz, CDCl3): δ = 7.20 (d, J = 7.0 Hz, 2
H), 7.13 (td, J = 7.4, 1.3 Hz, 2 H), 7.04 (td, J = 7.2, 0.8 Hz, 2 H),
6.96 (d, J = 7.6 Hz, 2 H), 6.12 (t, J = 4.5 Hz, 2 H), 2.93 (t, J =
7.8 Hz, 4 H), 2.46–2.41 (m, 2 H) ppm. 13C NMR (100 MHz,
CDCl3): δ = 138.8, 136.3, 135.2, 128.5, 127.8, 127.2, 126.8, 125.6,
Supporting Information (see footnote on the first page of this arti-
cle): Copies of the 1H NMR and 13C NMR spectra for all com-
pounds.
Acknowledgments
This work was funded by the National Research Foundation of
Korea through the National creative Research Laboratory (NCRL)
(grant number 2012-0001245).The authors thank Dr. Sung Ho Kim
at the KBSI (Daegu) for obtaining the HRMS data. P. H. thanks
Prof. S. Chang (KAIST) for helpful discussions.
28.7, 23.8 ppm. IR (solid): ν = 3060, 2881, 2829, 1484, 1449, 1426,
˜
[1] a) T. Wirth, Tetrahedron 1999, 55, 1; b) Y. Tang, S. Ye, X. L.
Sun, Synlett 2005, 2720; c) N. Petragnani, H. A. Stefani, Tetra-
hedron 2005, 61, 1613; d) S. Ranganathan, K. M. Muraleed-
haran, N. K. Vaish, N. Jayaraman, Tetrahedron 2004, 60, 5273;
e) V. K. Aggarwal, C. L. Winn, Acc. Chem. Res. 2004, 37, 611;
f) J. V. Comasseto, R. E. Barrientos-Astigarraga, Aldrichim.
Acta 2000, 33, 66; g) L. Engman, Acc. Chem. Res. 1985, 18,
274; h) N. Petragnani, H. A. Stefani, Tellurium in Organic Syn-
thesis 2nd ed., Academic Press, London, 2007; i) P. J. Stang,
V. V. Zhdankin, in: Comprehensive Organic Functional Group
Transformations (Ed.: S. V. Ley), Elsevier, Cambridge, 2003,
vol. 2, chapter 2; j) S. Patai, Z. Rappoport (Eds.), The Chemis-
try of Organic Selenium and Tellurium Compounds, Wiley,
Chichester, UK, 1986, vol. 1; k) K. Y. Irgolic, in: Houben-Weyl
Methods of Organic Chemistry, 4th ed. (Ed.: D. Klamann),
Thieme, Stuttgart, Germany, 1990, vol. E12b.
910, 768 cm–1. HRMS (EI): calcd. for C20H18 258.1409; found
258.1408.
Synthesis of 3,4-Dihydronaphthalene-1-carbaldehyde (6f):[14] To a
solution of cycloalkenyl telluride (0.3 mmol) in THF (1.5 mL) at
–78 °C under a nitrogen atmosphere was dropwise added a solution
of nBuLi (1.6 m in hexanes, 1.1 equiv.). After 20 min of stirring at
this temperature, DMF (1.5 equiv.) was added. The mixture was
stirred for 1 h at –78 °C, then diluted with ethyl acetate (2 ϫ
15 mL), and washed with water (2ϫ 10 mL). The organic layer
was separated, dried with MgSO4, and concentrated under reduced
pressure. The crude product was purified by silica gel flash
chromatography (EtOAc/hexane, 1:30) to give 6f (63%, 30.0 mg).
1
Rf = 0.2 (EtOAc/hexane, 1:30); colorless oil. H NMR (400 MHz,
CDCl3): δ = 9.69 (s, 1 H), 8.21–8.19 (m, 1 H), 7.28–7.18 (m, 3 H),
7.03 (t, J = 4.7 Hz, 1 H), 2.82 (t, J = 7.8 Hz, 2 H), 2.62–2.56 (m,
3 H) ppm. 13C NMR (100 MHz, CDCl3): δ = 192.7, 152.9, 138.1,
135.7, 129.4, 128.3, 127.7, 126.7, 125.8, 27.1, 24.3 ppm. IR (film):
[2] a) D. L. Klayman, W. H. Gunther (Eds.), Organic Selenium
Compounds: Their Chemistry and Biology, John Wiley & Sons,
New York, 1973, p. 68; b) T. Wirth (Ed.), Topics in Current
Chemistry, vol. 208: Organoselenium Chemistry – Modern De-
velopments in Organic Synthesis Springer, Berlin, 2000; c) A.
Ogawa, in: Main Group Metals in Organic Synthesis (Eds.: H.
ν = 2941, 2835, 2722, 1689, 1489, 1452, 1231, 765, 737 cm–1
.
˜
HRMS (EI): calcd. for C11H10O 158.0732; found 158.0730.
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Job/Unit: O21763
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Date: 12-03-13 12:48:54
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D. Eom, S. Park, Y. Park, K. Lee, G. Hong, P. H. Lee
FULL PAPER
Yamamoto, K. Oshima), Wiley-VCH, Weinheim, Germany,
2004, vol. 2, p. 813; d) C. W. Nogueira, G. Zeni, J. B. T. Rocha,
Chem. Rev. 2004, 104, 6255.
G. Zeni, Tetrahedron Lett. 2001, 42, 8563; g) G. Zeni, D. Alves,
A. L. Braga, H. A. Stefani, C. W. Nogueira, Tetrahedron Lett.
2004, 45, 4823; h) C. Raminelli, J. Gargalaka Jr, C. C. Silviera,
J. V. Comasseto, Tetrahedron Lett. 2004, 45, 4927; i) Q. Xu, X.
Huang, J. Yuan, J. Org. Chem. 2005, 70, 6948; j) A. L. Braga,
L. H. Andrade, C. C. Silviera, A. V. Moro, G. Zeni, Tetrahe-
dron Lett. 2001, 42, 8563.
[3]
a) J. V. Comasseto, L. W. Ling, N. Petragnani, H. A. Stefani,
Synthesis 1997, 373; b) A. L. Braga, A. Reckziegel, C. C. Silvi-
era, J. V. Comasseto, Synth. Commun. 1994, 24, 1165; c) J. W.
Sung, W. B. Jang, D. Y. Oh, Tetrahedron Lett. 1996, 37, 7537;
d) B. W. Jang, D. Y. Oh, C.-W. Lee, Tetrahedron Lett. 2000, 41,
5103; e) A. L. Braga, E. F. Alves, C. C. Silviera, L. H. Andrade,
Tetrahedron Lett. 2000, 41, 161; f) M. J. Dabdoub, V. B. Dab-
doub, M. A. Pereira, Tetrahedron Lett. 2001, 42, 1595; g) C.-
Q. Zhao, J.-L. Li, J. B. Meng, Y.-M. Wang, J. Org. Chem. 1998,
63, 4170; h) J. P. Marino, H. N. Nguyen, J. Org. Chem. 2002,
67, 6291; i) A. L. Braga, F. Vargas, G. Zeni, C. C. Silviera,
L. H. Andrade, Tetrahedron Lett. 2002, 43, 4399; j) C. C. Silvi-
era, A. L. Braga, R. B. Guerra, Tetrahedron Lett. 2002, 43,
3395; k) J. M. Gil, D. Y. Oh, J. Org. Chem. 1999, 64, 2950.
a) C. W. Nogueira, G. Zeni, J. B. T. Rocha, Chem. Rev. 2004,
104, 6255; b) G. Mugesh, W. W. du Mont, H. Sies, Chem. Rev.
2001, 101, 2125; c) M. J. Parnham, E. Graf, Prog. Drug Res.
1991, 36, 9; d) C. W. Nogueira, E. B. Quinhones, E. A. C. Jung,
G. Zeni, J. B. T. Rocha, Inflammation Res. 2003, 52, 56.
a) K. C. Nicolaou, N. A. Petasis, Selenium in Natural Products
Synthesis CIS, Philadelphia, 1984; b) C. Paulmier, Selenium
Reagents and Intermediates in Organic Synthesis Pergamon,
Oxford, UK, 1986; c) D. Liotta (Ed.), Organoselenium Chemis-
try, Wiley, Chichester, UK, 1987; d) A. Krief, L. Hevesi, Organ-
oselenium Chemistry I: Functional Group Transformations,
Springer, Berlin, 1988; e) T. G. Back (Ed.), Organoselenium
Chemistry: A Practical Approach, Oxford University Press, Ox-
ford, UK, 1999; f) H. J. Reich, Acc. Chem. Res. 1979, 12, 22;
g) D. Liotta, Acc. Chem. Res. 1984, 17, 28; h) G. Mugesh, H. B.
Singh, Acc. Chem. Res. 2002, 35, 226.
[8] For hydroselenation of alkynes, see: a) G. Zeni, M. P. Stracke,
C. W. Nogueira, A. L. Braga, P. H. Menezes, H. A. Stefani,
Org. Lett. 2004, 6, 1135; b) J. V. Comasseto, C. A. Brandt, Syn-
thesis 1987, 146; c) V. P. Ananikov, D. A. Malyshev, I. P. Belets-
kaya, G. G. Aleksandrov, I. L. Eremenko, J. Organomet. Chem.
2003, 679, 162; d) S. Kawaguchi, M. Kotani, S. Atobe, A. No-
moto, M. Sonoda, A. Ogawa, Organometallics 2011, 30, 6766;
e) V. P. Ananikov, N. V. Orlov, I. P. Beletskaya, Organometallics
2007, 26, 740; f) I. Kamiya, E. Nishinaka, A. Ogawa, J. Org.
Chem. 2005, 70, 696; g) M. Cai, Y. Wang, W. Hao, Green Chem.
2007, 9, 1180; h) H. Sashida, K. Ohyanagi, M. Minoura, K.
Akiba, J. Chem. Soc. Perkin Trans. 1 2002, 606; i) H. Sashida,
K. Ohyanagi, Chem. Pharm. Bull. 2005, 53, 60; j) C. Peppe,
E. S. Lang, G. N. Ledesma, L. B. Castro, O. S. R. Barros, P. A.
Mello, Synlett 2005, 3091; Wittig olefination: k) C. C. Silviera,
M. L. Begnini, P. Boeck, A. L. Braga, Synthesis 1997, 221; for
nucleophilic substitution of alkenyl halides, see: l) H. J. Cristau,
B. Chabaud, R. Labaudiniere, H. Christol, J. Org. Chem. 1986,
51, 875; m) M. Tiecco, L. Testaferri, M. Tingoli, D. Chianelli,
M. Montanucci, Tetrahedron Lett. 1984, 25, 4975; n) L. Tes-
taferri, M. Tiecco, M. Tingoli, D. Chianelli, Tetrahedron 1986,
42, 63; o) L. Testaferri, M. Tiecco, M. Tingoli, D. Chianelli,
Tetrahedron 1986, 42, 4577; p) A. L. Braga, A. Reckziegel,
C. C. Silveira, J. V. Comasseto, Synth. Commun. 1994, 24, 1165;
q) B. C. Ranu, K. Chattopadhyay, S. Banerjee, J. Org. Chem.
2006, 71, 423; r) D. Chang, W. Bao, Synlett 2006, 1786; s) Z.
Wang, H. Mo, W. Bao, Synlett 2007, 91.
[4]
[5]
[6]
a) Z. Rappoport (Ed.), The Chemistry of Organic Selenium and
Tellurium Compounds, John Wiley & Sons, New York, 2012,
vol. 3; b) M. Tingoli, M. Tiecco, L. Testaferri, A. Temperini,
G. Pelizzi, A. Bacchi, Tetrahedron 1995, 51, 4691; c) L.-S. Zhu,
X. Huang, Synth. Commun. 1997, 27, 39; d) X. Fang, M. Jiang,
R. Hu, M. Cai, Synth. Commun. 2008, 38, 4170; e) F. Alonso,
I. P. Beletskaya, M. Yus, Chem. Rev. 2004, 104, 3079; f) I. P.
Beletskaya, V. P. Ananikov, Chem. Rev. 2011, 111, 1596; g) J. V.
Comasseto, J. Organomet. Chem. 1983, 253, 131; h) J. V. Com-
asseto, N. Petragnani, J. Organomet. Chem. 1978, 152, 295; i)
J. V. Comasseto, L. W. Ling, N. Petragnani, H. A. Stefani, Syn-
thesis 1997, 373; j) J. V. Comasseto, J. Organomet. Chem. 1983,
253, 131; k) O. S. D. Barros, E. S. Lang, C. A. F. de Oliveira,
C. Peppe, G. Zeni, Tetrahedron Lett. 2002, 43, 7921; l) M. J.
Dabdoub, V. B. Dabdoub, M. A. Pereira, Tetrahedron Lett.
2001, 42, 1595; m) M. J. Dabdoub, A. C. M. Baroni, E. J. Len-
ardão, T. R. Gianeti, G. R. Hurtado, Tetrahedron 2001, 57,
4271; n) M. J. Dabdoub, T. M. Cassol, A. C. F. Batista, Tetra-
hedron Lett. 1996, 37, 9005; o) G. Perin, E. J. Lenardão, R. G.
Jacob, R. B. Panatieri, Chem. Rev. 2009, 109, 1277; p) C. C.
Silviera, S. R. Mendes, L. Wolf, J. Braz. Chem. Soc. 2010, 21,
2138; q) S.-i. Kawaguchi, M. Kotani, S. Atobe, A. Nomoto,
M. Sonoda, A. Ogawa, Organometallics 2011, 30, 6766; r) A. L.
Braga, T. Barcellos, M. W. Paixão, A. M. Deobald, M. Godoi,
H. Stefani, R. Cella, A. Sharma, Organometallics 2008, 27,
4009; s) B. C. Ranu, K. Chattopadhyay, S. Banerjee, J. Org.
Chem. 2006, 71, 423; t) A. V. Moro, C. W. Nogueira, N. B. V.
Barbosa, P. H. Menezes, J. B. T. Rocha, G. Zeni, J. Org. Chem.
2005, 70, 5257.
[9]
a) R. E. Barrientos-Astigarraga, P. Castelani, C. Y. Sumida,
J. V. Comsaaeto, Tetrahedron Lett. 1999, 40, 7717; b) T. G.
Back, R. J. Bethell, M. Parvez, J. A. Taylor, D. Wehrli, J. Org.
Chem. 1999, 64, 7426; c) J. P. Mariano, H. N. Nguyen, J. Org.
Chem. 2002, 67, 6291; d) M. Koketsu, M. Kanoh, Y. Yama-
mura, H. Ishihara, Tetrahedron Lett. 2005, 46, 1479; e) C. C.
Silviera, R. B. Guerra, J. V. Comasseto, Tetrahedron Lett. 2007,
48, 5121; f) B. Gogoi, A. Sperana, D. F. Back, R. Brandão,
C. W. Nogueira, G. Zeni, J. Org. Chem. 2009, 74, 3469; g) A. L.
Stein, F. N. Bilheri, J. T. da Rocha, D. F. Back, G. Zeni, Chem.
Eur. J. 2012, 18, 10602; h) A. Sperana, B. Gogoi, S. Pinton,
D. F. Back, P. H. Menezes, G. Zeni, J. Org. Chem. 2011, 76,
6789.
a) X. Wang, L. Zhou, W. Lu, Curr. Org. Chem. 2010, 14, 289;
b) K. Komeyama, R. Igawa, K. Takaki, Chem. Commun. 2010,
46, 1748; c) R. S. Menon, A. D. Findlay, A. C. Bissember,
M. G. Banwell, J. Org. Chem. 2009, 74, 8901; d) H. C. Shen,
Tetrahedron 2008, 64, 3885; e) R. Skouta, C.-J. Li, Tetrahedron
2008, 64, 4917; f) C. D. Zotto, J. Wehbe, D. Virieux, J.-M. Cam-
pagne, Synlett 2008, 2033; g) R. Li, S. Wang, W. Lu, Org. Lett.
2007, 9, 2119; h) C. Nevado, A. M. Echavarren, Synthesis 2005,
167; i) L. A. Goj, T. B. Gunnoe, Curr. Org. Chem. 2005, 9, 671;
j) Y. Luo, Z. Li, C.-J. Li, Org. Lett. 2005, 7, 2675; k) C. E.
Song, D.-u. Jung, S. Y. Choung, E. J. Roh, S.-g. Lee, Angew.
Chem. 2004, 116, 6309; Angew. Chem. Int. Ed. 2004, 43, 6183;
l) H. Inoue, N. Chatani, S. Muari, J. Org. Chem. 2002, 67, 1414;
m) A. Fürstner, V. Mamane, J. Org. Chem. 2002, 67, 6264; n)
C. Jia, D. Piao, J. Oyamada, W. Lu, T. Kitamura, Y. Fujiwara,
Science 2000, 287, 1992; o) N. Chatani, H. Inoue, T. Ikeda,
S. Murai, J. Org. Chem. 2000, 65, 4913; p) S. A. Worlikar, T.
Kesharwani, T. Yao, R. C. Larock, J. Org. Chem. 2007, 72,
1347; q) L. Zhang, S. A. Kozmin, J. Am. Chem. Soc. 2004, 126,
10204; r) Y. Zhang, R. P. Hsung, X. Zhang, J. Huang, B. W.
Slafer, A. Davis, Org. Lett. 2005, 7, 1047; s) J. Mo, D. Eom, E.
Lee, P. H. Lee, Org. Lett. 2012, 14, 3684; t) S. Kim, D. Kang,
C.-H. Lee, P. H. Lee, J. Org. Chem. 2012, 77, 6530; u) J. Mo,
[10]
[7]
a) N. Petragnani, Tellurium in Organic Synthesis Academic
Press, London, 1994; b) G. Zeni, D. D. Lüdtke, R. B. Panatieri,
A. L. Braga, Chem. Rev. 2006, 106, 1032; c) Y. Nishibayashi,
C. S. Cho, S. Uemura, J. Organomet. Chem. 1996, 507, 197; d)
K. Ohe, H. Takahashi, S. Uemura, N. Sugita, J. Org. Chem.
1987, 52, 4859; e) G. Zeni, C. W. Nogueira, J. M. Pena, C. Pilis-
sao, P. H. Menezes, A. L. Braga, J. B. T. Rocha, Synlett 2003,
579; f) A. L. Braga, L. H. Andrade, C. C. Silviera, A. V. Moro,
10
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Date: 12-03-13 12:48:54
Pages: 12
Catalytic Intramolecular Hydroarylation
P. H. Lee, Org. Lett. 2010, 12, 2570; v) D. Kang, J. Kim, S. Oh, [15] a) G. Zeni, C. W. Nogueira, J. M. Pena, C. Pilissao, P. H.
P. H. Lee, Org. Lett. 2012, 14, 5636; w) D. Eom, J. Mo, P. H.
Lee, Z. Gao, S. Kim, Eur. J. Org. Chem. 2013, 533.
a) A. L. Braga, C. C. Silviera, A. Reckziegel, P. H. Menezes,
Tetrahedron Lett. 1993, 34, 8041; b) L. W. Bieber, M. F.
da Silva, P. H. Menezes, Tetrahedron Lett. 2004, 45, 2735; c)
D. S. Rampon, R. Giovenardi, T. L. Silva, R. S. Rambo, A. A.
Merlo, P. H. Schneider, Eur. J. Org. Chem. 2011, 7066.
Menezes, A. L. Braga, J. B. T. Rocha, Synlett 2003, 579; b)
M. J. Dabdoub, V. B. Dabdoub, J. P. Marino, Tetrahedron Lett.
2000, 41, 437; c) R. Cella, R. L. O. R. Cunha, A. E. S. Reis,
D. C. Pimenta, C. F. Klitzke, H. A. Stefani, J. Org. Chem. 2006,
71, 244.
[11]
[16] Y. Nishibayashi, C. S. Cho, K. Ohe, S. Uemura, J. Organomet.
Chem. 1996, 526, 335.
[17] A. L. Braga, C. R. B. Rhoden, G. Zeni, C. C. Silviera, L. H.
Andrade, J. Organomet. Chem. 2003, 682, 35.
[18] A. M. DeBerardinis, M. Turlington, L. Pu, Angew. Chem. 2011,
123, 2416; Angew. Chem. Int. Ed. 2011, 50, 2368.
Received: December 31, 2012
[12]
M. J. Dabdoub, J. V. Comasseto, Organometallics 1988, 7, 84.
[13] H. Okamura, M. Miura, K. Kosugi, H. Takei, Tetrahedron
Lett. 1980, 21, 87.
[14] E. J. Lenardao, R. Cella, R. G. Jacob, T. B. da Silva, G. Perin,
J. Braz. Chem. Soc. 2006, 17, 1031.
Published Online: ᭿
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11

Job/Unit: O21763
/KAP1
Date: 12-03-13 12:48:54
Pages: 12
D. Eom, S. Park, Y. Park, K. Lee, G. Hong, P. H. Lee
FULL PAPER
Hydroarylation
D. Eom, S. Park, Y. Park, K. Lee,
G. Hong, P. H. Lee* ....................... 1–12
Brønsted Acid Catalyzed Intramolecular
Hydroarylation for the Synthesis of Cyclo-
Trifluoromethanesulfonic acid catalyzed
intramolecular hydroarylation of alkynyl
selenides and tellurides is developed for the
preparation of cycloalkenyl selenide and
selenides and tellurides can be easily con-
verted into a variety of valuable functional-
ities, including cyclic olefins, allylic al-
cohols, enynes, 1,3-dienes, and α,β-unsatu-
rated aldehydes.
alkenyl Selenides and Tellurides
Keywords: Synthetic methods / Hydroaryl-
ation / Brønsted acids / Alkenes / Sel-
enium / Tellurium
telluride derivatives through
a selective
6- and 7-endo mode. The cycloalkenyl
12
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