Silver-catalyzed coupling reactions of alkyl halides with indenyllithiums

Article abstract of DOI:10.1016/j.tet.2010.06.030

Coupling reactions of tertiary and secondary alkyl halides with indenyllithiums proceeded effectively in the presence of a catalytic amount of silver bromide to provide tertiary- and secondary-alkyl-substituted indene derivatives in good yields.

Full text of DOI:10.1016/j.tet.2010.06.030

Tetrahedron 66 (2010) 5993e5999
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Silver-catalyzed coupling reactions of alkyl halides with indenyllithiums
,
b
,
a,
Hidenori Someya a, Hideki Yorimitsu a , Koichiro Oshima
*
*
a Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto-daigaku Katsura, Nishikyo-ku, Kyoto 615-8510, Japan
b Department of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan
a r t i c l e i n f o
a b s t r a c t
Article history:
Coupling reactions of tertiary and secondary alkyl halides with indenyllithiums proceeded effectively in
the presence of a catalytic amount of silver bromide to provide tertiary- and secondary-alkyl-substituted
indene derivatives in good yields.
Received 25 May 2010
Received in revised form
10 June 2010
Accepted 10 June 2010
Available online 16 June 2010
Ó 2010 Elsevier Ltd. All rights reserved.
Keywords:
Coupling reaction
Silver
CarboneCarbon bond formation
Alkyl halide
1. Introduction
2. Results and discussion
Owing to the high nucleophilicity and the ready availability of
organolithiums, coupling reactions of alkyl halides with organo-
lithiums have been widely used for carbonecarbon bond forma-
tions in organic synthesis.1 The reaction of primary alkyl halides can
proceed smoothly without any catalyst. However, the use of steri-
cally bulky secondary alkyl halides as substrates in the coupling
reactions often results in affording the corresponding coupling
products in low yields, which is due to competitive side reactions,
such as elimination to alkenes and reduction to alkanes.
2.1. Optimization and scope of alkyl halides
Treatment of 3-bromo-3-methyl-1-phenylbutane (1a) with
2 equiv of indenyllithium in the presence of 5 mol % AgBr in Et2O
afforded the corresponding alkylated indene 2a in 90% yield (Table
1, entry 1).13 The reaction afforded 1-alkylindenes selectively, and
no isomerization to 3-alkylindene occurred despite the presence of
basic indenyllithium. Indenyllithium was prepared through
deprotonative lithiation of indene with sec-butyllithium in Et2O at
Recent progress of transition-metal-catalyzed coupling re-
actions of alkyl halides enables us to use secondary alkyl halides as
well as primary ones as substrates in the coupling reactions.2 While
there are many reports in which Mg,3 Zn,4 Sn,5 B,6 or Si7 is used as
the metal of organometallic reagent, the use of organolithium is
less investigated.8 Moreover, the reactions of tertiary alkyl halides
are still rare and have to be established.3a,b,9
Table 1
Effects of solvents and silver salts
5 mol% AgX
1
Li
Ph
Ph
Br
solvent, 10 h
2
3
/ Et2O, hexane
1a
2a
Recently, we have reported silver-catalyzed coupling reactions
of alkyl halides with Grignard reagents.9,10 In these reactions, ter-
tiary and secondary alkyl halides can be employed as substrates.
Here, we report silver-catalyzed coupling reactions of tertiary and
secondary alkyl halides with indenyllithium derivatives. Indene
framework can be found both in a large number of drug candi-
dates11 and in various metallocene complexes.12 The new efficient
route to modified indenes would thus be important.
Entry
Solvent
Yield of 2ab (%)
Entry
X
Yield of 2ab (%)
1a
Et2O
THF
CPME
hexane
90
10
56
64
5d
6d
7d
8d
I
Cl
NO3
OTf
2e
30f
26g
74
2a
3a
4a,c
a
Performed with 2.0 equiv of indenyllithium in the presence of 5 mol % AgBr.
Based on NMR analysis.
Indenyllithium was prepared in hexane.
Performed in Et2O.
Compound 1a was recovered in 88% yield.
Compound 1a was recovered in 62% yield.
Compound 1a was recovered in 40% yield.
b
c
d
e
f
* Corresponding authors. Tel.: þ81 75 753 4010; fax: þ81 75 753 3970; e-mail
addresses: yori@kuchem.kyoto-u.ac.jp (H. Yorimitsu), oshima@orgrxn.mbox.media.
kyoto-u.ac.jp (K. Oshima).
g
0040-4020/$ e see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2010.06.030

5994
H. Someya et al. / Tetrahedron 66 (2010) 5993e5999
0 ꢀC for 30 min.14 When AgBr was not added, only a trace amount of
2a was detected.15,16 The reactions performed in other ethereal
solvents, such as THF and cyclopentyl methyl ether (CPME), resul-
ted in lower yields (entries 2 and 3). The reaction in hexane, which
was the solvent of sec-butyllithium, resulted in moderate yield
(entry 4).17 Other silver halides, such as AgI and AgCl, were not
effective (entries 5 and 6). When we used AgNO3 instead of AgBr,
the reaction was sluggish (entry 7).18 The reaction with AgOTf
resulted in slightly lower yield than that with AgBr (entry 8).
The silver-catalyzed coupling reactions of various alkyl halides
are summarized in Table 2. Cyclic tertiary alkyl bromide 1b also
underwent the reaction smoothly (entry 2). It should be noted that
the reaction of 1b was not stereospecific, which is highly suggestive
of the existence of an intermediate having an sp2-hybridized car-
bon center.9a Since the reaction of 1-bromoadamantane (1c) was
slow, CPME was used as a cosolvent and the reaction was per-
formed under refluxing conditions (entry 3). Tertiary alkyl iodides
1d was too reactive under the reaction conditions (entry 4). The
reaction of tertiary alkyl chloride 1e required a prolonged reaction
time and a high temperature in CPME/Et2O, and the coupling
product was a 88/12 mixture of 1-alkyl- and 3-alkylindene de-
rivatives through deprotonation of 2a by indenyllithium under the
reaction conditions (entry 5). Both cyclic and acyclic secondary
alkyl bromides reacted smoothly in refluxing Et2O (entries 6 and
7).19 The substrates having functional groups, such as THP ether and
sulfonamide could be also employed (entries 8 and 9). The coupling
reaction of dibromide 1j proceeded selectively at the sp3-hybrid-
ized brominated carbon, although palladium-catalyzed coupling
reactions of aryl halides with organolithiums can proceed smoothly
(entry 10).8a Secondary alkyl iodides 1k can be employed (entry 11).
However, cyclohexyl chloride resisted the reaction, being converted
to 2f in only 17% yield.
Table 2
Silver-catalyzed coupling reactions of various alkyl halidesa
5 mol% AgBr
1
Li
Alkyl
Alkyl
X
Et2O, 10 h
2
3
/ Et2O, hexane
2.2. Application
1
2
The silver-catalyzed coupling reaction could proceed effectively
in a gram-scale (Scheme 1). Treatment of 1.88 g of tertiary alkyl
bromide 1l (8.0 mmol) with indenyllithium (16 mmol) under the
silver-catalyzed conditions afforded 1.82 g of 2j (84% yield). The
same reaction in a 0.5 mmol-scale afforded 2j in 73% yield.
Entry
Alkyl-X
1
Temp.
0 ꢀ
2
Yieldb (%)
86
1
2
1a
C
2a
Ph
Br
Br
t
Bu
1bc
Reflux
Reflux
2b
74d,e
5 mol% AgBr
1.0 eq
n
3
4
5
6
7
1c
1d
1e
1f
2c
2d
2a
2e
2f
61f,g,h
2.0 eq
C8H17
Br
Br
s
BuLi
1l 1.88 g (8.0 mmol)
H
n
C8H17
0 ꢀ
C
31
Et O,
Et2O, 25 °C, 10 h
0 °C
2
I
1 h
2j 1.82 g (84%)
(0.5 mmol scale : 73%)
3a
2.2 eq
Reflux
Reflux
Reflux
38f,h,i,j
Ph
Ph
Cl
Br
Scheme 1. Gram-scale coupling reaction.
85k
Treatment of 2j with sec-butyllithium followed by the addition
of chlorotrimethylsilane afforded the corresponding indenylsilane
derivative 4 in high yield (Scheme 2). Indenylsilanes are known
to be converted into the corresponding indenyltitanium tri-
chlorides, which are the precursors of syndiospecific catalysts for
ZieglereNatta polymerization of styrene.12a
1g
65
Br
O
O
8
1h
1i
Reflux
Reflux
Reflux
2g
2h
2i
72k
86k
79k
Br
9
Ts
N
1.1 eq
1.5 eq
Cl TMS
s
9
n
BuLi
Ph
Br
C8H17
n
Br
9
C8H17
25 °C
Et2O,
Et O,
0 °C
21.5 h
12 h
TMS
4 97%
2j
10
1j
Scheme 2. Synthesis of indenylsilane derivative.
Br
2
11
1k
Reflux
2f
70
The silver-catalyzed conditions were applicable to other stabi-
lized organolithiums (Scheme 3). The reactions of both tertiary and
secondary alkyl bromides with fluorenyllithium provided the cor-
responding 9-alkylfluorenes in good yields. The coupling reactions
can be a useful tool because fluorene frameworks are known to
have attractive optical properties.20 The regiocontrolled synthesis
of 1,3-dialkylindene could be achieved by the silver-catalyzed
coupling reaction with organolithium derived from 2j. The alkyl
moiety, which resulted from the alkyl halides, was substituted at
the 1-position of the 1,3-dialkylated indenes and the regioisomer
was not detected.21
I
a
Conditions: 1 (0.50 mmol), indenyllithium (1.0 mmol) in Et2O (3.0 mL).
Isolated yields.
b
c
d
e
f
cis/trans¼84:16.
cis/trans¼35:65.
Performed for 12 h.
Temperature of oil bath was 90 ꢀC.
Performed with 3.0 equiv of indenyllithium for 20 h.
Performed in CPME/Et2O (1/1).
Compound 2a/3-alkylindene¼88/12.
Performed for 40 h.
g
h
i
j
k
Mixtures (e1/1) of diastereomers.

H. Someya et al. / Tetrahedron 66 (2010) 5993e5999
5995
The following experiments revealed that monoindenylsilver(0)/
ate complex25,26 is reactive enough to effect the coupling reaction
(Table 3). A reaction mixture prepared from equimolar amounts of
AgBr and indenyllithium failed to promote the reaction of 1a (entry
1). In contrast, a 1/2 mixture of AgBr and indenyllithium was highly
reactive to yield 2a in 90% yield (entry 2). Three equivalents of the
indenyllithium based on AgBr did not improve the efficiency sig-
nificantly (entry 3). Although the exact feature of the catalytically
active species is not clear, these results support our proposed
mechanism shown in Scheme 4.
Table 3
Reactions with stoichiometric silver bromide
0.25 mmol
Scheme 3. Silver-catalyzed coupling reactions with other organolithiums.
X mmol
0.3 mmol
AgBr
Ph
Br
s
1a
BuLi
H
Et2O, 0 °C
0 °C
0 °C, 5 h
30 min
1 h
2.3. Mechanistic consideration
3a
1.1 x X mmol
We proposed a draft mechanism shown in Scheme 4. Formation
of electron-rich silver(0)-ate complex9,22 initially takes place
through the reaction of AgBr with 2 equiv of indenyllithium (A). The
ate complex effects single electron transfer to alkyl halide to form
the corresponding alkyl radical as cobalt- and manganese/ate
complexes do (B).23 The radical is trapped by indenylsilver(I) to
yield oxidative adduct (C). Reductive elimination gives the coupling
product (D), and the initial silver/ate complex is regenerated by the
action of the remaining indenyllithium (E).24
1a
Ph
7
2a
Entry
X/mmol
Yield of 2a/%a
Recovery of 1aa (%)
Yield of 7/mmola
1
2
3
0.3
0.6
0.9
<5
90
93
96
0
0
0.14
0.15
0.14
a
Based on NMR analysis.
3. Conclusion
LiBr
AgI
We have developed silver-catalyzed coupling reactions of alkyl
halides with indenyllithiums. The silver-catalyzed coupling re-
actions can afford tertiary- and secondary-alkyl-substituted
indenes and fluorenes in good yields.
2.0 eq
R
Br
Li
(B)
(C)
R
–
(A)
Ag0
Li+
R
AgII
AgBr
4. Experimental
4.1. General
0.5 eq
(E)
(D)
4.1.1. Instrumentation. 1H NMR (500 MHz) and 13C NMR
(125.7 MHz) spectra were taken on a Varian UNITY INOVA 500
Ag0
LiBr
spectrometer and were recorded in CDCl3. Chemical shifts (d) are in
Li
parts per million relative to tetramethylsilane at 0.00 ppm for 1H
and relative to CDCl3 at 77.23 ppm for 13C unless otherwise noted.
IR spectra were determined on a SHIMADZU FTIR-8200PC spec-
trometer. TLC analyses were performed on commercial glass plates
bearing a 0.25-mm layer of Merck Silica gel 60F254. Florisil
R
Scheme 4. Plausible mechanism.
(75e150 mm, 100e200 mesh) was used for filtration. Silica gel
The initial reduction of silver(I) salt to silver(0) is justified as
follows. Treatment of AgBr (0.30 mmol) with indenyllithium
(0.60 mmol) in Et2O at 0 ꢀC for 30 min afforded 1H,10H-1,10-biin-
dene (7) (0.14 mmol, dr¼73/27) (Scheme 5). The formation of 7, the
amount of which is roughly equal to a half of AgBr used, indicates
that Ag(I) would be reduced to Ag(0).
(Wakogel 200 mesh) was used for column chromatography. Mass
(EI) were determined on a JASCO IR-810 spectrometer. Elemental
analyses were carried out at the Elemental Analysis Center of Kyoto
University.
4.1.2. Materials. Unless otherwise noted, materials obtained from
commercial suppliers were used without further purification. Silver
bromide, silver chloride, silver nitrate, 1H-indene, and cyclopentyl
methyl ether were purchased from Wako Pure Chemicals. Silver
iodide, butyllithium (1.6 M in hexane solution), 9H-fluorene, and
hexane were purchased from Nacalai Tesque. Diethyl ether and
tetrahydrofuran were purchased from Kanto Chemical Co., stored
under nitrogen, and used as it is. Secondary butyllithium (1.0 M in
cyclohexane/hexane solution) was also purchased from Kanto
0.6 mmol 0.3 mmol
s
AgBr
BuLi
H
NH4Cl aq.
7 0.14 mmol (dr = 73/27)
Et2O, 0 °C
1 h
0 °C
30 min
3a
0.66 mmol
(0.47 eq based on AgBr)
Scheme 5. A mechanistic consideration.

5996
H. Someya et al. / Tetrahedron 66 (2010) 5993e5999
Chemical Co. Silver trifluoromethanesulfonate was purchased from
Aldrich. All reactions were carried out under argon atmosphere.
were extracted with ethyl acetate (30 mLꢁ3). The combined or-
ganic layer was passed through Florisil, dried over Na2SO4, and
concentrated. Silica gel column purification (hexane/ethyl
acetate¼80/1) of the crude product provided the corresponding
coupling product 2a (112.8 mg, 0.43 mmol) in 86% isolated yield.
4.2. Experimental procedures
4.2.1. Synthesis of 3-bromo-3-methyl-1-phenylbutane (1a). 2-
Methyl-4-phenyl-2-butanol (4.1 g, 25 mmol) was placed in a 100-
mL reaction flask. Then hydrobromic acid (47% solution, 12.9 g,
75 mmol) was added dropwise to the reaction mixture. After being
stirred for 1 day at 25 ꢀC, the reaction mixture was poured into
ethylene glycol (20 mL). The products were extracted with hexane
(30 mLꢁ2). The combined organic layer was dried over Na2SO4 and
concentrated. Distillation of the crude oil (1 Torr, 110 ꢀC) afforded
tertiary alkyl bromide 1a (4.2 g 18.4 mmol) in 74% isolated yield.
4.2.5. Silver-catalyzed coupling reaction in gram-scale. Silver bro-
mide (75.1 mg, 0.40 mmol) in Et2O (8 mL) was placed in a 100-mL
reaction flask. Indenyllithium prepared by treatment of 1H-indene
(2.1 mL, 17.6 mmol) with sec-butyllithium (1.0 M in cyclohexane/
hexane solution, 16 mL, 16 mmol) in Et2O (16 mL) at 0 ꢀC for 1 h,
was added to the mixture at room temperature. Substrate 1l (1.88 g,
8.0 mmol) in Et2O (16 mL) was then added to the reaction mixture.
After being stirred vigorously for 10 h at room temperature, the
reaction mixture was poured into a saturated ammonium chloride
solution (30 mL). The products were extracted with ethyl acetate
(30 mLꢁ3). The combined organic layer was passed through Flo-
risil, dried over Na2SO4, and concentrated. Silica gel column puri-
fication (hexane) of the crude product provided the corresponding
coupling product 2j (1.82 g, 6.7 mmol) in 84% isolated yield.
4.2.2. Synthesis of 3-chloro-3-methyl-1-phenylbutane (1e). 2-
Methyl-4-phenyl-2-butanol (4.9 g, 30 mmol) was placed in a 100-
mL reaction flask. Hydrochloric acid (11 M solution, 11 mL,
121 mmol) was then added dropwise to the reaction mixture. After
being stirred for 1 day at 25 ꢀC, the reaction mixture was poured
into ethylene glycol (20 mL). The products were extracted with
hexane (30 mLꢁ2). The combined organic layer was dried over
Na2SO4 and concentrated. Silica gel column purification (hexane) of
the crude oil afforded tertiary alkyl chloride 1e (3.3 g, 17.8 mmol) in
93% isolated yield.
4.2.6. Synthesis of 3-(1,1-dimethylnonyl)-1-trimethylsilyl-1H-indene
(4). Indene derivative 2j (0.41 g, 1.5 mmol) in Et2O (1.5 mL) was
placed in a 30-mL reaction flask. Then, sec-butyllithium (1.0 M in
cyclohexane/hexane solution, 1.65 mL, 1.65 mmol) was added
dropwise to the mixture at 0 ꢀC. After the mixture was stirred at
0 ꢀC for 1.5 h, chlorotrimethylsilane (0.29 mL, 2.25 mmol) was
added to the reaction mixture at 0 ꢀC. The reaction mixture was
stirred at room temperature for 12 h. Then, the reaction mixture
was poured into water (20 mL). The products were extracted with
ethyl acetate (20 mLꢁ3). The combined organic layer was dried
over Na2SO4, and concentrated. Silica gel column purification
(hexane) of the crude product provided the corresponding inden-
ylsilane derivative 4 (0.50 g, 1.45 mmol) in 97% isolated yield. (Silica
4.2.3. Synthesis of 3-bromo-1-(4-bromophenyl)butane (1j). Mag-
nesium (turnings, 0.36 g, 15 mmol) and Et2O (5 mL) were placed in
a 100-mL reaction flask. 4-Bromobenzyl bromide (2.5 g, 10 mmol)
in Et2O (10 mL) was added dropwise to the reaction mixture at 0 ꢀC.
After the mixture was stirred for 2 h, THF (10 mL) and 1,2-epox-
ypropane (1.4 mL, 20 mmol) were successively added at 0 ꢀC. The
reaction mixture was stirred for 2 h at room temperature. Then, the
reaction mixture was poured into a saturated ammonium chloride
solution. The products were extracted with ethyl acetate
(20 mLꢁ2). The combined organic layer was dried over Na2SO4 and
concentrated. Silica gel column purification (hexane/ethyl
acetate¼2/1) of the crude oil afforded 4-(4-bromophenyl)-2-buta-
nol (0.84 g, 3.7 mmol) in 37% isolated yield. This alcohol and
dichloromethane (4 mL) were placed in a 30-mL reaction flask.
Then, triethylamine (1.0 mL, 7.4 mmol), methanesulfonyl chloride
(0.43 mL, 5.6 mmol), and 4-(dimethylamino)pyridine (0.01 mmol,
1.2 mg) were successively added to the reaction mixture. After
being stirred for 4 h at room temperature, the reaction mixture was
poured into a saturated ammonium chloride solution. The products
were extracted with ethyl acetate (20 mLꢁ2). The combined or-
ganic layer was dried over Na2SO4 and concentrated. The crude oil
in acetone (4 mL) was placed in a 30-mL reaction flask. Lithium
bromide (0.96 g, 11 mmol) was then added to the reaction mixture.
After being stirred for 12 h in refluxing acetone, the reaction mix-
ture was poured into water. The products were extracted with
hexane (20 mLꢁ2). The combined organic layer was dried over
Na2SO4 and concentrated. Silica gel column purification (hexane) of
the crude oil afforded 1j (0.66 g, 2.3 mmol) in 61% isolated yield.
Gel 60 N (spherical, neutral) 40e100 mm, which was purchased
from Kanto Chemical Co., was used for column chromatography in
this case.)
4.2.7. General procedure for silver-catalyzed coupling reactions of
alkyl halides with fluorenyllithiums. The synthesis of 5a is repre-
sentative (Scheme 3). Silver bromide (4.7 mg, 0.025 mmol) in Et2O
(1 mL) was placed in a 30-mL reaction flask. Fluorenyllithium,
which was prepared through treatment of 9H-fluorene (182.8 mg,
1.1 mmol) with butyllithium (1.6 M in cyclohexane/hexane solu-
tion, 0.63 mL, 1.0 mmol) in Et2O (3 mL) at 0 ꢀC for 1 h, was added to
the reaction mixture at ꢂ20 ꢀC. Then, substrate 1a (113.6 mg,
0.50 mmol) in Et2O (2 mL) was added at the same temperature.
After being stirred vigorously for 10 h at ꢂ20 ꢀC, the reaction
mixture was poured into a saturated ammonium chloride solution
(30 mL). The products were extracted with ethyl acetate (30 mLꢁ3).
The combined organic layer was passed through Florisil, dried over
Na2SO4, and concentrated. Silica gel column purification (hexane/
ethyl acetate¼50/1) of the crude product provided the corre-
sponding coupling product 5a (110.4 mg, 0.35 mmol) in 71% iso-
lated yield.
4.2.4. General procedure for silver-catalyzed coupling reactions of
alkyl halides with indenyllithiums. The reaction of 1a with inden-
yllithium is representative (Table 2, entry 1). Silver bromide
(4.7 mg, 0.025 mmol) in Et2O (1 mL) was placed in a 30-mL reaction
flask. Indenyllithium, which was prepared by treatment of 1H-
indene (0.13 mL, 1.1 mmol) with sec-butyllithium (1.0 M in cyclo-
hexane/hexane solution,1.0 mL, 1.0 mmol) in Et2O (3 mL) at 0 ꢀC for
1 h, was added to the reaction mixture at 0 ꢀC. Then, substrate 1a
(113.6 mg, 0.50 mmol) in Et2O (2 mL) was added. After being stirred
vigorously for 10 h at 0 ꢀC, the reaction mixture was poured into
a saturated ammonium chloride solution (30 mL). The products
4.2.8. General procedure for synthesis of 1,3-dialkylindenes. The
synthesis of 6a is representative (Scheme 3). Silver bromide
(4.7 mg, 0.025 mmol) in Et2O (1 mL) was placed in a 30-mL reaction
flask. Indenyllithium derivative, which was prepared through
treatment of 2j (297.5 mg, 1.1 mmol) with sec-butyllithium (1.0 M
in cyclohexane/hexane solution, 1.0 mL, 1.0 mmol) in Et2O (3 mL) at
0 ꢀC for 1.5 h, was added to the reaction mixture at 0 ꢀC. Then,
substrate 1a (113.6 mg, 0.50 mmol) in Et2O (2 mL) was added at the
same temperature. After being stirred vigorously for 12 h at 0 ꢀC,
the reaction mixture was poured into a saturated ammonium

H. Someya et al. / Tetrahedron 66 (2010) 5993e5999
5997
chloride solution (30 mL). The products were extracted with ethyl
acetate (30 mLꢁ3). The combined organic layer was passed through
Florisil, dried over Na2SO4, and concentrated. Purification by silica
gel column chromatography (hexane/ethyl acetate¼80/1), which
was followed by gel permeation chromatography, of the crude
product provided the corresponding coupling product 6a (84.6 mg,
0.20 mmol) in 41% isolated yield.
(s,1H), 6.60 (d, J¼5.5 Hz,1H), 6.80 (d, J¼5.5 Hz,1H), 7.13 (t, J¼7.5 Hz,
1H), 7.23 (t, J¼7.5 Hz, 1H), 7.31 (d, J¼7.5 Hz, 1H), 7.54 (d, J¼7.5 Hz,
1H); 13C NMR (CDCl3)
d 29.03, 37.03, 37.28, 41.01, 62.02, 121.03,
124.17, 125.53, 126.53, 131.77, 137.09, 145.00, 145.72; found: C,
91.22; H, 8.60%. Calcd for C19H22: C, 91.14; H, 8.86%. Mp 64e65 ꢀC.
4.3.7. 1-(1,1-Dimethylethyl)-1H-indene (2d)15. Colorless oil. IR
(neat) 3063, 2963, 2870, 1458, 1366, 1226, 764, 725 cmꢂ1; 1H NMR
4.3. Characterization data of new compounds
(CDCl3)
d
1.03 (s, 9H), 3.27 (s, 1H), 6.55 (dd, J¼6.0, 2.0 Hz, 1H), 6.81
(dt, J¼6.0, 1.0 Hz, 1H), 7.14 (t, J¼7.5 Hz, 1H), 7.24 (t, J¼7.5 Hz, 1H),
Compounds 1c, 1d, 1g, 1k, 3a, and 3b were commercially
available. Compound 1b,27 1f,28 1h,9b 1i,9b and 1l3b were found in
the literature.
7.32 (d, J¼8.0 Hz, 1H), 7.54 (d, J¼7.5 Hz, 1H); 13C NMR (CDCl3)
d
28.77, 34.35, 61.56, 121.06, 124.37, 125.04, 126.57, 131.70, 138.22,
145.61, 145.97; found: C, 90.45; H, 9.63%. Calcd for C13H16: C, 90.64;
H, 9.36%.
4.3.1. 3-Bromo-3-methyl-1-phenylbutane (1a). Colorless oil. IR
(neat) 3024, 2932, 1604, 1497, 1450, 1103, 740, 702 cmꢂ1
;
1H NMR
4.3.8. 1-(1-Methyl-3-phenylpropyl)-1H-indene (2e) (56/44 mixture
of diastereomers). Yellow oil. IR (neat) 2924, 2862, 1605, 1458, 1373,
(CDCl3)
(m, 2H), 7.18e7.22 (m, 3H), 7.27e7.31 (m, 2H); 13C NMR (CDCl3)
33.11, 34.49, 49.66, 67.69, 126.19, 128.63, 128.70, 141.81; found: C,
d
1.82 (s, 6H), 2.09 (ddd, J¼8.0, 4.5, 3.5 Hz, 2H), 2.84e2.87
763, 740 cmꢂ1; 1H NMR (CDCl3)
d
0.56 (d, J¼7.0 Hz, 0.44ꢁ3H), 1.08
d
(d, J¼7.0 Hz, 0.56ꢁ3H), 1.35 (m, 1H), 1.70 (m, 0.44ꢁ1H), 1.91 (m,
0.44ꢁ1H), 2.26 (m, 1H), 2.42 (m, 0.56ꢁ1H), 2.62 (m, 0.56ꢁ1H), 2.77
(m, 1H), 3.48 (br s, 0.56ꢁ1H), 3.56 (br s, 0.44ꢁ1H), 6.47 (dd, J¼6.0,
2.0 Hz, 0.44ꢁ1H), 6.50 (dd, J¼5.5, 2.0 Hz, 0.56ꢁ1H), 6.81 (dd, J¼5.5,
2.5 Hz, 0.56ꢁ1H), 6.85 (dd, J¼5.5, 2.5 Hz, 0.44ꢁ1H), 7.04 (d,
J¼7.5 Hz, 1H), 7.13e7.19 (m, 0.44ꢁ1Hþ1H), 7.21e7.25 (m, 4H),
58.33; H, 6.68%. Calcd for C11H15Br: C, 58.17; H, 6.66%.
4.3.2. 3-Chloro-3-methyl-1-phenylbutane (1e). Colorless oil. IR
(neat) 2932, 2893, 1604, 1458, 1373, 1110, 748, 702 cmꢂ1 1H NMR
;
(CDCl3)
d
1.64 (s, 6H), 2.04 (ddd, J¼8.0, 5.0, 4.5 Hz, 2H), 2.82 (dt,
J¼8.0, 4.5 Hz, 2H), 7.18e7.22 (m, 3H), 7.27e7.31 (m, 2H); 13C NMR
7.30e7.36 (m, 0.56ꢁ1Hþ2H); 13C NMR (CDCl3)
d 14.88, 18.27, 34.20,
(CDCl3)
d
31.87, 32.69, 48.17, 70.76, 126.15, 128.61, 128.68, 141.99;
34.36, 34.39, 34.41, 34.67, 38.27, 55.48, 56.55, 121.12, 122.96, 123.38,
124.73, 124.84, 125.82, 126.00, 126.60, 126.64, 128.34, 128.49,
128.56, 128.62, 128.63, 131.82, 132.39, 136.54, 137.48, 142.66, 142.76,
145.12, 145.34, 146.46, 147.17; found: C, 91.81; H, 8.15%. Calcd for
C19H20: C, 91.88; H, 8.12%.
found: C, 72.41; H, 8.19%. Calcd for C11H15Cl: C, 72.32; H, 8.28%.
4.3.3. 3-Bromo-1-(4-bromophenyl)butane (1j). Yellow oil. IR (neat)
2924, 2862, 1489, 1450, 1072, 1001, 826 cmꢂ1 1H NMR (CDCl3)
;
d
1.72 (d, J¼6.5 Hz, 3H), 2.00 (m, 1H), 2.10 (m, 1H), 2.71 (m, 1H), 2.82
(m, 1H), 4.04 (m, 1H), 7.09 (dt, J¼8.5, 2.0 Hz, 2H), 7.41 (dt, J¼8.5,
2.0 Hz, 2H); 13C NMR (CDCl3)
26.74, 33.59, 42.62, 50.73, 120.08,
4.3.9. 1-Cyclohexyl-1H-indene (2f). Colorless oil. IR (neat) 3063,
d
2924, 2855, 1450, 1366, 772, 718 cmꢂ1 1H NMR (CDCl3)
; d 0.90 (m,
130.51, 131.76, 140.06; found: C, 41.20; H, 4.19%. Calcd for C10H12Br2:
C, 41.13; H, 4.14%.
J¼1H), 1.05e1.18 (m, 2H), 1.20e1.35 (m, 3H), 1.61 (dm, 2H), 1.77 (m,
1H), 1.87e2.02 (m, 2H), 3.40 (t, J¼2.0 Hz, 1H), 6.52 (dd, J¼5.5,
2.0 Hz, 1H), 6.80 (dd, J¼5.5, 2.0 Hz, 1H), 7.17 (td, J¼7.5, 1.0 Hz, 1H),
7.23 (t, J¼7.5 Hz, 1H), 7.33 (d, J¼7.5 Hz, 1H), 7.41 (d, J¼7.5 Hz, 1H);
4.3.4. 1-(1,1-Dimethyl-3-phenylpropyl)-1H-indene (2a). Yellow oil.
IR (neat) 3024, 2963, 2862, 1605, 1458, 1366, 763, 702 cmꢂ1
;
1H
13C NMR (CDCl3)
d 26.73, 26.73, 27.12, 28.54, 32.47, 40.53, 56.76,
NMR (CDCl3)
d
1.05 (s, 3H), 1.07 (s, 3H), 1.66e1.77 (m, 2H), 2.69 (t,
121.03, 123.29, 124.66, 126.52, 131.53, 137.78, 145.15, 146.90; found:
C, 90.67; H, 9.22%. Calcd for C15H18: C, 90.85; H, 9.15%.
J¼8.5 Hz, 2H), 3.46 (t, J¼2.0 Hz, 1H), 6.57 (dd, J¼6.0, 2.0 Hz, 1H),
6.83 (dd, J¼6.0, 2.0 Hz, 1H), 7.13e7.19 (m, 4H), 7.22e7.29 (m, 3H),
7.32 (d, J¼7.0 Hz, 1H), 7.54 (d, J¼7.5 Hz, 1H); 13C NMR (CDCl3)
4.3.10. 2-((10-(1H-Inden-1-yl)undecyl)oxy)tetrahydropyran
(53/47 mixture of diastereomers). Yellow oil. IR (neat) 2924, 2855,
1458, 1358, 1072, 1034, 772, 725 cmꢂ1 1H NMR (CDCl3)
0.46 (d,
(2g)
d
26.22, 26.28, 31.10, 37.07, 43.96, 59.64, 121.24, 124.52, 124.98,
125.89, 126.65, 128.56, 128.62, 132.00, 137.74, 143.30, 145.69,
145.72; found: C, 91.67; H, 8.51%. Calcd for C20H22: C, 91.55; H,
8.45%.
;
d
J¼6.5 Hz, 0.53ꢁ3H), 0.98 (d, J¼6.5 Hz, 0.47ꢁ3H), 1.03 (m, 1H),
1.09e1.47 (m, 14H), 1.49e1.64 (m, 6H), 1.72 (m, 1H), 1.84 (m, 1H),
2.19 (m, 1H), 3.38 (ddt, J¼10.5, 10.0, 6.5 Hz, 1H), 3.49 (m, 1H), 3.73
(ddt, J¼10.5, 10.0, 6.5 Hz, 1H), 3.87 (m, 1H), 4.57 (m, 1H), 6.47 (dd,
J¼6.0, 2.0 Hz, 0.47ꢁ1H), 6.49 (dd, J¼5.5, 2.0 Hz, 0.53ꢁ1H), 6.81 (dd,
J¼6.0, 2.0 Hz, 0.47ꢁ1H), 6.84 (dd, J¼5.5, 2.0 Hz, 0.53ꢁ1H), 7.17 (m,
1H), 7.24 (m, 1H), 7.33 (d, J¼7.5 Hz, 1H), 7.39 (m, 1H); 13C NMR
4.3.5. 1-(1-Methyl-4-(1,1-dimethylethyl)cyclohexyl)-1H-indene (2b)
(cis/trans¼35/65 mixture of diastereomers)29. White solid. IR (Nujol)
3063, 2939, 2862, 1458, 1366, 1227, 1150, 1103, 1026, 926, 756,
725 cmꢂ1
;
1H NMR (CDCl3)
d
0.34 (s, 0.35ꢁ3H), 0.68 (s, 0.65ꢁ3H),
0.85 (s, 0.65ꢁ9H), 0.92 (s, 0.35ꢁ9H), 0.95 (m, 0.65ꢁ1H), 1.12e1.32
(m, 0.35ꢁ1Hþ2H), 1.47e1.81 (m, 0.65ꢁ1Hþ4H), 1.99 (m, 1H), 2.37
(m, 0.35ꢁ1H), 3.20 (br s, 0.65ꢁ1H), 3.85 (br s, 0.35ꢁ1H), 6.53 (dd,
J¼5.5, 2.0 Hz, 0.35ꢁ1H), 6.58 (dd, J¼5.5, 2.0 Hz, 0.65ꢁ1H), 6.81(m,
1H), 7.13 (m, 1H), 7.23 (m, 1H), 7.32 (t, J¼7.0 Hz, 1H), 7.45 (d,
J¼7.5 Hz, 0.35ꢁ1H), 7.54 (d, J¼7.5 Hz, 0.65ꢁ1H); 13C NMR (CDCl3)
(CDCl3) d 14.86, 18.21, 19.94 (2C), 25.74 (2C), 26.45, 26.48, 27.97,
28.09, 29.67, 29.72, 29.75 (2C), 29.83, 29.84, 29.87, 29.97, 30.00,
30.08, 31.02 (2C), 32.85, 34.89, 35.13, 36.57, 55.62, 56.61, 62.56,
62.58, 67.91 (2C), 99.07, 99.09, 121.03, 121.05, 122.91, 123.42, 124.63,
124.74, 126.47, 126.53, 131.49, 132.11, 136.83, 137.99, 145.14, 145.42,
146.69, 147.48; found: C, 80.64; H, 10.30%. Calcd for C25H38O2: C,
81.03; H, 10.33%.
d
18.62, 22.84, 22.97, 23.09, 23.18, 23.96, 27.76, 27.87, 32.60, 32.80,
36.51, 37.06, 37.75, 38.15, 38.38, 40.20, 48.30, 48.32, 52.22, 63.58,
121.04, 121.17, 124.26, 124.30, 124.95, 125.41, 126.44, 126.55, 131.61,
131.77, 137.56, 138.10, 145.60, 145.78, 145.80, 146.06; found: C,
89.20; H,10.72%. Calcd for C20H28: C, 89.49; H,10.51%. Mp 54e55 ꢀC.
4.3.11. N-(10-(1H-Inden-1-yl)undecyl)-N-(phenylmethyl)-4-methyl-
benzenesulfonamide (2h) (54/46 mixture of diastereomers). Color-
less oil. IR (neat) 3063, 2924, 2855, 1458, 1342, 1157, 733 cmꢂ1; 1H
NMR (CDCl3)
d
0.47 (d, J¼6.5 Hz, 0.46ꢁ3H), 0.98 (d, J¼6.5 Hz,
4.3.6. 1-(1-Adamantyl)-1H-indene (2c). White solid. IR (Nujol)
0.54ꢁ3H), 0.98e1.57 (m, 16H), 2.18 (m, 1H), 2.43 (s, 0.54ꢁ3H), 2.44
(s, 0.46ꢁ3H), 3.04e3.09 (m, 2H), 3.46 (br s, 0.54ꢁ1H), 3.50 (br s,
0.46ꢁ1H), 4.30 (s, 0.54ꢁ2H), 4.31 (s, 0.46ꢁ2H), 6.46 (dd, J¼6.0,
2854, 1450, 1366, 1096, 756, 716 cmꢂ1; 1H NMR (CDCl3)
d
1.58e1.64
(m, 6H), 1.66e1.71 (dm, 3H), 1.82 (dm, 3H), 1.95 (br s, 3H), 3.14

5998
H. Someya et al. / Tetrahedron 66 (2010) 5993e5999
2.0 Hz, 0.46ꢁ1H), 6.49 (dd, J¼6.0, 2.0 Hz, 0.54ꢁ1H), 6.81 (dd, J¼6.0,
2.0 Hz, 0.54ꢁ1H), 6.84 (dd, J¼6.0, 2.0 Hz, 0.46ꢁ1H), 7.16 (m, 1H),
7.22e7.34 (m, 9H), 7.39 (t, J¼7.5 Hz, 1H), 7.72 (dd, J¼8.5, 5.0 Hz, 2H);
124.66,125.23, 125.96, 126.84, 126.99, 127.08, 127.14, 128.55, 128.62,
141.77, 142.09, 142.58, 145.82, 146.90; found: C, 92.60; H, 7.40%.
Calcd for C23H22: C, 92.57; H, 7.43%. Mp 72e73 ꢀC.
13C NMR (CDCl3)
d 14.91, 18.26, 21.72 (2C), 26.80, 26.84, 27.95, 28.07,
28.09, 28.15, 29.20, 29.27, 29.53, 29.61, 29.62, 29.75, 29.79, 30.03,
32.82, 34.90, 35.14, 36.53, 48.27, 48.32, 52.05, 52.08, 55.63, 56.63,
121.06, 121.07, 122.92, 123.40, 124.64, 124.76, 126.50, 126.55, 127.42,
127.43, 127.90 (2C), 128.49, 128.50, 128.72 (2C), 129.87 (2C), 131.53,
132.14, 136.81, 136.86, 136.88, 137.51 (2C), 137.95, 143.30, 143.31,
145.15, 145.43, 146.70, 147.46; HRMS (m/z) obsd 529.3011
4.3.17. 3-(1,1-Dimethylnonyl)-1-(1,1-dimethyl-3-phenylpropyl)-1H-
indene (6a). Colorless oil. IR (neat) 2932, 2855, 1605, 1458, 1366,
763 cmꢂ1; 1H NMR (CDCl3)
d
0.84 (t, J¼7.0 Hz, 3H), 1.01 (s, 3H), 1.04
(s, 3H), 1.06e1.25 (m, 12H), 1.30 (s, 3H), 1.31 (s, 3H), 1.62e1.84 (m,
4H), 2.65e2.73 (m, 2H), 3.33 (d, J¼2.0 Hz,1H), 6.18 (d, J¼2.0 Hz, 1H),
7.12 (t, J¼7.5 Hz,1H), 7.16e7.30 (m, 6H), 7.54 (dd, J¼11.5, 7.5 Hz, 2H);
(D
¼ꢂ0.6 ppm), calcd for C34H43O2NS 529.3015.
13C NMR (CDCl3)
d 14.30, 22.86, 25.15, 26.25, 26.37, 28.21, 28.27,
29.49, 29.68, 30.53, 31.10, 32.08, 36.67, 37.21, 41.11, 44.04, 56.92,
122.10, 123.83, 125.08, 125.85, 126.02, 128.53, 128.60, 131.38, 143.41,
4.3.12. 1-(3-(4-Bromophenyl)-1-methylpropyl)-1H-indene (2i) (54/46
mixture of diastereomers). Yellow oil. IR (neat) 3064, 2924, 2862,
145.02, 147.64, 151.63; found: C, 89.58; H, 10.49%. Calcd for C31H44
C, 89.36; H, 10.64%.
:
1488, 1373, 1072, 1001, 764 cmꢂ1 1H NMR (CDCl3)
; d 0.56 (d,
J¼7.0 Hz, 0.46ꢁ3H), 1.09 (d, J¼7.0 Hz, 0.54ꢁ3H), 1.28 (m, 1H), 1.66
(m, 0.46ꢁ1H), 1.86 (m, 0.54ꢁ1H), 2.22 (m, 1H), 2.35 (dt, J¼14.0,
8.0 Hz, 0.54ꢁ1H), 2.55 (m, 0.46ꢁ1H), 2.72 (m, 1H), 3.46 (t, J¼2.0 Hz,
0.46ꢁ1H), 3.53 (t, J¼2.0 Hz, 0.54ꢁ1H), 6.45 (dd, J¼5.5, 2.0 Hz,
0.54ꢁ1H), 6.49 (dd, J¼5.5, 2.0 Hz, 0.46ꢁ1H), 6.82 (dd J¼5.5,
2.0 Hz, 0.54ꢁ1H), 6.85 (dd, J¼5.5, 2.0 Hz, 0.46ꢁ1H), 6.90 (d,
J¼8.5 Hz, 1H), 7.10 (d, J¼8.5 Hz, 1H), 7.16 (m, 1H), 7.23e7.36 (m, 4H),
4.3.18. 3-(1,1-Dimethylnonyl)-1-(1-methyl-3-phenylpropyl)-1H-
indene (6b) (51/49 mixture of diastereomers). Colorless oil. IR (neat)
2924, 2855, 1605, 1458, 1381, 741, 694 cmꢂ1; 1H NMR (CDCl3)
d 0.50
(d, J¼7.0 Hz, 0.49ꢁ3H), 0.84 (t, J¼7.0 Hz, 0.49ꢁ3H), 0.84 (t, J¼7.0 Hz,
0.51ꢁ3H),1.06 (d, J¼7.0 Hz, 0.51ꢁ3H),1.06e1.25 (m,12H),1.30e1.35
(m, 7H), 1.64 (m, 1H), 1.71 (m, 0.49ꢁ1H), 1.80 (m, 1H), 1.91 (m,
0.51ꢁ1H), 2.21 (m, 1H), 2.39 (dt, J¼14.0, 8.5 Hz, 0.49ꢁ1H), 2.59 (m,
0.51ꢁ1H), 2.78 (m, 1H), 3.36 (br s, 0.51ꢁ1H), 3.44 (br s, 0.49ꢁ1H),
6.06 (d, J¼2.0 Hz, 0.49ꢁ1H), 6.10 (d, J¼2.0 Hz, 0.51ꢁ1H), 7.03 (d,
J¼6.5 Hz, 1H), 7.11e7.16 (m, 2H), 7.19e7.24 (m, 3H), 7.32 (dd, J¼14.5,
7.42 (d, J¼8.5 Hz, 1H); 13C NMR (CDCl3)
d 14.90, 18.45, 33.52, 33.75,
33.98, 34.17, 34.52, 37.96, 55.42, 56.51, 119.50, 119.70, 121.16, 121.17,
122.96, 123.26,124.79, 124.89,126.66,126.71, 130.33,130.39,131.44,
131.65, 131.95, 132.49, 136.38, 137.19, 141.54, 141.66, 145.08, 145.26,
146.39, 146.98; found: C, 69.43; H, 5.83%. Calcd for C19H19Br: C,
69.73; H, 5.85%.
7.0 Hz, 2H), 7.54 (dd, J¼7.5, 2.5 Hz, 1H); 13C NMR (CDCl3)
d 14.30,
14.31, 14.66, 18.42, 22.86, 22.87, 25.12 (2C), 28.14, 28.15, 28.25 (2C),
29.47, 29.51, 29.67, 29.71, 30.52, 30.53, 32.08 (2C), 34.05, 34.20,
34.45, 34.59, 34.94, 36.69, 36.79, 38.43, 41.08 (2C), 52.95, 54.14,
122.07, 122.09, 123.01, 123.46, 124.11, 124.23, 125.75, 125.97 (2C),
126.02, 128.38, 128.50, 128.59, 128.64, 129.78, 130.88, 142.72,
142.89, 144.51, 144.70, 148.45, 149.19, 151.81, 152.50; found: C,
89.51; H, 10.79%. Calcd for C30H42: C, 89.49; H, 10.51%.
4.3.13. 1-(1,1-Dimethylnonyl)-1H-indene (2j). Colorless oil. IR (neat)
2924, 2855, 1466, 1366, 763, 725 cmꢂ1 1H NMR (CDCl3)
; d 0.89 (t,
J¼6.5 Hz, 3H), 0.93 (s, 3H), 0.93 (s, 3H), 1.24e1.34 (m, 10H),
1.35e1.46 (m, 4H), 3.39 (br s, 1H), 6.53 (dd, J¼5.5, 2.0 Hz, 1H), 6.80
(dd, J¼5.5, 2.0 Hz, 1H), 7.13 (td, J¼7.5, 1.0 Hz, 1H), 7.23 (m, 1H), 7.32
(d, J¼8.0 Hz, 1H), 7.48 (d, J¼7.5 Hz, 1H); 13C NMR (CDCl3)
d 14.35,
22.91, 24.41, 26.03, 26.20, 29.59, 29.93, 30.77, 32.14, 36.88, 42.07,
59.52, 121.09, 124.34, 124.98, 126.48, 131.65, 138.17, 145.74, 145.94;
found: C, 88.82; H, 11.28%. Calcd for C20H30: C, 88.82; H, 11.18%.
4.3.19. 1H,1H0-1,10-Biindene (7) (73/27 mixture of diastereomers).
White solid. IR (Nujol) 2924, 2855,1458,1373, 964, 802, 756 cmꢂ1; 1H
NMR (CDCl3)
d
4.16 (s, 0.27ꢁ2H), 4.19 (s, 0.73ꢁ2H), 5.85 (dd, J¼5.5,
1.0 Hz, 0.73ꢁ2H), 6.34 (dd, J¼6.0, 1.0 Hz, 0.27ꢁ2H), 6.70 (d, J¼5.5 Hz,
0.73ꢁ2H), 6.73 (d, J¼6.0 Hz, 0.27ꢁ2H), 6.88 (d, J¼7.5 Hz, 0.27ꢁ2H),
7.04 (t, J¼7.5 Hz, 0.27ꢁ2H), 7.21e7.32 (m, 4H), 7.34 (d, J¼7.0 Hz,
4.3.14. 3-(1,1-Dimethylnonyl)-1-trimethylsilyl-1H-indene (4). Yellow
oil. IR (neat) 2932, 2855, 1458, 1381, 1249, 1034, 841, 763 cmꢂ1; 1H
NMR (CDCl3)
d
ꢂ0.06 (s, 9H), 0.84 (t, J¼7.5 Hz, 3H), 1.09e1.14 (m,
0.73ꢁ2H), 7.62 (d, J¼7.0 Hz, 0.73ꢁ2H); 13C NMR (CDCl3)
d 50.92, 51.37,
2H), 1.15e1.27 (m, 10H), 1.33 (s, 6H), 1.71e1.82 (m, 2H), 3.33 (d,
J¼2.0 Hz, 1H), 6.26 (d, J¼2.0 Hz, 1H), 7.14 (t, J¼7.5 Hz, 1H), 7.22 (t,
J¼7.5 Hz, 1H), 7.41 (d, J¼7.5 Hz, 1H), 7.66 (d, J¼7.5 Hz, 1H); 13C NMR
121.27, 121.43, 122.87, 122.99, 124.89, 125.07, 127.08, 127.12, 132.13,
132.31,136.25,136.91, 144.72,144.86, 145.20,146.02; found: C, 93.81;
H, 6.04%. Calcd for C18H14: C, 93.87; H, 6.13%. Mp 77e78 ꢀC.
(CDCl3)
d
ꢂ2.11,14.30, 22.86, 25.20, 28.44, 28.45, 29.51, 29.78, 30.63,
32.10, 36.72, 41.53, 44.10, 122.12, 123.13, 123.20, 124.26, 129.61,
Acknowledgements
143.33, 147.51, 149.67; HRMS (m/z) obsd 342.2740 (
calcd for C23H38Si 342.2743.
D¼ꢂ0.8 ppm),
This work was supported by Grants-in-Aid for Scientific Re-
search from the Ministry of Education, Culture, Sports, Science, and
Technology, Government of Japan. H.S. acknowledges JSPS for fi-
nancial support.
4.3.15. 9-(1,1-Dimethyl-3-phenylpropyl)-9H-fluorene
(5a). White
solid. IR (Nujol) 2924, 2854,1604,1450,1381,1281,1173, 741 cmꢂ1; 1H
NMR (CDCl3)
d
1.02 (s, 6H), 1.73 (dt, J¼9.0, 5.0 Hz, 2H), 2.76 (dt, J¼9.0,
5.0 Hz, 2H), 3.97 (s, 1H), 7.17e7.24 (m, 5H), 7.28 (t, J¼8.0 Hz, 2H), 7.34
Supplementary data
(t, J¼7.0 Hz, 2H), 7.59 (d, J¼8.0 Hz, 2H), 7.72 (d, J¼7.0 Hz, 2H); 13C NMR
(CDCl3)
d 26.40, 31.02, 37.96, 42.96, 56.29, 119.76, 125.92, 126.24,
1H and 13C NMR spectra of 1a, 1e, 1j, and the products. Sup-
plementary data associated with this article can be found in the
online version, at doi:10.1016/j.tet.2010.06.030. These data include
MOL files and InChIKeys of the most important compounds de-
scribed in this article.
126.61, 127.20, 128.54, 128.63, 142.42, 143.11, 145.97; found: C, 91.97;
H, 7.89%. Calcd for C24H24: C, 92.26; H, 7.74%. Mp 67e68 ꢀC.
4.3.16. 9-(1-Methyl-3-phenylpropyl)-9H-fluorene (5b). White solid.
IR (Nujol) 2924, 2731, 1458, 1373, 740, 702 cmꢂ1 1H NMR (CDCl3)
;
d
0.72 (d, J¼6.5 Hz, 3H), 1.61 (m, 1H), 1.77 (m, 1H), 2.41 (m, 1H), 2.65
References and notes
(ddd, J¼13.5, 10.0, 6.5 Hz, 1H), 2.75 (ddd, J¼13.5, 10.0, 6.0 Hz, 1H),
4.02 (d, J¼3.0 Hz, 1H), 7.14e7.20 (m, 3H), 7.24e7.30 (m, 4H),
7.33e7.37 (m, 2H), 7.46e7.48 (m, 2H), 7.74 (dd, J¼7.0, 4.5 Hz, 2H);
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13C NMR (CDCl3)
d 16.07, 34.37, 36.24, 36.83, 52.69, 119.83, 119.91,

H. Someya et al. / Tetrahedron 66 (2010) 5993e5999
5999
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13. When the catalytic amount of AgBr was reduced from 5 mol %, a prolonged
reaction time was needed. Reoptimization of the reaction time should be
required.
14. The silver-catalyzed reactions with indenylmagnesium bromide/LiBr complex
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17. In the silver-catalyzed reactions with Grignard reagents (Ref. 9), Et2O was also
the suitable solvent for the coupling reactions. This fact indicates that silver
catalyst coordinated by Et2O and/or indenyllithium the reactivity of which is
controlled by Et2O are important.
18. In each case, indene was recovered by the protonation of the unreacted in-
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Ref. 3b and 27.
€
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