1,2-Silyl migration in 1-halonaphthalenes catalyzed by I2

Article abstract of DOI:10.1002/hc.21434

1-Halo-8-hydrosilylnaphthalenes undergo 1,2-silyl migration to form 1-halo-7-silylnaphthalenes. The influence of the substituents on the silicon atom, the solvent effect, and the D-labeling experiments are investigated. The migration process may include four steps: (a) generation of acid (HI) by the reaction of the hydrosilane with I₂, (b) protonation of the naphthalene ring, (c) silyl group migration in the protonated intermediate, and (d) deprotonation of the naphthalene ring.

Full text of DOI:10.1002/hc.21434

Received: 29 May 2018
DOI: 10.1002/hc.21434
Revised: 1 August 2018
Accepted: 2 August 2018
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R E S E A R C H A R T I C L E
1,2-Silyl migration in 1-halonaphthalenes catalyzed by I2
Tomomi Shimizu1
Shogo Morisako2
Yohsuke Yamamoto2
Atsushi Kawachi3
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1Department of Applied Chemistry,
Graduate School of Science and
Engineering, Hosei University, Tokyo,
Japan
2Department of Chemistry, Graduate
School of Science, Hiroshima University,
Hiroshima, Japan
3Department of Chemical Science and
Technology, Faculty of Bioscience and
Applied Chemistry, Hosei University,
Tokyo, Japan
Abstract
1-Halo-8-hydrosilylnaphthalenes undergo 1,2-silyl migration to form
1-halo-7-silylnaphthalenes. The influence of the substituents on the silicon atom, the
solvent effect, and the D-labeling experiments are investigated. The migration pro-
cess may include four steps: (a) generation of acid (HI) by the reaction of the hy-
drosilane with I2, (b) protonation of the naphthalene ring, (c) silyl group migration in
the protonated intermediate, and (d) deprotonation of the naphthalene ring.
Correspondence
Atsushi Kawachi, Department of Chemical
Science and Technology, Faculty of
Bioscience and Applied Chemistry, Hosei
University, Tokyo, Japan.
Email: kawachi@hosei.ac.jp
Funding information
Grant-in-Aid for Scientific Research on
Innovative Areas “Stimuli-responsive
Chemical Species for the Creation of
Functional Molecules”, Grant/Award
Number: 15H00961
for these migrations was discussed to be relief of steric
compression.
1
INTRODUCTION
|
Silyl migrations have received much attention in terms of
mechanistic considerations as well as synthetic utilities be-
cause the migratory aptitudes of silyl groups are higher than
those of organyl groups.[1] Silyl migrations can be classified
as neutral, cationic, anionic, and radical migrations. Although
anionic migrations have been well studied, cationic migra-
tions have been less thoroughly explored. As a typical exam-
ple of the cationic migration, 1,2-bis(trimethylsilyl)benzene I
underwent 1,2-rearrangement to its 1,3-disilyl isomer II in an
acid-catalyzed manner (Scheme 1).[2] 1,8-bis(trimethylsilyl)
naphthalene III similarly afforded 1,7-disilyl isomer IV.
1-Silylnaphthalene V also underwent 1,2-rearrangement to
its 2-silyl isomer VI (Scheme 1).[3] The main driving force
Here we report cationic 1,2-silyl migration in
1-halo-8-(hydrosilyl)naphthalenes 1 and 2, during which a
hydrosilyl group at the eight-position undergoes migration to
the seven-position to form 3 and 4, respectively, upon stand-
ing, on silica gel, or in the presence of catalytic amounts of
I2 (Scheme 2).
2
RESULTS AND DISCUSSION
Preparation of 1-halo-8-
|
2.1
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silylnaphthalenes
1-Halo-8-silylnaphthalenes 1, 2, 5, and 6 were pre-
pared in good yields by lithium-halogen exchange of
1,8-dihalonaphthalenes 7 with n-BuLi and the subsequent
treatment with chlorosilanes (XR2SiCl) (Scheme 3).[4–6]
Contract grant sponsor: The Ministry of Education, Culture, Sports, Science
and Technology, Japan.
Contract grant number: 15H00961.
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Heteroatom Chemistry. 2018;e21434.
https://doi.org/10.1002/hc.21434
wileyonlinelibrary.com/journal/hc
© 2018 Wiley Periodicals, Inc.
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2 of 10
SHIMIZU et al.
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Methoxysilane 5a was also obtained by chlorination of 1a
with trichloroisocyanuric acid (TCCA) and alcoholysis of 8
(Scheme 4).[7,8] Reduction of 5a with LiAlD4 afforded deu-
terated silane 1a-D (Scheme 5).[9] The structures were char-
acterized by NMR spectroscopy.
Steric repulsion in 1 was supported by the NMR spectra.
1
The H resonances of the proton on the silicon atom in 1
and 2 were deshielded, whereas the 29Si resonances of the
silicon atom of the hydrosilyl group were shielded compared
with the corresponding values of silylnaphthalenes 11 and
12, respectively, as shown in Table 3. This behavior can be
explained in terms of the van der Waals effect[11]; the ste-
ric repulsion between the hydrosilyl group and the halogen
atom causes a decrease in the electron density on the hy-
drogen atom and an increase in the electron density on the
silicon atom. The van der Waals effect is also indicated by
the IR spectra (Table 3); the ν(Si-H) absorptions in 1 and
2 appeared at higher frequencies than those in 11 and 12,
respectively.
2.2
Silyl migration in 1-halo-8-
|
silylnaphthalenes
Upon standing in air for 3 days, 1-iodo-8-silylnaphthalene 1b
underwent
1,2-silyl
migration
to
afford
1-iodo-7-silylnaphthalene 3b.1 No other product was ob-
served in the 1H NMR spectra as shown in Figure 1. The silyl
migration also occurred when 1b was subjected to column
1
chromatography on silica gel eluted with hexane. The H
The molecular structures of 2a and 2b were revealed by
X-ray crystallographic analysis (Figures 2 and 3).[12,13] Each
molecule is distorted owing to the steric repulsion between
the halogen atom and the silyl group. The substituents are not
coplanar with the naphthalene ring. The dihedral angles of
Si-C8-C1-Y are 23.6° (Y = Br (2a)) and 27.5° (Y = I (2b)).
The atomic distance between Si and Y (3.22 Å (Y = Br (2a));
3.42 Å (Y = I (2b)) is longer than the mean distance between
C1 and C8 on the naphthalene ring.
DFT calculations also supported the existence of ste-
ric repulsion.[14] The structures of 1b and 3b were op-
timized at the B3LYP/6-31G(d)+LANL2DZ level of
theory, as shown in Figure 4. 7-Silylnaphthalene 3b is
more stable than 8-silylnaphthalene 1b by 56.3 kcal/mol.
8-Silylnaphthalene 1b is highly distorted, such extent that
the dihedral angle of Si-C8-C1-I is 24.4°. In contrast,
7-silylnaphthalene 3b is almost planar, as the dihedral
angle of Si-C7-C1-I is 0°.
resonance of the proton bonded to the silicon atom was
shifted upfield from δ = 5.66 ppm in 1b to δ = 4.59 ppm in
3b.
ThesilylmigrationwaspromotedbyacatalyticamountofI2
(Scheme 6). The silyl migration in 1-halo-8-silylnaphthalenes
1, 2, and 6 was monitored by 1H NMR spectroscopy. A solu-
tion of the substrate in CDCl3 or C6D6 was treated with I2
(5 mol%) in an NMR tube for 5 minutes or less, and the reac-
tion mixture was directly subjected to 1H NMR spectroscopy.
The yields of the products were estimated by using cyclohex-
ane as an internal standard.
The results of these experiments are summarized in
Table 1. Dimethylsilyl derivatives 1 produced the migrated
products 3 in 33%-81% yields in addition to protodesilylated
products 9 in 19%-64% yields. Diphenylsilyl derivatives 2
afforded migrated products 4 in 10%-21% yields with pro-
todesilylated products 9 (34%-56% yields) and 2 (30%-45%
yields). The amount of I2 was also significant, as only pro-
todesilylated products 9 were obtained from 1, 2, and 6 in
the presence of 50 mol% I2. The migrated products were ob-
tained in higher yields in hexane and C6D6 than in CDCl3.
Dimethylsilyl derivatives 1 produced the migrated products
in higher yields than diphenylsilyl derivatives 2.
2.4
Reaction mechanism of silyl migration
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To gain further insight into the reaction mechanism of
silyl migration, D-labeling experiments were performed
(Scheme 7). Deuterated silane 1a-D was treated with I2 under
the conditions used for the nondeuterated compounds. In the
presence of 4 mol% I2, 3a-D (56%), 9a-D (5%), and 9a (37%
yield) were obtained. In contrast, when 50 mol% I2 was used,
9a-D (52%) and 9a (43%) were obtained, but 3a-D was not
obtained.
The migration reactions of 1 and 2 were also performed
in a reaction flask in hexane or hexane-toluene, and migrated
products 3 and 4 were isolated in 38%-83% yields, as sum-
marized in Table 2.
According to the literature[2,3,10] and the D-labeling ex-
periments, the reaction mechanism is postulated as follows
(Scheme 8). (a) Reaction of 1-DSi with catalytic amounts of
I2 affords iodosilylnaphthalene 1-I and DI.[15] (b) Reaction of
1-DSi with DI yields Wheland complex IntA-DSiD.[16] (c) A
hydrosilyl group in IntA-DSiD migrates to the cationic car-
bon at the 7-position to form IntB-DSiD. (d) Iodide (or an-
other nucleophile) attacks the hydrogen at the 7-position in
IntB-DSiD to afford 3-DSiD. Alternatively, iodide (or another
nucleophile) attacks the silyl group in IntA-DSiD to produce
2.3
Structures of 1-halo-8-
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silylnaphthalenes
Thedrivingforceforsilylmigrationmaybereliefofstericcom-
pression, as discussed for the reactions of 1,2-disilylbenzene,
1,2-disilylnaphthalene, and 1-silylnaphthalene.[2,3,10]
1The migration was observed even under nitrogen atmosphere, but it was
slow (ca. 3 months).

SHIMIZU et al.
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Me2
(MeO)Si
SiMe3
SiMe3
Si
Br
DMe2
Br
CF3COOH
THF
Me3Si
LiAlD4 (x 1)
THF
r.t., 4 h
Me3Si
Me3Si
I
II
1a-D
5a
Me
3Si
SiMe3
SiMe3
HI
SCHEME 5 Preparation of 1-halo-8-deuteriosilylnaphthalene
1a-D
benzene
III
IV
HPhMeSi
HI
HPhMeSi
benzene
V
VI
SCHEME 1 Silyl migration in 1,2-disilylbenzene I,
1,8-disilylnaphthalene III, and 1-silylnaphthalene V
Y
Si
Y
XR2
XR2Si
FIGURE 1 1H NMR spectra of 1-iodo-8-silylnaphthalene 1b
and 1-iodo-7-silylnaphthalene 3b
1a: R = Me, X = H, Y = Br
1b: R = Me, X = H, Y = I
2a: R = Ph, X = H, Y = Br
2b: R = Ph, X = H, Y =I
3a: R = Me, X = H, Y = Br
3b: R = Me, X = H, Y = I
4a: R = Ph, X = H, Y = Br
4b: R = Ph, X = H, Y = I
DI, which is generated by the reaction of 1-DSi and I2 in the
initial step. Thus, the extent of D-incorporation depends on
the amount of I2.
SCHEME 2 1,2-Silyl migration in 1-halo-8-silylnaphthalenes 1
and 2
desilylated naphthalene 9-D. After DI is consumed, 1-DSi
reacts with HI to form IntA-DSiH, IntB-DSiH, and finally
3-DSiH in manners similar to the reaction of 1-DSi with DI.
D-incorporation into the naphthalene ring is induced only by
3
CONCLUSION
|
1-Halo-8-(hydrosilyl)naphthalenes 1 and 2 underwent 1,2-
silyl migration to afford 1-halo-7-silylnaphthalenes 3 and
Y
Y
Li
Y
Si
Y
XR2
n-BuLi (x 1.1)
XR2SiCl (x 1.2)
– 78 °C to r.t.
Et2O or
Et2O-THF
– 78 °C, 1 h
7a: Y = Br
7b: Y = I
1, 2, or 6
1a: R = Me, X = H, Y = Br 2a: R = Ph, X = H, Y = Br
1b: R = Me, X = H, Y = I
SCHEME 3 Preparation of 1-halo-8-
silylnaphthalenes 1, 2, 5, and 6
2b: R = Ph, X = H, Y = I
6a: R = Me, X = Me, Y = Br
Me2
MeOH (x 1.1)
Et3N (x 1.1)
HMe
2Si
Br
ClMe2Si
Br
(MeO)Si
Br
TCCA (x 1)
hexane
r.t., 6 h
THF
r.t., 1 h
SCHEME 4 Preparation of 1-halo-8-
(methoxy)silylnaphthalene 5a
1a
8
5a

4 of 10
SHIMIZU et al.
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Y
XR2Si
Y
Y
TABLE 3 Selected 1H and 29Si resonances in 1, 2, 11, and 12
I2 (5 mol%)
solvent
XR2Si
+
ν (Si-H)
R
X
Y
1H (δ)
29Si (δ)
(cm−1
)
9
1, 2, or 6
3, 4, or 10
1a
1b
2a
2b
11
12
Me
Me
Ph
Ph
Me
Ph
H
H
H
H
H
H
Br
I
Br
I
H
H
5.19
5.66
6.43
6.90
4.96
5.92
−13.43
−18.78
−16.98
−17.83
−20.41
−20.57
2164
2158
2162
2137
2123
2108
1a: R = Me, X = H, Y = Br
1b: R = Me, X = H, Y = I
2a: R = Ph, X = H, Y = Br
2b: R = Ph, X = H, Y =I
6a: R = Me, X = Me, Y = Br
3a: R = Me, X = H, Y = Br
3b: R = Me, X = H, Y = I
4a: R = Ph, X = H, Y = Br
4b: R = Ph, X = H, Y = I
10a: R = Me, X = Me, Y = Br
9a: Y = Br
9b: Y = I
SCHEME 6 1,2-Silyl migration in 1-halo-8-silylnaphthalenes 1,
2, and 6 catalyzed by I2
TABLE 1 1,2-Silyl migration reactions in an NMR tube
Y
XR2Si
Y
Y
I2 (5 mol%)
XR2Si
+
solvent
r.t.
1, 2, or 6
3, 4, or 10
9
R
X
Y
Solvent
Time (min)
Products (yield (%))a
1a
1a
1b
1b
2a
2b
6a
Me
Me
Me
Me
Ph
H
Br
Br
I
CDCl3
1
5
1
3
1
1
1
1a (0)
3a (33)
9a (64)
9a (56)
9b (35)
9b (19)
9a (34)
9b (56)
9a (0)
H
C6D6
1a (0)
3a (41)
3b (46)
3b (81)
4a (21)
4b (10)
11a (0)
H
CDCl3
C6D6
1b (0)
H
I
1b (0)
H
Br
I
CDCl3
CDCl3
CDCl3
2a (45)
2b (30)
6a (100)
Ph
H
Me
Me
Br
aThe yields were estimated in the 1H NMR spectra using cyclohexane as internal standard.
TABLE 2 1,2-Silyl migration reactions in a flask to isolate 3 and 4
Y
XR2 Si
Y
I2 (5 mol%)
XR2Si
solvent
r.t., 1 h
1 or 2
3 or 4
R
X
Y
Solvent
Products
Yield (%)a
1a
1b
2a
2b
Me
H
Br
Hexane
3a
3b
4a
4b
83
43
40
38
Me
Ph
Ph
H
H
H
I
Hexane
Br
I
Hexane-toluene
Hexane-toluene
aIsolated yields.

SHIMIZU et al.
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4. The driving force for the silyl migration may be relief of
steric compression, which was supported by the NMR spec-
tra and DFT calculations. D-labeling experiments were also
performed to obtain further insight into the reaction mecha-
nism of silyl migration. It was postulated that the migration
process may include four steps: (a) generation of acid (HI) by
the reaction of the hydrosilane with I2, (b) protonation of the
naphthalene ring, (c) silyl group migration in the protonated
intermediate, and (d) deprotonation of the naphthalene ring.
4
EXPERIMENTAL SECTION
General considerations
|
4.1
|
1H (400 MHz), 13C (100 MHz), and 29Si (79.5 MHz) NMR spec-
tra were recorded using a Bruker Avance III 400 spectrometer.
1H and 13C chemical shifts were referenced to the internal CDCl3
(δ(1H) = 7.26 ppm; δ(13C) = 77.00 ppm). 29Si chemical shifts
were referenced to external tetramethylsilane (δ = 0 ppm). The
mass spectra (EI) were recorded at 70 eV using a JEOL JMS-
Q1000GC Mk II mass spectrometer in our laboratory. Column
chromatography was performed using silica gel 60N (63-210
mesh, Kanto Chemical Co., Inc., Tokyo, Japan). Thin layer chro-
matography (TLC) was performed on plates of silica gel 60 F254
(Merck, Darmstadt, Germany).
FIGURE 3 Molecular structure of 2b; thermal ellipsoids are
drawn at the 30% probability level and H atoms, except for H1, are
omitted for clarity
Chemical Industries, Ltd., Osaka, Japan), and TCCA (Wako
Pure Chemical Industries, Ltd.) were used as received.
Chlorodimethylsilane (Tokyo Chemical Industry Co., Ltd.)
was distilled under a nitrogen atmosphere over calcium hy-
dride. Chlorotrimethylsilane (Tokyo Chemical Industry Co.,
Ltd.) was treated with small pieces of sodium under a nitro-
gen atmosphere to remove dissolved HCl, and the superna-
tant was used. Triethylamine (Tokyo Chemical Industry Co.,
Ltd.) was distilled under a nitrogen atmosphere over calcium
hydride. 1,8-Dibromonaphthalene and 1,8-diiodonaphthalene
were prepared according to the literature methods.[4,5] THF
and Et2O were distilled under a nitrogen atmosphere over
sodium benzophenone ketyl. Hexane was distilled under a
nitrogen atmosphere over sodium. All reactions were carried
out under an inert gas atmosphere.
4.2
Materials
|
1-Bromonaphthalene (Tokyo Chemical Industry Co., Ltd.,
Tokyo, Japan), n-butyllithium in hexane (Kanto Chemical
Co., Inc.), chlorodiphenylsilane (Shin-Etsu Chemical Co.,
Ltd., Tokyo, Japan), lithium aluminum hydride (Wako Pure
4.3
Experimental details
|
4.3.1
1-Bromo-8-(dimethylsilyl)
|
naphthalene (1a) (CAS No. 1313372-01-8)
A solution of n-BuLi in hexane (1.64 mol/L, 2.68 mL,
4.40 mmol) was added dropwise to
a solution of
1,8-dibromonaphthalene (7a) (1.14 g, 4.00 mmol) in Et2O
(40 mL) at −78°C. After the reaction mixture was stirred at
this temperature for 1 hour, chlorodimethylsilane (0.50 mL,
4.50 mmol) was added via a syringe. Then, the mixture was
warmed to room temperature. The solvent was removed in
vacuo, and the residue (1161 mg) was subjected to column
chromatography on silica gel eluted with hexane (Rf = 0.52)
1
to give 1a (891 mg, 84% yield) as a colorless oil. H NMR
(CDCl3) δ 0.60 (d, J = 4 Hz, 6H), 5.19 (sept, J = 4 Hz,
1H), 7.30 (t, J = 8 Hz, 1H), 7.46 (t, J = 8 Hz, 1H), 7.84
(dd, J = 8 Hz, J = 1 Hz, 1H), 7.87 (dd, J = 8 Hz, J = 1 Hz,
1H), 7.88 (dd, J = 8 Hz, J = 1 Hz, 1H), 8.02 (dd, J = 8 Hz,
FIGURE 2 Molecular structure of 2a; thermal ellipsoids are
drawn at the 30% probability level and H atoms, except for H1, are
omitted for clarity

6 of 10
SHIMIZU et al.
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FIGURE 4 Optimized structures of
1b (left) and 3b (right)
J = 1 Hz, 1H). 13C{1H}NMR(CDCl3)δ0.94, 123.16, 125.43,
J = 1 Hz, 1H), 7.82 (dd, J = 7 Hz, J = 1 Hz, 1H), 7.86 (dd,
J = 8 Hz, J = 1 Hz, 1H), 7.91 (dd, J = 8 Hz, J = 1 Hz, 1H).
13C{1H} NMR (CDCl3) δ 123.70, 125.43, 126.09, 127.88,
129.14, 129.43, 131.86, 132.45, 134.30, 135.63, 136.09,
137.05, 141.82 (signals corresponding to the two ipso carbons
in the phenyl groups were not observed). 29Si NMR (CDCl3)
δ −16.98 (d, 1JSi-H = 213 Hz). MS(EI) m/z: 389 (M+[81Br], 4),
387 (M+[79Br], 4), 311 (M+–Br, 100), 231 (M+–Br–Ph, 81).
IR (Nujol) (cm−1) 2725, 2162 (ν(Si-H)), 1585, 1309, 1190,
1115, 974, 868, 818, 731, 696. Anal. Calcd for C22H17BrSi: C,
67.86; H, 4.40; Found: C, 67.73; H, 4.42.
125.83, 129.43, 131.25, 132.26, 136.00, 136.63, 136.76,
1
138.49. 29Si NMR (CDCl3) δ −13.43 (d, JSi-H = 199 Hz).
MS(EI) m/z: 266 (M+[81Br], 28), 264 (M+[79Br], 28), 251
(M+[79Br]–Me, 98), 249 (M+[81Br]–Me, 100), 169 (M+–Me–
Br, 71). IR (Nujol) (cm−1) 3025, 2723, 2164 (ν(Si-H)), 1597,
1377, 1306, 1250, 1149, 980, 918, 772, 723.
4.3.2
1-Iodo-8-(dimethylsilyl)naphthalene
|
(1b) (CAS No. 105090-68-4)
A solution of n-BuLi in hexane (1.60 mol/L, 2.06 mL,
3.30 mmol) was added dropwise to
a solution of
4.3.4
(2b)
1-Iodo-8-(diphenylsilyl)naphthalene
|
1,8-diiodonaphthalene (7b) (1.14 g, 3.00 mmol) in THF–
Et2O (20 mL/20 mL) at −78°C. After the reaction mixture
was stirred at this temperature for 1 hour, chlorodimethylsi-
lane (0.39 mL, 3.60 mmol) was added via a syringe. Then,
the mixture was warmed to room temperature. The reaction
mixture was washed with brine, dried over Na2SO4, and
concentrated in vacuo to give 1b (850 mg, 91% yield) as a
yellow oil. 1H NMR (CDCl3) δ 0.60 (d, J = 4 Hz, 6H), 5.66
(sept, J = 4 Hz, 1H), 7.12 (dd, J = 8 Hz, J = 7 Hz, 1H), 7.43
(dd, J = 8 Hz, J = 7 Hz, 1H), 7.79 (dd, J = 8 Hz, J = 1 Hz,
1H), 7.84 (dd, J = 7 Hz, J = 1 Hz, 1H), 7.96 (dd, J = 7 Hz,
J = 1 Hz, 1H), 8.28 (dd, J = 7 Hz, J = 1 Hz, 1H). 13C {1H}
NMR (CDCl3) δ 1.22, 96.96, 125.07, 126.33, 130.29, 131.43,
135.77, 138.37, 138.73, 139.80, 141.02. 29Si NMR (CDCl3) δ
−18.78 (d, 1JSi-H = 201 Hz). MS(EI) m/z: 312 (M+, 27), 311
(M+–H, 27), 297 (M+–Me, 100), 169 (M+–I, 46). IR (Nujol)
(cm−1) 3053, 2158 (ν(Si-H)), 1594, 1540, 1304, 1248, 1142,
1047, 974, 893, 783, 652.
This compound was prepared in a manner similar to that used
for 1b and obtained as a pare yellow solid after column chro-
matography on silica gel eluted with hexane (Rf = 0.30). The
solid was recrystallized from hexane to give 2b (1.27 g) as
a pale yellow crystal in 73% yield. 1H NMR (CDCl3) δ 6.90
(s, 1H), 7.15 (t, J = 8 Hz, 1H), 7.31-7.41 (m, 7H), 7.47-
7.49 (m, 4H), 7.76 (d, J = 7 Hz, 1H), 7.84 (dd, J = 8 Hz,
J = 1 Hz, 1H), 7.88 (dd, J = 8 Hz, J = 1 Hz, 1H), 8.24 (dd,
J = 7 Hz, J = 1 Hz, 1H). 13C{1H} NMR (CDCl3) δ 97.58,
125.08, 126.60, 127.91, 129.15, 130.33, 132.21, 134.30,
135.77, 137.23, 140.21, 141.21, 142.23 (signals correspond-
ing to the two ipso carbons in the phenyl groups were not ob-
1
served). 29Si NMR (CDCl3) δ −17.83 (d, JSi-H = 215 Hz).
MS(EI) m/z 435 (M+–H, 4), 358 (M+–Ph, 23), 307 (M+–I,
11), 231 (M+–Ph–I, 100). IR (Nujol) (cm−1) 2727, 2137
(ν(Si-H)), 1604, 1300, 985, 857, 777, 729, 687. Anal. Calcd
for C22H17ISi: C, 60.55; H, 3.93; Found: C, 60.36; H, 4.01.
4.3.3
1-Bromo-8-(diphenylsilyl)
|
naphthalene (2a)
4.3.5
1-Bromo-8-[(methoxy)dimethylsilyl]
|
naphthalene (5a)
This compound was prepared in a manner similar to that used
for 1a and obtained as a pale yellow solid after column chro-
matography on silica gel eluted with hexane (Rf = 0.25). The
solid was recrystallized from hexane to give 2a (1.28 g) as a
pale yellow crystal in 82% yield. 1H NMR (CDCl3) δ 6.43 (s,
1H), 7.30-7.42 (m, 8H), 7.49-7.52 (m, 4H), 7.78 (dd, J = 7 Hz,
A solution of 1a (248 mg, 0.94 mmol) in hexane (1.5 mL)
was added dropwise to a suspension of TCCA (217 mg,
0.94 mmol) in hexane (0.5 mL) at 0°C, and the reaction mix-
ture was stirred at room temperature for 6 hour. After filtering
the reaction mixture, the solvent was removed in vacuo to

SHIMIZU et al.
7 of 10
|
H
Br
D
Br
H
Br
Si
Br
DMe2
a)
I2
C6D6
DMe2Si
+
+
9a
37%
43%
3a-D
56%
0%
9a-D
5%
52%
1a-D
a)4 mol%:
SCHEME 7 D-labeling experiment
for 1,2-silyl migration in 1a-D
a)50 mol%:
DR2Si
Y
IR
2Si
Y
I2
+
D I
1-DSi
1-I
D
I
I
DR2Si
H
D
Y
D
Y
D
H
Y
DR2Si
DR2Si
Y
DR2Si
DR2Si
H
I
+
H
I
IntA-DSi
D
1-DSi
IntB-DSiD
3-DSiD
H
DR2Si
H
H
Y
Y
Y
H
Y
DR2Si
DR2Si
H
I
+
H
I
1-DSi
IntA-DSiH
IntB-DSiH
3-DSi
H
I
I
DR2Si
H
D
Y
D
Y
D
Y
DR2Si
H
+
ISi(D)R2
SCHEME 8 Plausible mechanism of
1,2-silyl migration in 1-D
IntA-DSiD
IntB-DSiD
9-D
afford 1-bromo-8-[(chloro)dimethylsilyl]naphthalene (8) as a
colorless oil. THF (2 mL), MeOH (0.04 mL, 1.06 mmol), and
Et3N (0.15 mL, 1.16 mmol) were added to the oil, which was
then stirred for 1 hour at room temperature. The solvent was
removed in vacuo, and the residue (389 mg) was subjected
to column chromatography on silica gel eluted with hexane-
AcOEt (20:1) (Rf = 0.50) to give 5a (180 mg, 65% yield)
1,8-dibromonaphthalene (7a) (286 mg, 1.00 mmol) in THF
(10 mL) at −78°C. After the reaction mixture was stirred at
this temperature for 1 hour, chlorotrimethylsilane (0.15 mL,
1.20 mmol) was added via a syringe. Then, the mixture was
warmed to room temperature. The solvent was removed in
vacuo, and the residue (343 mg) was subjected to column
chromatography on silica gel eluted with hexane (Rf = 0.63)
1
1
as a colorless oil. H NMR (CDCl3) δ 0.71 (s, 6H), 3.47 (s,
to give 6a (217 mg, 78% yield) as a colorless oil. H NMR
3H), 7.30 (dd, J = 8 Hz, J = 7 Hz, 1H), 7.51 (dd, J = 8 Hz,
J = 7 Hz, 1H), 7.81-7.85 (m, 2H), 7.87 (dd, J = 7 Hz,
J = 1 Hz, 1H), 8.20 (dd, J = 7 Hz, J = 1 Hz, 1H). 13C{1H}
NMR (CDCl3) δ 2.69, 50.55, 122.09, 125.40, 125.70, 129.40,
131.15, 132.03, 136.11, 136.21, 136.90, 137.64. 29Si{1H}
NMR (CDCl3) δ 6.73. MS(EI) m/z: 296 (M+[81Br], 8), 294
(M+[79Br], 7), 281 (M+[81Br]–Me, 100), 279 (M+[79Br]–Me,
98), 266 (M+[81Br]–2Me, 73), 264 (M+[79Br]–2Me, 71), 215
(M+–Br, 91). IR (Nujol) (cm−1) 3055, 1547, 1306, 1254,
1095, 978, 868, 814, 787. Anal. Calcd for C13H15BrOSi: C,
52.88; H, 5.12; Found: C, 52.64; H, 5.13.
(CDCl3) δ 0.60 (s, 9H), 7.30 (dd, J = 8 Hz, J = 7 Hz, 1H),
7.45 (dd, J = 8 Hz, J = 7 Hz, 1H), 7.82 (dd, J = 7 Hz,
J = 1 Hz, 1H), 7.84 (dd, J = 7 Hz, J = 1 Hz, 1H), 7.89 (dd,
J = 7 Hz, J = 1 Hz, 1H), 8.01 (dd, J = 7 Hz, J = 1 Hz, 1H).
13C{1H} NMR (CDCl3) δ 4.57, 122.35, 125.13, 125.61,
129.46, 130.83, 132.30, 136.06, 137.02, 137.65, 138.62.
29Si{1H} NMR (CDCl3) δ −2.70. MS(EI) m/z: 280 (M+[81Br],
12), 278 (M+[79Br], 11), 265 (M+[81Br]–Me, 100), 263
(M+[79Br]–Me, 98), 183 (M+–Me–Br, 87). IR (Nujol) (cm−1)
3055, 1547, 1493, 1304, 1250, 1192, 978, 870, 834, 766, 702.
4.3.7
1-Bromo-8-[(deuterio)dimethylsilyl]
|
naphthalene (1a-D)
4.3.6
1-Bromo-8-(trimethylsilyl)
|
naphthalene (6a) (CAS No. 124153-82-8)
A solution of 5a (480 mg, 1.60 mmol) in THF (4 mL) was
addeddropwisetoasuspensionofLiAlD4 (68 mg,1.60 mmol)
in THF (2 mL) at 0°C, and the reaction mixture was stirred at
A solution of n-BuLi in hexane (1.64 mol/L, 0.67 mL,
1.10 mmol) was added dropwise to
a solution of

8 of 10
SHIMIZU et al.
|
room temperature for 4 hour. Me3SiCl (0.20 mL, 1.60 mmol)
was added dropwise to the reaction mixture at 0°C, and the
reaction mixture was stirred at room temperature for 2 hour.
After the solvents were removed in vacuo; the residue was
diluted with hexane (10 mL) and filtered. The filtrate was
subjected to bulb-to-bulb distillation (110-120°C/1.5 mm
Hg) to give 1a-D (128 mg, 30% yield) as a colorless oil. The
D-labeling was evidenced by comparison with the spectra
on silica gel eluted with hexane (Rf = 0.48) to give 3b
1
(106 mg, 83% yield) as a yellow oil. H NMR (CDCl3) δ
0.46 (d, J = 4 Hz, 6H), 4.59 (sept, J = 4 Hz, 1H), 7.19 (dd,
J = 8 Hz, J = 7 Hz, 1H), 7.64 (dd, J = 8 Hz, J = 1 Hz, 1H),
7.73 (d, J = 8 Hz, 1H), 7.82 (d, J = 8 Hz, 1H), 8.09 (dd,
J = 7 Hz, J = 1 Hz, 1H), 8.26 (d, J = 1 Hz, 1H). 13C{1H}
NMR (CDCl3) δ −3.76, 100.00, 127.33, 127.58, 128.87,
131.09, 133.44, 134.57, 137.45, 137.56, 138.67. 29Si NMR
1
1
of 1a. H NMR (CDCl3) δ 0.62 (s, 6H), 7.31 (t, J = 8 Hz,
(CDCl3) δ −16.21 (d, JSi-H = 190 Hz). MS(EI) m/z: 312
1H), 7.47 (dd, J = 8 Hz, J = 7 Hz, 1H), 7.84 (dd, J = 8 Hz,
J = 1 Hz, 1H), 7.87 (dd, J = 7 Hz, J = 1 Hz, 1H), 7.89 (dd,
J = 8 Hz, J = 1 Hz, 1H), 8.05 (dd, J = 7 Hz, J = 1 Hz, 1H).
13C{1H} NMR (CDCl3) δ 0.86, 123.16, 125.42, 125.81,
129.42, 131.24, 132.23, 135.98, 136.62, 136.71, 138.50. 29Si
(M+, 51), 297 (M+–Me, 25), 185 (M+–I, 100). IR (Nujol)
(cm−1) 3051, 2119 (ν(Si-H)), 1925, 1585, 1303, 1252, 1200,
1093, 879, 788, 642. Anal. Calcd for C12H13ISi: C, 46.16;
H, 4.20; Found: C, 45.87; H, 3.98.
1
NMR (CDCl3) δ −13.62 (t, JSi-D = 152 Hz). MS(EI) m/z:
4.3.10
1-Bromo-7-(diphenylsilyl)
267 (M+[81Br], 22), 265 (M+[79Br], M+[81Br]–H, 38), 263
(M+[79Br]–H, 18), 252 (M+[89Br]–H, 98), 250 (M+[79Br]–
Me, 100), 186 (M+–Me–Br, 75). IR (Nujol) (cm−1) 3055,
2898, 1564 (ν(Si-D)), 1493, 1417, 1358, 1306, 1248, 1192,
1051, 978, 866, 823, 795, 768, 706.
|
naphthalene (4a)
A solution of 2a (156 mg, 0.4 mmol) and iodine (4 mg,
0.02 mmol, 5 mol%) in hexane–toluene (1.0 mL/1.0 mL) was
stirred at room temperature for 1 hour. The reaction mixture
was washed with saturated Na2S2O3 solution (0.5 mL) and
dried over Na2SO4. The solvents were removed in vacuo. The
residue (110 mg) was subjected to column chromatography
on silica gel eluted with hexane (Rf = 0.20) to give 4a (59 mg,
4.3.8
1-Bromo-7-(dimethylsilyl)
|
naphthalene (3a)
1
A solution of 1a (106 mg, 0.40 mmol) and iodine (4 mg,
0.02 mmol, 5 mol%) in hexane (1.0 mL) was stirred at room
temperature for 1 hour. The reaction mixture was washed with
saturated Na2S2O3 solution (0.5 mL) and dried over Na2SO4.
The solvent was removed in vacuo. The residue (91 mg) was
subjected to column chromatography on silica gel eluted with
hexane (Rf = 0.58) to give 3a (46 mg, 43% yield) as colorless
38% yield) as a yellow solid. H NMR (CDCl3) δ 5.67 (s,
1H), 7.36 (t, J = 8 Hz, 1H), 7.40-7.49 (m, 6H), 7.64-7.67 (m,
4H), 7.70 (d, J = 8 Hz, 1H), 7.79-7.84 (m, 3H), 8.57 (s, 1H).
13C{1H} NMR (CDCl3) δ 123.24, 127.08, 127.64, 127.81,
128.14, 129.97, 130.16, 131.36, 132.14, 132.92, 133.01,
135.28, 135.84, 135.98. 29Si NMR (CDCl3) δ −17.60 (d, 1JSi-
H = 203 Hz). MS(EI) m/z: 390 (M+[81Br], 29), 388 (M+[79Br],
28), 309 (M+–Br, 100). IR (Nujol) (cm−1) 2723, 2671, 2127
(ν(Si-H)), 1587, 1377, 1109, 968, 802, 729. Anal. Calcd for
C22H17BrSi: C, 67.86; H, 4.40; Found: C, 67.85; H, 4.43.
1
oil. H NMR (CDCl3) δ 0.47 (d, J = 4 Hz, 6H), 4.60 (sept,
J = 4 Hz, 1H), 7.33 (t, J = 8 Hz, 1H), 7.67 (dd, J = 8 Hz,
J = 1 Hz, 1H), 7.78-7.83 (m, 3H), 8.44 (d, J = 1 Hz, 1H).
13C{1H} NMR (CDCl3) δ −3.75, 123.06, 126.67, 127.37,
127.81, 130.04, 131.06, 131.24, 133.52, 135.03, 137.04. 29Si
4.3.11
(4b)
1-Iodo-7-(diphenylsilyl)naphthalene
1
|
NMR (CDCl3) δ −16.04 (d, JSi-H = 190 Hz). MS(EI) m/z:
266 (M+[81Br], 31), 264 (M+[79Br], 30), 251 (M+[81Br]–
Me, 100), 249 (M+[79Br]–Me, 99), 169 (M+–Me–Br, 33).
IR (Nujol) (cm−1) 3053, 2958, 2900, 2723, 2121 (ν(Si-H)),
1545, 1415, 1354, 1306, 1250, 1150, 881, 825, 761. Anal.
Calcd for C12H13BrSi: C, 54.34; H, 4.94; Found: C, 54.22;
H, 4.80.
This compound was prepared in a manner similar to the
used for 4a and obtained as a yellow solid (70 mg, 40%
yield) after column chromatography on silica gel eluted
with hexane (Rf = 0.18). 1H NMR (CDCl3) δ 5.64 (s,
1H), 7.21 (t, J = 8 Hz, 1H), 7.39-7.48 (m, 6H), 7.60-7.68
(m, 5H), 7.74 (d, J = 8 Hz, 1H), 7.82 (d, J = 8 Hz, 1H),
8.10 (dd, J = 7 Hz, J = 1 Hz, 1H), 8.36 (s, 1H). 13C{1H}
NMR (CDCl3) δ 100.15, 127.73, 127.82, 128.14, 128.86,
129.97, 132.17, 132.91, 133.42, 133.62, 134.85, 135.86,
4.3.9
(3b)
1-Iodo-7-(dimethylsilyl)naphthalene
|
1
A solution of 1b (125 mg, 0.40 mmol) and iodine (4 mg,
0.02 mmol, 5 mol%) in hexane (1.0 mL) was stirred at room
temperature for 1 hour. The reaction mixture was washed
with saturated Na2S2O3 solution (0.5 mL) and dried over
Na2SO4. The solvent was removed in vacuo. The resi-
due (123 mg) was subjected to column chromatography
137.67, 141.15. 29Si NMR (CDCl3) δ −17.83 (d, JSi-
H = 201 Hz). MS(EI) m/z: 436 (M+, 36), 358 (M+–Ph,
26), 309 (M+–I, 100), 231 (M+–I–Ph, 57). IR (Nujol)
(cm−1) 2725, 2669, 2129 (ν(Si-H)), 1589, 1377, 1109,
802, 729. Anal. Calcd for C22H17ISi: C, 60.55; H, 3.93;
Found: C, 60.44; H, 3.96.

SHIMIZU et al.
9 of 10
|
4.3.12
1-(Dimethylsilyl)naphthalene (11)
4.4
X-ray crystallographic analysis
|
|
(CAS No. 30274-80-5)
X-ray crystallographic data for 2a and 2b were collected
using a SMART APEX-II CCD diffractometer with graphite-
monochromated Mo-Kα radiation (λ = 0.71073 Å) at 173 K
at the Department of Chemistry, Graduate School of Science,
Hiroshima University. The structures were solved by direct
methods using SIR 97[12] and refined by a full-matrix least-
squares procedure based on F2 with SHELX-97.[13] All non-
hydrogen atoms were refined anisotropically. Hydrogen
atoms were located at the expected positions by a geometri-
cal calculation and refined isotropically or found on the dif-
ference Fourier map and refined isotropically.
Crystal data for 2a: C22H17BrSi, fw 389.35, monoclinic,
P21/c (No. 14), a = 10.1994(7) Å, b = 16.3064(12) Å,
c = 11.1616(8) Å, β = 107.9380(10)°, V = 1766.1(2) Å3,
Z = 4, Dcalcd = 1.464 g/cm3, R(I > 2σ(I)) = 0.0221, Rw(all
data) = 0.0608, GOF = 1.033, T = 173 K.
A solution of n-BuLi in hexane (1.64 mol/L, 2.59 mL,
4.24 mmol) was added dropwise to
a solution of
1-bromonaphthalene (800 mg, 3.86 mmol) in Et2O
(10 mL) at 0°C. After the reaction mixture was stirred
at this temperature for 1 hour, chlorodimethylsilane
(0.50 mL, 4.59 mmol) was added via a syringe. Then, the
mixture was warmed to room temperature. The solvent
was removed in vacuo, and the residue (1157 mg) was
subjected to column chromatography on silica gel eluted
with hexane (Rf = 0.53) to give 11 (811 mg, 79% yield)
1
as a colorless oil. H NMR (CDCl3) δ 0.57 (d, J = 4 Hz,
6H), 4.96 (sept, J = 4 Hz, 1H), 7.51-7.61 (m, 3H), 7.80
(dd, J = 7 Hz, J = 1 Hz, 1H), 7.91-7.95 (m, 2H), 8.20 (dd,
J = 8 Hz, J = 1 Hz, 1H). 13C{1H} NMR (CDCl3) δ −3.26,
125.15, 125.51, 125.90, 127.58, 128.94, 129.99, 133.20,
133.61, 135.60, 136.96. 29Si NMR (CDCl3) δ −20.41 (d,
1JSi-H = 204 Hz). MS(EI) m/z: 186 (M+, 66), 171 (M+–Me,
100). IR (Nujol) (cm−1) 3048, 2123 (ν(Si-H)), 1506, 1376,
1250, 1146, 985, 883, 839, 779.
Crystal data for 2b: C22H17ISi, fw 436.34, monoclinic,
P21/c (No. 14), a = 10.2281(9) Å, b = 16.1277(14) Å,
c = 11.3827(10) Å, β = 106.6440(10)°, V = 1799.0(3) Å3,
Z = 4, Dcalcd = 1.611 g/cm3, R(I > 2σ(I)) = 0.0182, Rw(all
data) = 0.0485, GOF = 1.087, T = 173 K.
CCDC-1842169 (2a) and CCDC-1842170 (2b) contain
the supplementary crystallographic data for this paper. These
data can be obtained free of charge from the Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
4.3.13
1-(Diphenylsilyl)naphthalene (12)
|
(CAS No. 100447-84-5)
This compound was prepared in a manner similar to that
used for 11 and obtained as a colorless solid after column
chromatography on silica gel eluted with hexane (Rf = 0.33).
The solid was recrystallized from hexane to give 12 (969 mg)
4.5
Computational methods
1
|
as a pale yellow crystal in 81% yield. H NMR (CDCl3) δ
5.92 (s, 1H), 7.41-7.50 (m, 9H), 7.59-7.64 (m, 5H), 7.89 (d,
J = 8 Hz, 1H), 7.94 (d, J = 8 Hz, 1H), 8.07 (d, J = 8 Hz, 1H).
13C{1H} NMR (CDCl3) δ 125.24, 125.72, 126.16, 128.09,
128.25, 128.81, 129.80, 130.79, 131.42, 133.23, 133.27,
135.98, 136.83, 137.37. 29Si NMR (CDCl3) δ −20.57 (d, 1JSi-
H = 200 Hz). MS(EI) m/z: 310 (M+, 82), 231 (M+–Ph, 100).
IR (Nujol) (cm−1) 2727, 2663, 2108 (ν(Si-H)), 1587, 1305,
1109, 982, 787, 771, 731, 698.
Computations were executed with the Gaussian 09 pro-
gram package[14] at Research Center for Computing and
Multimedia Studies, Hosei University. The structures of 1b
and 3b were optimized at the B3LYP/(6-31G(d) for H, C, and
Si; LANL2DZ for I) level of theory. The frequency calcula-
tions were carried out for each compound at the same level
as in the structure optimization to confirm the absence of any
imaginary frequencies.
4.3.14
Typical procedure for NMR
ACKNOWLEDGMENTS
|
experiments: reaction of 1-halo-8-
silylnaphthalenes with I2 in CDCl3
This work was partially supported by a Grant-in-Aid for
Scientific Research on Innovative Areas “Stimuli-responsive
Chemical Species for the Creation of Functional Molecules”
(15H00961) from the Ministry of Education, Culture, Sports,
Science and Technology, Japan.
To a solution of a 1-halo-8-silylnaphthalene (0.040 mmol) and
cyclohexane (20 μL) in CDCl3 (0.60 mL) in a J. Young NMR
tube was added I2 (0.5 mg, 2.0 μmol) in one portion at room tem-
perature. The reaction mixture was shaken at room temperature
for 1 minute, and the sample was directly subjected to 1H NMR
spectroscopy. The yields of the products were estimated from
the integral ratios using cyclohexane as an internal standard.
ORCID
Atsushi Kawachi
http://orcid.org/0000-0001-7306-7669

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SHIMIZU et al.
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How to cite this article: Shimizu T, Morisako S,
Yamamoto Y, Kawachi A. 1,2-Silyl migration in
1-halonaphthalenes catalyzed by I2. Heteroatom
Chem. 2018;e21434. https://doi.org/10.1002/hc.21434
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