Preparation of α-silyl- or α,α-bis(silyl)-substituted alkylcopper reagents and their synthetic use

Article abstract of DOI:10.1016/j.tet.2005.01.101

Treatment of chlorobis(methyldiphenylsilyl)methyllithium with various alkyl and aryl Grignard reagents and CuCN·2LiCl afforded 1,1- disilylalkylcopper species. The aerobic oxidation of the resulting copper reagents provided a variety of acylsilanes in good yields. Meanwhile, treatment of dichloro(methyldiphenylsilyl)methyllithum with Bu₂CuLi·LiCN provided 1-cyano-1-silylalkylcopper species via consecutive double 1,2-migration of alkyl and cyano groups.

Full text of DOI:10.1016/j.tet.2005.01.101

Tetrahedron 61 (2005) 3361–3369
Preparation of a-silyl- or a,a-bis(silyl)-substituted alkylcopper
reagents and their synthetic use
a,
Junichi Kondo,a Atsushi Inoue,a Yuki Ito,a Hiroshi Shinokubob, and Koichiro Oshima
*
*
aDepartment of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto Daigaku Katsura, Nishikyo-ku,
Kyoto 615-8510, Japan
bDepartment of Chemistry, Graduate School of Science, Kyoto University, Sakyo-ku, Kyoto 606-8502, Japan
Received 2 November 2004; revised 29 November 2004; accepted 21 January 2005
Abstract—Treatment of chlorobis(methyldiphenylsilyl)methyllithium with various alkyl and aryl Grignard reagents and CuCN$2LiCl
afforded 1,1-disilylalkylcopper species. The aerobic oxidation of the resulting copper reagents provided a variety of acylsilanes in good
yields. Meanwhile, treatment of dichloro(methyldiphenylsilyl)methyllithum with Bu2CuLi$LiCN provided 1-cyano-1-silylalkylcopper
species via consecutive double 1,2-migration of alkyl and cyano groups.
q 2005 Elsevier Ltd. All rights reserved.
1. Introduction
In this context, we have chosen the combination of lithium
carbenoid, copper cyanide, and Grignard reagents/organo-
lithium compounds (Scheme 1).
Organocuprates and organocoppers are highly important
tools for organic synthesis, and numerous reports have been
published on the preparative methods and reactions.1 There
are several types of copper reagents, such as the classical
Gilman cuprates, cyanocuprates, hetero-cuprates, alkyl-
copper borontrifluoride complexes, and so on.2 Most of
them are prepared according to two approaches: (1)
transmetalation from organolithium or magnesium com-
pounds with copper salts and (2) direct metalation of
organic halides with active copper.
Here we wish to report the 1,2-migration reaction of the
alkyl group from copper to the adjacent carbon bearing a
chlorine atom in copper carbenoid reagents.5 We also
describe the reaction protocol in which organocuprates
enable sequential introduction of two different groups into
a,a-dichlorosilylmethyllithium.6
2. Results and discussion
1,2-Migration of an alkyl group on the metal center in metal
carbenoid reagents is a typical reaction of an organometallic
complex.3 This process has been successfully utilized in
alkylation of a-haloalkylmetals (metalZZn, B, Al, Cu, Mn,
etc.) and allows facile introduction of an alkyl group to the
organometallic reagents.4 The method would provide us
with a facile route to a wide variety of metal reagents from
relatively simple and easily accessible organometallics.
2.1. Preparation of 1,1-disilylalkylcoppers and their
conversion into various acylsilanes via aerobic oxidation
An addition of n-BuLi to a THF solution of (Ph2MeSi)2CCl2
(1)7 at K78 8C provided chlorodisilylmethyllithium 2
quantitatively via chlorine–lithium exchange in 10 min.
Then, lithium carbenoid 2 was then treated with n-BuMgBr
Scheme 1.
Keywords: Carbenoids; 1,2-Migration; Organocopper reagents; Halogen–lithium exchange; Grignard reagents.
* Corresponding authors. Tel.: C81 75 753 4010; fax: C81 75 753 3970 (H.S.); tel.: C81 75 383 2441; fax: C81 75 383 2438 (K.O.);
e-mail addresses: hshino@kuchem.kyoto-u.ac.jp; oshima@orgrxn.mbox.media.kyoto-u.ac.jp
0040–4020/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2005.01.101

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J. Kondo et al. / Tetrahedron 61 (2005) 3361–3369
Scheme 2.
(1.2 equiv in THF) and CuCN$2LiCl (1.2 equiv in THF),
and the mixture was stirred at 0 8C. After 1 h stirring in the
presence of a copper salt, the requisite organocopper species
3b was generated via a 1,2-alkyl migration (Scheme 2).8
Hexane (5 mL) and NH4Cl aq (10 mL) were added, and the
mixture was exposed to air with stirring for 0.5 h. During
this period, the aqueous layer turned blue, indicating that
copper(I) was oxidized to copper(II). Extractive workup
followed by purification afforded acylsilane 4b in 81%
yield.
species in the presence of 4 equiv of pyridine to yield
benzoylsilane 6a in 84% yield. Additionally, several
features deserve to be pointed out. As shown in entries 2
and 3, p-FC6H4MgBr and C6F5MgBr, which are electron-
deficient and less nucleophilic arylmagnesiums, can be
efficiently employed. Interestingly, 2-thienyllithium which
usually acts as a non-transferable or dummy ligand1,11 in
mixed homocuprates or mixed higher order cyanocuprates,
provided none of acylsilanes. However, an addition of
magnesium bromide to 2-thienyllithium resulted in the
formation of the corresponding acylsilane 6d in good yields
(Table 2, entries 4 and 5). Furthermore, this reaction
procedure can be applied to the synthesis of various
aroylsilanes in entries 6–10. It enables to introduce silyl
carbonyl groups into large p-conjugated system such as
tolan, naphthalene, and phenanthrene.
Oxidation of the a,a-disilylalkylcopper species 3a–h with
air provided the corresponding acylsilanes in good yields
(Table 1). Several features of this reaction are noteworthy.
Various primary and secondary Grignard reagents can be
employed in the reaction. Interestingly, the reaction with
crotylmagnesium chloride yielded 3-pentenoylsilane 4h
without contamination of 2-methyl-3-butenoylsilane (entry
8). Unfortunately, these intermediary copper species did not
react with electrophiles such as either alkyl halides or acyl
chlorides. Aerobic oxidation of organocoppers often results
in the Ullmann coupling reaction.9 In these cases, however,
the Ullmann-type coupling products were not observed at
all: no dimerization reaction of the disilylalkyl group nor
coupling between the disilylalkyl group and the cyano group
proceeded. We presume that the reasons for the selective
formation of acylsilanes would be the bulkiness of the
disilylalkyl moiety and the absence of a cyano ligand on the
copper(I) center in copper species 3.
Further application of (silyldichloromethyl)disilane 8 to the
procedure described above worked well to yield benzoyl-
disilane 10 selectively in 51% yield (Scheme 3). Curiously,
the diphenylmethylsilyl group was cleaved selectively and
benzoylsilane 6a was not obtained at all.
Table 2. Synthesis of aroylsilanes via aerobic oxidation
Entry
ArMgX
6 Yield/%
Furthermore, we found that various aromatic Grignard
reagents can be employed favorably in this reaction protocol
(Table 2). Unfortunately, disilylphenylmethylcopper under
the standard conditions caused considerable hydrolysis due
to the increased reactivity of the benzylic copper (entry 1).10
In this case, however, oxidation of the intermediary copper
1
2
3
PhMgBr
p-FC6H4MgBr
C6F5MgBr
6a 84
6b 72
6c 76
a
4
5
6
7
—
6d 75
6e 80
6f 85
Table 1. Preparation of 1,1-disilylalkylcoppers and their aerobic oxidation
Entry
RMgX
4 Yield/%
8
9
6g 82
6h 41
1
2
EtMgBr
n-BuMgBr
4a 75
4b 81
3
4c 75
4
5
4d 65
4e 88
i-PrMgBr
10
6i 73
6
7
4f 84
4g 47
MeMgBr
a Disilylacetonitrile 7 instead of silyl(2-thienyl)ketone 6d was obtained in
81% yield.
8
4h 47

J. Kondo et al. / Tetrahedron 61 (2005) 3361–3369
3363
of the intermediary coppers 13 with allyl bromide proceeded
successfully to furnish the allylated compounds 15a and
15b.
Next, we attempted double butylation of 11 by utilizing
Bu2CuLi$LiCN which is widely known as a cyano-Gilman
cuprate. Contrary to our expectations, it turned out to
provide butylation–cyanation product 16a in good yield
Scheme 3.
Scheme 4.
without the formation of dibutylated silane 14a (Scheme 6).
The reaction with sBu2CuLi$LiCN and Me2CuLi$LiCN
also furnished a-cyano silanes 17b in 56% yield and 17c in
23% yield, respectively. Furthermore, in the case of
Ph2CuLi$LiCN, the reaction fashion was reversed to obtain
the diphenylated product 14b in a moderate yield.
The intermediary copper species 16a reacted with a variety
of electrophiles such as allyl bromide, methyl iodide, acyl
chlorides, and aldehydes.14 Table 3 summarizes the trapping
experiment of the a-cyanoalkylcopper species. The reaction
with aldehydes provided a,b-unsaturated nitriles 19e and
19f/19f0 via the Peterson elimination of the initial adducts.15
In entry 7, aerobic oxidation of this copper reagent in the
presence of pyridine afforded pentanoyl cyanide (19g) in a
moderate yield.
Scheme 5.
2.2. Consecutive double alkylation of a,a-dichloro-
silylmethyllithium by organocopper reagents
In addition to alkylation–cyanation, consecutive butylation–
phenylation was accomplished by sequential treatment of
dichloromethyllithium 12 with BuCu and PhMgBr. The
employment of BuCu derived from BuLi and copper iodide
worked nicely to provide the desired butylation–phenylation
product 21. The resulting copper compound 20 can be
coupled with allyl bromide and acetyl chloride to give the
corresponding adducts in moderate yields. The use of a
combination of BuLi and CuCN for butylation of 12
resulted in a formation of significant amount of the
alkylation–cyanation product (Scheme 7).
We next contemplated introduction of two different alkyl
groups into dihalo carbenoids via double 1,2-migration
(Scheme 4).
An addition of n-BuLi to a solution of dichloromethylsilane
1112 in THF at K78 8C resulted in the quantitative
deprotonation to yield silyldichloromethyllithium 12.
Then, this dihalo-lithium carbenoid was added to organo-
copper reagents derived from copper cyanide. As expected
from Scheme 1, the use of the copper reagent prepared by
premixing butylmagnesium bromide with CuCN in a 2:1
ratio at 0 8C yielded the dibutylated product 14a via the
consecutive migration in good yield after aqueous workup
(Scheme 5).13 The use of phenylmagnesium bromide
instead of BuMgBr also afforded the diphenylated product
14b in 67% yield. The addition of allyl bromide before
quenching resulted in trapping of the intermediary copper
species to provide 15a and 15b. The nucleophilic trapping
3. Conclusion
We have developed an easy and simple procedure which
enables us to synthesize various kinds of acylsilanes from
dichlorodisilylmethane and the corresponding Grignard
Scheme 6.

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J. Kondo et al. / Tetrahedron 61 (2005) 3361–3369
Table 3. Consecutive butylation–cyanation followed by C–C bond
formation
4. Experimental
4.1. General information
Melting points were obtained a Yanako MP-50929 melting
1
point apparatus and are uncorrected. H NMR (300 MHz),
13C NMR (75.3 MHz) and 19F NMR (282.5 MHz) spectra
were taken on a Varian GEMINI 300 spectrometer in CDCl3
as a solvent, and chemical shifts were given in d value with
tetramethylsilane as an internal standard. IR spectra were
determined on a SHIMADZU FTIR-8200PC spectrometer.
Mass spectra were determined on a JEOL JMS-700
spectrometer. TLC analyses were performed on commercial
glass plates bearing 0.25 mm layer of Merk Silica gel
60F254. Column chromatography was done with silica gel
(Wakogel 200 mesh). The analyses were carried out at the
Elemental Analysis Center of Kyoto University. Tetra-
hydrofuran (THF) was freshly distilled from sodium
benzophenone ketyl before use. Grignard reagents were
prepared from the corresponding alkyl halide and Mg
turning (Nacalai tesque, INC). Unless otherwise noted,
materials obtained from commercial suppliers were used
without further purification.
Entry
1
Electrophile
Product
Yield/%
71
CH2]CHCH2Br
19a
19b
2
3
MeI
70
54
CH3COCl
19c
4
PhCOCl
57
19d
19e
4.1.1. Preparation of dichlorobis(methyldiphenylsilyl)-
methane (1). n-BuLi (21 mL, 1.6 M solution in hexane,
33 mmol) was added to a solution of diisopropylamine
(4.9 mL, 35 mmol) in THF (20 mL) dropwise at 0 8C, and
the mixture was stirred for 0.5 h. To a pre-cooled solution of
dichloromethane (0.96 mL, 15 mmol) and (chloro)methyl-
diphenylsilane (6.3 mL, 30 mmol) in THF (30 mL) was
added the resultant solution dropwise at K78 8C via a
cannula. After the mixture was stirred for 0.5 h, the cooling
bath was removed. After stirring for 0.5 h at room
temperature, the mixture was poured into 1 M HCl and
extracted with ethyl acetate. The combined organic layers
were dried over anhydrous Na2SO4 and concentrated in
vacuo. Recrystallization of the residual white solid from
hexane/ethyl acetate provided dichlorobis(methyldiphenyl-
silyl)methane (1, 6.1 g, 12.8 mmol) in 85% yield: Mp
138 8C; IR (nujol) 1427, 1254, 1107, 843, 802, 723,
5
6
7
PhCHOa
75 (Z/ER99/1)
57 (Z/EZ54/45)
51
cC6H11CHOb
19f/19f0
air(O2)c
19g
a Conditions: Bu2CuLi$LiCN (1.1 equiv), electrophile (2.0 equiv) were
employed.
b Bu2CuLi$LiCN (1.1 equiv), RCHO (3.0 equiv), Me3SiCl (4.5 equiv) were
employed. Me3SiCl was used as a Lewis acid.
c The resultant copper reagent was exposed to air in the presence of 2 equiv
pyridine at 0 8C for 30 min.
reagents. Treatment of chlorodisilylmethyllithium with
various Grignard reagents and CuCN$2LiCl efficiently
affords 1,1-disilylalkylcopper species. The aerobic oxi-
dation of the resulting organocoppers provides a variety of
acylsilanes in good yields. In a second part, we have also
demonstrated a very different reactivity between two types
of cyanocuprates prepared from CuCN and either Grignard
reagents or lithium reagents. Treatment of silyldichloro-
methyllithium with the copper species prepared from
BuMgBr and CuCN (2BuMgBr/CuCN) provides dibutyl-
ation products. On the other hand, Bu2CuLi$LiCN (cyano-
Gilman cuprate) yields butylation–cyanation products.
1
696 cmK1; H NMR (CDCl3) d 0.22 (s, 6H), 7.34 (dd, JZ
7.5, 8.1 Hz, 8H), 7.43 (t, JZ7.5 Hz, 4H), 7.72 (d, JZ
8.1 Hz, 8H); 13C NMR (CDCl3) d K4.0, 71.4, 127.7, 130.1,
133.2, 136.3. Found: C, 67.91; H, 5.40%. Calcd for
C27H26Cl2Si2: C, 67.90; H, 5.49%.
4.2. General procedure for the preparation of acylsilanes
(4a) from dichlorodisilylmethane
Under argon atmosphere, to a solution of dichlorobis-
(methyldiphenylsilyl)methane (1, 239 mg, 0.5 mmol) in
Scheme 7.

J. Kondo et al. / Tetrahedron 61 (2005) 3361–3369
3365
THF (3 mL) was added butyllithium (0.31 mL, 1.6 M
solution in hexane, 0.5 mmol) dropwise at K78 8C and
the solution was stirred for 5 min. Ethylmagnesium bromide
(0.6 mL, 1.0 M solution in THF, 0.6 mmol) and CuCN$
2LiCl (0.6 mL, 1.0 M solution in THF, 0.6 mmol) were
added successively at K78 8C. After stirring for 1 h at 0 8C,
saturated aqueous NH4Cl (10 mL) and hexane (5 mL) were
added. The mixture was stirred vigorously for 0.5 h under
air at room temperature and then extracted with hexane. The
organic layers were dried over anhydrous Na2SO4 and
concentrated in vacuo. Purification by silica gel column
chromatography provided 1-(methyldiphenylsilyl)-1-propa-
none (4b, 95 mg, 0.37 mmol) in 75% yield as colorless oil.
Spectral data for this compound were identical with those
reported in the literature.16
7.36–7.48 (m, 6H), 7.59 (dd, JZ1.5, 8.1 Hz, 4H); 13C NMR
(CDCl3) d K5.6, 36.9, 128.3, 130.3, 132.7, 135.1, 243.9.
Found: C, 74.71; H, 6.79%. Calcd for C15H16OSi: C, 74.95;
H, 6.71%. Spectral data for this compound were identical
with those reported in the literature.18
4.2.7. 1-(Methyldiphenylsilyl)-3-penten-1-one (E/ZZ
60/40) (4h). RfZ0.46 (hexane/ethyl acetateZ10/1); color-
less oil; IR (neat) 1645, 1429, 1254, 1113, 996, 793, 729,
1
698 cmK1; H NMR (CDCl3) d 0.75 (s, 1.8H), 0.76 (s,
1.2H), 1.45 (d, JZ6.6 Hz, 1.2H), 1.60 (d, JZ4.8 Hz, 1.8H),
3.32 (dd, JZ1.2, 5.4 Hz, 1.2H), 3.40 (d, JZ6.9 Hz, 0.8H),
5.25–5.42 (m, 1.2H), 5.37–5.50 (m, 0.4H), 5.54–5.67 (m,
0.4H), 7.35–7.50 (m, 6H), 7.55–7.66 (m, 4H); 13C NMR
(CDCl3) d K5.2, K5.1, 13.1, 18.1, 48.0, 53.2, 120.7, 121.9,
128.1, 128.1, 128.2, 130.1, 130.1, 130.2, 132.6, 132.7,
135.0, 241.5, 242.1. HRMS (m/z) Found: 128.1270. Calcd
for C18H20OSi: 280.1283.
4.2.1. 1-(Methyldiphenylsilyl)-1-pentanone (4b). RfZ
0.58 (hexane/ethyl acetateZ10/1); colorless oil; IR (neat)
3474, 2932, 1722, 1643, 1429, 1254, 1113, 793, 729,
1
698 cmK1; H NMR (CDCl3) d 0.75 (s, 3H), 0.79 (t, JZ
4.2.8. Benzoylmethyldiphenylsilane (6a, known com-
pound). Under argon atomosphere, to a solution of
dichlorobis(methyldiphenylsilyl)methane (1, 239 mg,
0.5 mmol) in THF (3 mL) was added butyllithium
(0.31 mL, 1.6 M solution in hexane, 0.5 mmol) dropwise
at K78 8C and the solution was stirred for 5 min.
Phenylmagnesium bromide (0.6 mL, 1.0 M solution in
THF, 0.6 mmol) and CuCN$2LiCl (0.6 mL, 1.0 M solution
in THF, 0.6 mmol) were added successively at K78 8C.
After stirring for 1 h at 0 8C, pyridine (0.16 mL, 2.0 mmol)
was added. The mixture was stirred for 1 h under air at 0 8C
and then extracted with hexane. The organic layers were
dried over anhydrous Na2SO4 and concentrated in vacuo.
Purification by silica gel column chromatography provided
benzoylmethyldiphenylsilane (6a, 127 mg, 0.42 mmol) in
84% yield as clear, yellow oil. Spectral data for this
compound were identical with those reported in the
literature.19 RfZ0.44 (hexane/ethyl acetateZ10/1); IR
(neat) 1612, 1589, 1576, 1447, 1429, 1252, 1209, 1173,
1111, 794, 729, 698 cmK1; 1H NMR (CDCl3) d 0.87 (s, 3H),
7.31–7.50 (m, 9H), 7.60 (dd, JZ1.5, 7.5 Hz, 4H), 7.77 (dd,
JZ1.5, 8.4 Hz, 2H); 13C NMR (CDCl3) d K3.3, 128.2,
128.2, 128.5, 130.0, 132.9, 133.7, 135.1, 141.7, 232.0.
Found: C, 79.68; H, 6.06%. Calcd for C20H18OSi: C, 79.43;
H, 6.00%.
7.5 Hz, 3H), 1.18 (tq, JZ7.5, 7.5 Hz, 2H), 1.44 (tt, JZ7.5,
7.5 Hz, 2H), 2.65 (t, JZ7.5 Hz, 2H), 7.34–7.47 (m, 6H),
7.55–7.66 (m, 4H); 13C NMR (CDCl3) d K5.4, 13.7, 22.2,
24.1, 46.4, 128.3, 130.2, 133.0, 135.1, 245.1. Found: C,
76.79; H, 7.86%. Calcd for C18H22OSi: C, 76.54; H, 7.85%.
4.2.2. 1-(Methyldiphenylsilyl)-4-phenyl-1-butanone (4c,
known compound). Spectral data for this compound were
identical with those reported in the literature.17
4.2.3. 1-(Methyldiphenylsilyl)-5-hexen-1-one (4d). RfZ
0.45 (hexane/ethyl acetateZ10/1); colorless oil; IR (neat)
3071, 2936, 1643, 1429, 1254, 1113, 997, 912, 793, 729,
698 cmK1; 1H NMR (CDCl3) d 0.75 (s, 3H), 1.58 (tt, JZ6.9,
7.2 Hz, 2H), 1.94 (dt, JZ6.6, 6.9 Hz, 2H), 2.66 (t, JZ
7.2 Hz, 2H), 4.89 (d, JZ11.1 Hz, 1H), 4.90 (d, JZ16.2 Hz,
1H), 5.58–5.74 (m, 1H), 7.35–7.48 (m, 6H), 7.55–7.61 (m,
4H); 13C NMR (CDCl3) d K5.3, 21.2, 33.0, 48.8, 115.0,
128.2, 130.1, 132.8, 135.0, 138.1, 244.4. Found: C, 77.43;
H, 7.40%. Calcd for C19H22OSi: C, 77.50; H, 7.53%.
4.2.4. 2-Methyl-1-(methyldiphenylsilyl)-1-propanone
(4e). RfZ0.58 (hexane/ethyl acetateZ10/1); colorless oil;
a paleIR (neat) 2968, 1639, 1429, 1254, 1113, 986, 793,
1
729, 698 cmK1; H NMR (CDCl3) d 0.77 (s, 3H), 0.91 (d,
JZ6.9 Hz, 6H), 3.02 (sept, JZ6.9 Hz, 1H), 7.34–7.47 (m,
6H), 7.56–7.62 (m, 4H); 13C NMR (CDCl3) d K4.7, 16.5,
45.8, 128.1, 130.0, 133.2, 135.0, 247.1. Found: C, 76.16; H,
7.55%. Calcd for C17H20OSi: C, 76.07; H, 7.51%.
4.2.9. 4-Fluorobenzoylmethyldiphenylsilane (6b). RfZ
0.44 (hexane/ethyl acetateZ10/1); pale yellow oil; IR (neat)
3071, 1614, 1583, 1500, 1429, 1406, 1225, 1151, 1113, 843,
1
729 cmK1; H NMR (CDCl3) d 0.88 (s, 3H), 7.02 (t, JZ
9.0 Hz, 2H), 7.36–7.48 (m, 6H), 7.57–7.62 (m, 4H), 7.80
(dd, JZ5.4, 9.0 Hz, 2H); 13C NMR (CDCl3) d K3.2, (115.4,
115.7), 128.2, 130.0, (130.6, 130.7), 133.4, 134.9, (138.1,
138.7), (163.5, 166.9), 229.5; 19F NMR (CDCl3) d K105.3.
Found: C, 75.11; H, 5.42%. Calcd for C20H17FOSi: C,
74.97; H, 5.35%.
4.2.5. Cyclopentyl methyldiphenylsilyl ketone (4f). RfZ
0.45 (hexane/ethyl acetateZ10/1); colorless oil; IR (neat)
2957, 2866, 1638, 1429, 1254, 1111, 793, 729, 698 cmK1
;
1H NMR (CDCl3) d 0.77 (s, 3H), 1.40–1.53 (m, 6H), 1.60–
1.77 (m, 2H), 3.24–3.36 (m, 1H), 7.30–7.47 (m, 6H), 7.56–
7.62 (m, 4H); 13C NMR (CDCl3) d K4.8, 26.0, 26.9, 56.9,
128.1, 129.9, 133.2, 135.0, 245.1. Found: C, 77.43; H,
7.53%. Calcd for C19H22OSi: C, 77.50; H, 7.53%.
4.2.10. 2,3,4,5,6-Pentafluorobenzoylmethyldiphenyl-
silane (6c). RfZ0.56 (hexane/ethyl acetateZ10/1); yellow
oil; IR (neat) 3074, 1649, 1518, 1489, 1429, 1306, 1117,
974, 731, 698 cmK1; 1H NMR (CDCl3) d 0.85 (s, 3H), 7.36–
7.50 (m, 6H), 7.54–7.61 (m, 4H); 13C NMR (CDCl3) d
K5.5, 128.3, 130.6, 130.8, 135.0, 136.3, 138.2, 141.2,
141.6, 143.2, 143.7, 229.2; 19F NMR (CDCl3) d K160.1,
4.2.6. Acetylmethyldiphenylsilane (4g, known com-
pound). RfZ0.34 (hexane/ethyl acetateZ10/1); colorless
oil; IR (neat) 1643, 1429, 1340, 1254, 1113, 791, 731,
1
698 cmK1; H NMR (CDCl3) d 0.75 (s, 3H), 2.32 (s, 3H),

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J. Kondo et al. / Tetrahedron 61 (2005) 3361–3369
K150.4, K142.9. Found: C, 61.21; H, 3.36%. Calcd for
C20H13F5OSi: C, 61.22; H, 3.34%.
122.7, 126.7, 126.9, 127.2, 127.5, 127.7, 127.9, 128.3,
129.0, 130.1, 130.8, 131.8, 134.0, 134.6, 135.1, 138.2,
236.7. HRMS (m/z) Found: 402.1438. Calcd for C28H22OSi:
402.1440.
4.2.11. Methyldiphenylsilyl 2-thienyl ketone (6d). RfZ
0.53 (hexane/ethyl acetateZ5/1); yellow oil; IR (KBr)
3068, 1570, 1512, 1428, 1406, 1230, 1113, 1051, 788, 731,
4.2.17. Bis(methyldiphenylsilyl)acetonitrile (7). RfZ0.35
(hexane/ethyl acetateZ5/1); white solid; IR (neat) 2208,
1429, 1165, 1009, 816, 725, 696 cmK1; 1H NMR (CDCl3) d
0.32 (s, 6H), 2.32 (s, 1H), 7.27–7.45 (m, 16H), 7.56–7.63
(m, 4H); 13C NMR (CDCl3) d K3.9, 5.1, 71.8, 128.1, 128.2,
130.1, 130.2, 134.0, 134.7. Found: C, 77.81; H, 6.32; N,
3.17%. Calcd for C28H27NSi2: C, 77.54; H, 6.28; N, 3.23%.
1
706 cmK1; H NMR (CDCl3) d 0.88 (s, 3H), 6.97 (t, JZ
4.5 Hz, 1H), 7.34 (d, JZ4.5 Hz, 1H), 7.38–7.48 (m, 6H),
7.59 (d, JZ4.5 Hz, 1H), 7.61–7.65 (m, 4H); 13C NMR
(CDCl3) d K3.8, 128.2, 130.2, 133.2, 133.6, 134.6, 135.2,
151.2, 221.0. Found: C, 70.10; H, 5.33%. Calcd for
C18H16OSSi: C, 70.09; H, 5.23%.
4.2.12. (4-Phenylbenzoyl)methyldiphenylsilane (6e). RfZ
0.50 (hexane/ethyl acetateZ5/1); yellow oil; IR (neat)
4.2.18. 1-[Dichloro-(methyldiphenylsilyl)methyl]-1,1,2,
2,2-pentamethyldisilane (8). RfZ0.60 (hexane/ethyl
acetateZ30/1); colorless oil; IR (neat) 3072, 2953, 1429,
1400, 1248, 822 cmK1; 1H NMR (CDCl3) d K0.06 (s, 6H),
0.15 (s, 9H), 0.84 (s, 6H), 0.32 (s, 3H), 7.35–7.48 (m, 6H),
7.80–7.87 (m, 4H); 13C NMR (CDCl3) d K3.2, K3.0,
K0.7, 74.4, 127.7, 130.1, 133.5, 136.1. Found: C, 55.22; H,
6.93. Calcd for C19H28Cl2Si3: C, 55.44; H, 6.86%.
1
3069, 1593, 1556, 1429, 1217, 1177, 847, 486 cmK1; H
NMR (CDCl3) d 0.91 (s, 3H), 7.34–7.49 (m, 6H), 7.55–7.61
(m, 4H), 7.62–7.67 (m, 4H), 7.86 (d, JZ8.4 Hz, 2H); 13C
NMR (CDCl3) d K3.1, 127.0, 127.1, 128.0, 128.1, 128.6,
128.7, 129.9, 133.6, 135.0, 139.7, 140.2, 145.3, 230.8.
Found: C, 82.56; H, 5.99%. Calcd for C26H22OSi: C, 82.50;
H, 5.86%.
4.2.19. General procedure for the preparation of
1-benzoyl-1,1,2,2,2-pentamethyldisilane (10) from
dichlorosilylmethyldisilane 8. Under argon atmosphere,
to a solution of (dichlorosilylmethyl)disilane (8, 206 mg,
0.5 mmol) in THF (3 mL) was added butyllithium (0.31 mL,
1.6 M solution in hexane, 0.5 mmol) dropwise at K78 8C
and the solution was stirred for 5 min. Phenylmagnesium
bromide (0.6 mL, 1.0 M solution in THF, 0.6 mmol) and
CuCN$2LiCl (0.6 mL, 1.0 M solution in THF, 0.6 mmol)
were added successively at K78 8C. After stirring for 1 h at
0 8C, pyridine (0.16 mL, 2.0 mmol) was added. The mixture
was stirred for 1 h under air at 0 8C and then extracted with
hexane. The organic layers were dried over anhydrous
Na2SO4 and concentrated in vacuo. Purification by silica gel
column chromatography provided 1-benzoyl-1,1,2,2,2-
pentamethyldisilane (10, 61 mg, 0.27 mmol) in 51% yield.
RfZ0.38 (hexane/ethyl acetateZ20/1); IR (neat) 2955,
1614, 1591, 1576, 1447, 1429, 1113, 1055, 831, 799,
4.2.13. [4-(Phenylethynyl)benzoyl]diphenylsilane (6f).
RfZ0.35 (hexane/ethyl acetateZ10/1); yellow oil; IR
(neat) 3071, 2957, 1589, 1427, 1209, 1111, 756, 695 cmK1
;
1H NMR (CDCl3) d 0.90 (s, 3H), 7.19–7.33 (m, 9H), 7.35–
7.42 (m, 4H), 7.59–7.64 (m, 4H), 7.76 (d, JZ8.1 Hz, 2H);
13C NMR (CDCl3) d K3.3, 128.2, 128.2, 128.5, 130.0,
132.9, 133.7, 135.1, 141.7, 232.0. Found: C, 83.70; H,
5.41%. Calcd for C28H22OSi: C, 83.54; H, 5.51%.
4.2.14. 2-Naphthalene(methyldiphenylsilyl)methanone
(6g). RfZ0.59 (hexane/ethyl acetateZ5/1); yellow oil; IR
(neat) 3069, 2959, 1595, 1429, 1252, 1177, 1113, 727,
698 cmK1; 1H NMR (CDCl3) d 0.95 (s, 3H), 7.37–7.50 (m,
7H), 7.52–7.59 (m, 1H), 7.63–7.70 (m, 5H), 7.82 (d, JZ
8.1 Hz, 2H), 7.91 (dd, JZ1.8, 8.1 Hz, 1H), 8.24 (s, 1H); 13C
NMR (CDCl3) d K3.1, 122.4, 126.4, 127.6, 128.1, 128.3,
128.4, 129.6, 129.9, 132.3, 132.3, 133.8, 135.0, 135.3,
139.1, 231.2. Found: C, 81.50; H, 5.96%. Calcd for
C20H18OSi: C, 81.77; H, 5.72%.
1
692 cmK1; H NMR (CDCl3) d 0.13 (s, 9H), 0.43 (s, 6H),
7.45–7.57 (m, 3H), 7.78 (dd, JZ2.0, 13.5 Hz, 2H); 13C
NMR (CDCl3) d K3.8, K1.8, 128.1, 132.5, 133.8, 141.9,
236.2.
4.2.15. 1-Naphthalene(methyldiphenylsilyl)methanone
(6h). RfZ0.60 (hexane/ethyl acetateZ5/1); yellow oil; IR
(KBr) 3028, 1612, 1589, 1576, 1447, 1429, 1252, 1209,
1173, 1111, 794, 729, 698 cmK1; 1H NMR (CDCl3) d 0.89
(s, 3H), 7.30–7.46 (m, 7H), 7.48–7.59 (m, 2H), 7.62–7.66
(m, 4H), 7.75 (d, JZ7.5 Hz, 1H), 7.85 (d, JZ7.5 Hz, 1H),
7.91 (d, JZ8.1 Hz, 1H), 8.70 (d, JZ8.1 Hz, 1H); 13C NMR
(CDCl3) d K3.1, 124.1, 125.7, 126.4, 128.1, 128.2, 128.2,
128.7, 129.9, 131.3, 132.5, 133.8, 135.0, 139.1, 236.8.
Found: C, 81.63; H, 5.86%. Calcd for C24H20OSi: C, 81.77;
H, 5.72%.
4.2.20. General procedure for the preparation of
5-(methyldiphenylsilyl)nonane (14a). n-BuLi (0.31 mL,
1.6 M solution in hexane, 0.50 mmol) was added to a
solution of Ph2MeSiCHCl2 (11, 141 mg, 0.50 mmol) in
THF (5 mL) at K78 8C, and the mixture was stirred for
30 min. Then nBu2CuCN(MgBr)2 in THF, which was
prepared from n-BuMgBr (1.25 mL, 1.0 M solution in
THF, 1.25 mmol) and CuCN$2LiCl (0.55 mL, 1.0 M
solution in THF, 0.55 mmol) at 0 8C, was added to the
resulting solution at K78 8C. After stirring for 5 min, the
mixture was allowed to warm gradually to 0 8C. After
stirring the mixture for 1 h at 0 8C, the reaction was
quenched with diluted aqueous HCl (20 mL). The mixture
was extracted with hexane (10 mL!3), and the organic
layers were dried over anhydrous Na2SO4 and concentrated
in vacuo. Purification by silica gel column chromatography
provided 5-(methyldiphenylsilyl)nonane (14a, 127 mg,
0.39 mmol) in 78% yield as colorless oil: RfZ0.78
4.2.16. 9-Phenanthrene(methyldiphenylsilyl)methanone
(6i). RfZ0.42 (hexane/ethyl acetateZ5/1); yellow oil; IR
(KBr) 3021, 1591, 1428, 1245, 1112, 892, 788, 722,
1
696 cmK1; H NMR (CDCl3) d 0.94 (s, 3H), 7.37–7.49
(m, 6H), 7.52 (d, JZ3.9 Hz, 2H), 7.58–7.62 (m, 1H), 7.63–
7.66 (m, 1H), 7.67–7.71 (m, 4H), 7.71–7.74 (m, 1H), 8.00
(s, 1H), 8.63 (d, JZ8.1 Hz, 1H), 8.68 (d, JZ8.1 Hz, 1H),
8.75 (d, JZ8.1 Hz, 1H); 13C NMR (CDCl3) d K3.5, 122.6,

J. Kondo et al. / Tetrahedron 61 (2005) 3361–3369
3367
(hexane/ethyl acetateZ10/1); IR (neat) 3069, 2856, 1952,
1H NMR (CDCl3) d 0.76 (s, 3H), 0.85 (t, JZ7.2 Hz,
3H), 1.12–1.72 (m, 6H), 2.30 (dd, JZ4.2, 10.8 Hz, 1H),
7.38–7.51 (m, 6H), 7.56–7.66 (m, 4H); 13C NMR (CDCl3)
d K5.46, 13.90, 17.84, 22.01, 26.87, 32.01, 121.88,
128.06, 128.10, 130.16, 132.21, 132.50, 134.55. Found: C,
77.78; H, 7.80%. Calcd for C19H23NSi: C, 77.76; H,
7.90%.
1
1880, 1817, 1466, 1252, 1111, 787, 700 cmK1; H NMR
(CDCl3) d 0.58 (s, 3H), 0.81 (t, JZ7.2 Hz, 6H), 1.12–1.44
(m, 12H), 1.48–1.62 (m, 1H), 7.31–7.42 (m, 6H), 7.51–7.59
(m, 4H); 13C NMR (CDCl3) d K5.06, 14.10, 23.02, 23.61,
29.65, 31.77, 127.54, 128.76, 134.63, 137.26. Found: C,
81.19; H, 9.71%. Calcd for C22H32Si: C, 81.41; H, 9.94%.
4.2.21. 4-Butyl-4-(methyldiphenylsilyl)-1-octene (15a).
RfZ0.66 (hexane/ethyl acetateZ10/1); colorless oil; IR
(neat) 2957, 2858, 1636, 1427, 1254, 1105, 999, 910, 784,
4.2.25. 2-(Methyldiphenylsilyl)-3-methylpentanenitrile
(17b). RfZ0.37 (hexane/ethyl acetateZ10/1); colorless
oil; IR (neat) 2964, 2220, 1429, 1115, 793, 732, 700 cmK1
;
737, 700 cmK1; H NMR (CDCl3) d 0.66 (s, 3H), 0.78 (t,
1H NMR (CDCl3) d 0.77 (t, JZ7.4 Hz, 3H), 0.80 (s, 3H),
0.81 (s, 3H), 0.86 (t, JZ7.4 Hz, 3H), 0.93 (d, JZ6.6 Hz,
3H), 1.02 (d, JZ6.6 Hz, 3H), 1.20–1.77 (m, 6H), 2.38 (d,
JZ4.5 Hz, 1H), 2.53 (d, JZ3.0 Hz, 1H), 7.36–7.51 (m,
12H), 7.56–7.62 (m,4H), 7.63–7.69 (m, 4H); 13C NMR
(CDCl3) d K4.41, K4.11, 11.70, 11.76, 18.12, 20.31, 23.60,
26.03, 27.78, 30.88, 33.21, 33.36, 120.33, 120.79, 128.07,
128.11, 128.14, 130.07, 130.12, 130.15, 132.65, 132.84,
133.39, 133.52, 134.50, 134.55. Found: C, 77.87; H, 8.08%.
Calcd for C19H23NSi: C, 77.76; H, 7.90%.
1
JZ6.9 Hz, 6H), 1.06–1.24 (m, 8H), 1.44–1.60 (m, 4H), 3.32
(d, JZ7.5 Hz, 2H), 4.88–4.98 (m, 2H), 5.75 (ddt, JZ9.3,
16.5, 7.5 Hz, 1H), 7.30–7.38 (m, 6H), 7.60–7.66 (m, 4H);
13C NMR (CDCl3) d K3.21, 13.83, 23.56, 26.64, 29.14,
35.75, 40.74, 116.69, 127.59, 128.78, 135.53, 136.21,
137.63. Found: C, 82.13; H, 9.72%. Calcd for C25H36Si:
C, 82.35; H, 9.95%. HRMS (m/z) Found: 364.2571. Calcd
for C25H36Si: 364.2586.
4.2.22. (Methyldiphenylsilyl)diphenylmethane (14b).
RfZ0.59 (hexane/ethyl acetateZ10/1); colorless oil; IR
(neat) 3024, 1958, 1886, 1821, 1597, 1493, 1427, 1254,
1111, 999, 700 cmK1; 1H NMR (CDCl3) d 0.53 (s, 3H), 4.14
(s, 1H), 7.0–7.21 (m, 10H), 7.24–7.40 (m, 10H); 13C NMR
(CDCl3) d K3.58, 44.31, 125.23, 127.51, 128.06, 129.18,
129.26, 135.21, 135.62, 141.78. Found: C, 85.39; H, 6.77%.
Calcd for C26H24Si: C, 85.66; H, 6.64%.
4.2.26. 2-(Methyldiphenylsilyl)propanenitrile (17c). RfZ
0.31 (hexane/ethyl acetateZ10/1); colorless oil; IR (neat)
1
3072, 2224, 1429, 1261, 1114, 794, 731, 700 cmK1; H
NMR (CDCl3) d 0.78 (s, 3H), 1.33 (d, JZ7.5 Hz, 3H), 2.38
(q, JZ7.5 Hz, 1H), 7.40–7.52 (m, 6H), 7.59–7.69 (m, 4H);
13C NMR (CDCl3) d K6.11, 10.62, 12.49, 122.82, 128.19,
128.22, 130.31, 132.11, 132.36, 134.70. Found: C, 76.19; H,
6.90%. Calcd for C16H17NSi: C, 76.44; H, 6.82%.
4.2.23. 1-(Methyldiphenylsilyl)-1,1-diphenyl-3-butene
(15b). RfZ0.67 (hexane/ethyl acetateZ10/1); colorless
oil; IR (neat) 3053, 2957, 1599, 1493, 1427, 1254, 1105,
912, 791, 700 cmK1; 1H NMR (CDCl3) d 0.46 (s, 3H), 3.24
(d, JZ6.6 Hz, 2H), 4.89 (dd, JZ2.1, 10.5 Hz, 1H), 4.95 (dd,
JZ2.1, 17.1 Hz, 1H), 5.58 (ddt, JZ10.5, 17.1, 6.6 Hz, 1H),
7.11–7.23 (m, 10H), 7.23–7.28 (m, 4H), 7.28–7.41 (m, 6H);
13C NMR (CDCl3) d K3.12, 40.63, 45.66, 117.11, 125.22,
127.39, 127.45, 127.51, 128.05, 128.98, 129.17, 129.25,
129.93, 134.87, 135.20, 135.85, 135.94, 141.77, 143.42.
HRMS (m/z) Found: 404.1954. Calcd for C29H28Si:
404.1960.
4.2.27. 2-Butyl-2-(methyldiphenylsilyl)-pent-4-enenitrile
(19a). RfZ0.41 (hexane/ethylacetateZ10/1); colorless oil;
IR (neat) 2936, 2214, 1962, 1890, 1827, 1639, 1429, 1259,
1113, 922, 793, 729 cmK1; 1H NMR (CDCl3) d 0.81 (s, 3H),
0.80 (t, JZ7.2 Hz, 3H), 1.13–1.30 (m, 2H), 1.30–1.50 (m,
2H), 1.50–1.72 (m, 2H), 2.29 (dd, JZ7.2, 14.1 Hz, 1H),
2.48 (dd, JZ7.2, 14.1 Hz, 1H), 5.02 (d, JZ16.8 Hz, 1H),
5.08 (d, JZ9.9 Hz, 1H), 5.82 (ddt, JZ9.9, 16.8, 7.2 Hz,
1H), 7.38–7.49 (m, 6H), 7.70–7.76 (m, 4H); 13C NMR
(CDCl3) d K4.96, 13.82, 22.92, 27.39, 28.50, 32.71, 38.03,
118.74, 123.94, 128.03, 130.07, 132.50, 133.42, 134.61,
135.15, 135.19. Found: C, 79.34; H, 8.35%. Calcd for
C22H27NSi: C, 79.22; H, 8.16%.
4.2.24. General procedure for the preparation of
2-(methyldiphenylsilyl)hexanenitrile (17a). n-BuLi
(0.31 mL, 1.6 M solution in hexane, 0.50 mmol) was
added to a solution of Ph2MeSiCHCl2 (8, 141 mg,
0.50 mmol) in THF (5 mL) dropwise at K78 8C, and the
mixture was stirred for 30 min. Then nBu2CuLi$LiCN in
THF, which was prepared from n-BuLi (0.78 mL, 1.6 M
solution in THF, 1.25 mmol) and CuCN$2LiCl (0.55 mL,
1.0 M solution in THF, 0.55 mmol) at 0 8C, was added to the
resulting solution at K78 8C. After stirring for 5 min, the
mixture was allowed to warm gradually to 0 8C. And after
stirring the mixture for 1 h at 0 8C, the reaction was
quenched with dilute aqueous HCl (20 mL). The mixture
was extracted with ethyl acetate (10 mL !3), and the
organic layers were dried over anhydrous Na2SO4 and
concentrated in vacuo. Purification by silica gel column
chromatography provided 2-(methyldiphenylsilyl)hexane-
nitrile (17a, 116 mg, 0.39 mmol) in 79% yield as colorless
oil: RfZ0.38 (hexane/ethyl acetateZ10/1); IR (neat) 3072,
4.2.28. 2-Methyl-2-(methyldiphenylsilyl)hexanenitrile
(19b). RfZ0.48 (hexane/ethyl acetateZ5/1); colorless oil;
IR (neat) 2936, 2214, 1429, 1259, 1113, 793, 729, 700 cmK1
;
1H NMR (CDCl3) d 0.76 (s, 3H), 0.86 (t, JZ7.2 Hz, 3H),
1.33 (s, 3H), 1.19–1.36 (m, 3H), 1.42–1.54 (m, 2H), 1.68–
1.81 (m, 1H), 7.38–7.49 (m, 6H), 7.70–7.76 (m, 4H); 13C
NMR (CDCl3) d K6.27, 13.98, 19.28, 22.12, 22.83, 27.36,
34.08, 125.36, 128.03, 130.09, 132.11, 132.14, 135.22,
135.24. Found: C, 77.82; H, 8.22%. Calcd for C20H25NSi:
C, 78.12; H, 8.19%.
4.2.29. 2-Acetyl-2-(methyldiphenylsilyl)hexanenitrile
(19c). RfZ0.52 (hexane/ethyl acetateZ5/1); colorless oil;
IR (neat) 2930, 2205, 1632, 1429, 1286, 1121, 797, 738,
1
698 cmK1; H NMR (CDCl3) d 0.79 (s, 3H), 0.89 (t, JZ
7.2 Hz, 3H), 1.24–1.38 (m, 3H), 1.39–1.51 (m, 2H), 2.02 (s,
3H), 2.21 (t, JZ7.5 Hz, 2H), 7.40–7.47 (m, 6H), 7.55–7.61
(m, 4H); 13C NMR (CDCl3) d K1.49, 13.90, 18.92, 22.07,
2932, 2860, 2222, 1429, 1258, 1115, 793, 729, 700 cmK1
;

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J. Kondo et al. / Tetrahedron 61 (2005) 3361–3369
22.23, 26.55, 30.26, 120.65, 128.11, 130.21, 130.50, 133.91,
134.17, 134.62, 162.85. HRMS (m/z) Found: 335.1702.
Calcd for C21H25NOSi: 335.1705.
0.50 mmol) was added to a solution of Ph2MeSiCHCl2 (8,
141 mg, 0.50 mmol) in THF (5 mL) dropwise at K78 8C,
and the mixture was stirred for 30 min. Then n-BuCu in
THF, which was prepared with n-BuLi (0.34 mL, 1.6 M
solution in THF, 0.55 mmol) and CuI$LiI (0.55 mL, 1.0 M
solution in THF, 0.55 mmol) at K78 8C, was added to the
resultant solution at K78 8C. After stirring for 10 min., and
addition of PhMgBr (0.75 mL, 1.0 M solution in THF,
0.75 mmmol), the mixture was allowed to warm gradually
to K10 8C. And then the reaction was quenched with
diluted aqueous HCl (20 mL). The mixture was extracted
with ethyl acetate (10 mL!3), and the organic layers were
dried over anhydrous Na2SO4 and concentrated in vacuo.
Purification by silica gel column chromatography provided
1-(methyldiphenylsilyl)-1-phenylpentane (21, 93 mg,
0.27 mmol) in 54% yield as colorless oil: RfZ0.72
(hexane/ethyl acetateZ10/1); IR (neat) 2957, 1956, 1882,
4.2.30. 2-Benzoyl-2-(methyldiphenylsilyl)hexanenitrile
(19d). RfZ0.41 (hexane/ethyl acetateZ5/1); colorless oil;
IR (neat) 2959, 2206, 1746, 1429, 1258, 1115, 795,
1
698 cmK1; H NMR (CDCl3) d 0.40 (s, 3H), 0.88 (t, JZ
7.2 Hz, 3H), 1.23–1.36 (m, 2H), 1.38–1.51 (m, 2H), 2.29
(dd, JZ7.5, 8.1 Hz, 2H), 7.32–7.38 (m, 6H), 7.43–7.50 (m,
4H); 13C NMR (CDCl3) d K2.06, 13.91, 22.32, 27.80,
30.18, 97.32, 120.08. HRMS (m/z) Found: 397.1860. Calcd
for C26H27NOSi: 397.1862.
4.2.31. (Z)-2-Butyl-3-phenyl-acrylonitrile (determined
by NOESY) (19e). RfZ0.54 (hexane/ethyl acetateZ
10/1); colorless oil; IR (neat) 2959, 2208, 1730, 1448,
926, 750, 692 cmK1; 1H NMR (CDCl3) d 0.96 (t, JZ7.2 Hz,
3H), 1.33–1.47 (m, 2H), 1.65 (quint, JZ7.8 Hz, 2H), 2.41 (t,
JZ7.8 Hz, 2H), 6.93 (s, 1H), 7.34–7.46 (m, 3H), 7.68–7.78
(m, 2H); 13C NMR (CDCl3) d 13.85, 21.92, 30.41, 36.04,
111.54, 118.75, 128.41, 128.66, 129.69, 133.72, 143.09.
Found: C, 84.06; H, 8.20%. Calcd for C13H15N: C,
84.28; H, 8.16%. NOE (1H difference spectrum,
300 MHz, CDCl3) irradiation of d 2.41 (CH2)—enhance-
ment of signals at d 6.93 (CH, 1.6%); irradiation of d 6.93
(CH)—enhancement of signals at d 2.41 (CH2, 0.9%), d
7.68–7.78 (Ph, 0.7%)
1
1818, 1599, 1427, 1252, 1111, 789, 700 cmK1; H NMR
(CDCl3) d 0.42 (s, 3H), 0.77 (t, JZ6.6 Hz, 3H), 1.06–1.34
(m, 4H), 1.76–1.87 (m, 2H), 2.65 (dd, JZ5.1, 10.5 Hz, 1H),
6.86–6.92 (m, 2H), 7.04–7.19 (m, 4H), 7.24–7.49 (m, 6H),
7.50–7.58 (m, 3H); 13C NMR (CDCl3) d K5.22, 14.02,
22.45, 29.78, 31.43, 35.02, 124.48, 127.06, 127.43, 127.59,
127.78, 127.96, 128.36, 128.64, 128.91, 129.16, 134.54,
134.77, 135.16, 136.21, 142.34. HRMS (m/z) Found:
344.1963. Calcd for C24H28Si: 344.1960.
4.2.36. 4-(Methyldiphenylsilyl)-4-phenyl-1-octene (22).
RfZ0.68 (hexane/ethyl acetateZ20/1); colorless oil; IR
4.2.32. (Z)-2-Butyl-3-cyclohexyl-acrylonitrile (Z/EZ
55/45) (19f). RfZ0.62 (hexane/ethyl acetateZ10/1); color-
less oil; IR (neat) 2855, 2214, 1591, 1429, 1259, 1124, 858,
796, 698 cmK1; 1H NMR (CDCl3) d 0.91 (t, JZ7.5 Hz 3H),
1.20–1.24 (m, 4H), 1.24–1.42 (m, 4H), 1.45–1.55 (m, 2H),
1.62–1.78 (m, 6H), 2.18 (dt, JZ1.5, 6.9 Hz, 2H), 2.44–2.60
(m, 1H), 5.95 (d, JZ9.9 Hz, 1H); 13C NMR (CDCl3) d
13.80, 21.77, 25.36, 25.71, 30.23, 32.28, 33.92, 40.72,
112.34, 117.84, 152.73. HRMS (m/z) Found: 191.1677.
Calcd for C13H21N: 191.1674. NOE (1H difference
spectrum, 300 MHz, CDCl3) irradiation of d 2.18
(CH2)—enhancement of signals at d 5.95 (CH, 1.2%);
irradiation of d 5.95 (CH)—enhancement of signals at d
2.18 (CH2, 0.8%)
1
(neat) 2957, 1427, 1254, 1107, 784, 700 cmK1; H NMR
(CDCl3) d 0.59 (s, 3H), 0.81 (t, JZ7.2 Hz, 3H), 1.16–1.33
(m, 4H), 1.94–2.14 (m, 2H), 2.73–2.90 (m, 2H), 4.93 (dd,
JZ1.5, 10.2 Hz, 1H), 5.03 (dd, JZ1.5, 17.1 Hz, 1H), 5.65–
5.81 (m, 1H), 6.88–6.94 (m, 2H), 7.06–7.18 (m, 3H), 7.22–
7.31 (m, 4H), 7.32–7.42 (m, 6H); 13C NMR (CDCl3) d
K4.42, 14.12, 23.69, 25.94, 33.53, 36.34, 38.48, 116.52,
124.35, 127.25, 128.15, 128.88, 135.36, 135.58, 136.10,
143.95. HRMS (m/z) Found: 384.2258. Calcd for C27H32Si:
384.2273.
4.2.37. 3-(Methyldiphenylsilyl)-3-phenyl-heptan-2-one
(23). RfZ0.48 (hexane/ethyl acetateZ10/1); colorless oil;
IR (neat) 2957, 1659, 1429, 1217, 1119, 986, 793, 700 cmK1
;
4.2.33. (E)-2-Butyl-3-cyclohexyl-acrylonitrile (Z/EZ
55/45) (19f0). RfZ0.55 (hexane/ethyl acetateZ10/1); color-
less oil; IR (neat) 2855, 2214, 1591, 1429, 1259, 1124, 858,
797, 697 cmK1; 1H NMR (CDCl3) d 0.92 (t, JZ7.2 Hz, 3H),
1.04–1.43 (m, 8H), 1.43–1.80 (m, 8H), 2.19 (dt, JZ1.2,
7.2 Hz, 2H), 2.24–2.39 (m, 1H), 6.14 (d, JZ10.2 Hz, 1H);
13C NMR (CDCl3) d 13.87, 22.09, 25.39, 25.66, 28.39,
30.44, 31.98, 37.64, 113.12, 120.27, 152.78. HRMS
(m/z) Found: 191.1680. Calcd for C13H21N: 191.1674.
NOE (1H difference spectrum, 300 MHz, CDCl3)
irradiation of d 6.14 (CH2)—no enhancement of signals
at d 2.19 (CH2, 0.9%).
1H NMR (CDCl3) d 0.56 (s, 3H), 0.80 (t, JZ7.2 Hz, 3H),
1.13–1.37 (m, 6H), 1.99 (s, 3H), 6.84–6.90 (m, 2H), 7.13–
7.19 (m, 3H), 7.22–7.36 (m, 5H), 7.37–7.42 (m, 3H), 7.56–
7.60 (m, 2H); 13C NMR (CDCl3) d K3.49, 13.85, 23.65,
28.05, 33.46, 59.01, 125.75, 127.23, 127.37, 127.66, 128.62,
129.02, 134.78, 135.47, 135.89, 136.01, 139.61, 212.33.
HRMS (m/z) Found: 386.2071. Calcd for C26H30OSi:
386.2066.
Acknowledgements
4.2.34. 2-Oxo-hexanenitrile (19g, known compound).
Spectral data for this compound were identical with those
reported in the literature.20
This work was supported by Grants-in-Aid for Scientific
Research and COE Research from the Ministry of
Education, Culture, Sports, Science and Technology,
Government of Japan. J.K. acknowledges JSPS for financial
support.
4.2.35. Preparation of 1-(methyldiphenylsilyl)-1-phenyl-
pentane (21). n-BuLi (0.31 mL, 1.6 M solution in hexane,

J. Kondo et al. / Tetrahedron 61 (2005) 3361–3369
3369
10. Oxidation in the presence of aqueous NH4Cl provided
benzoylsilane in 55% yield and disilylphenylmethane in 16%
yield.
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