Chemo- and regioselective preparation of zinc enolate from thiol esters by palladium catalyzed cross-coupling reaction

Article abstract of DOI:10.1016/j.tet.2015.08.060

The palladium catalyzed cross-coupling reaction of thiol esters with bis(iodozincio)methane or 1,1-bis(iodozincio)ethane gave Reformatsky-type enolates. They can react with some electrophiles to give the corresponding adducts and were also trapped by silylation reagents to afford silyl enol ethers. As the method applicable to the thiol ester carrying ketone moiety, it afforded zinc enolates carrying ketone in the same molecule.

Full text of DOI:10.1016/j.tet.2015.08.060

Accepted Manuscript
Chemo- and Regioselective Preparation of Zinc Enolate from Thiol Esters by
Palladium Catalyzed Cross-coupling Reaction
Ryosuke Haraguchi, Zenichi Ikeda, Akihiro Ooguri, Sejiro Matsubara
PII:
S0040-4020(15)30014-4
10.1016/j.tet.2015.08.060
TET 27082
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 23 March 2015
Revised Date: 22 August 2015
Accepted Date: 24 August 2015
Please cite this article as: Haraguchi R, Ikeda Z, Ooguri A, Matsubara S, Chemo- and Regioselective
Preparation of Zinc Enolate from Thiol Esters by Palladium Catalyzed Cross-coupling Reaction,
Tetrahedron (2015), doi: 10.1016/j.tet.2015.08.060.
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Chemo- and Regioselective Preparation of Zinc Enolate
from Thiol Esters by Palladium Catalyzed Cross-coupling
Reaction
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info.
Ryosuke Haraguchi, Zenichi Ikeda, Akihiro Ooguri, and Sejiro Matsubara
Department of Material Chemistry, Graduate School of Engineering, Kyoto University

1
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Tetrahedron
journal homepage: www.elsevier.com
Chemo- and Regioselective Preparation of Zinc Enolate from Thiol Esters
by Palladium Catalyzed Cross-coupling Reaction
Ryosuke Haraguchi, Zenichi Ikeda, Akihiro Ooguri, and Sejiro Matsubara
Department of Material Chemistry, Graduate School of Engineering, Kyoto University, Kyoto Daigaku-Katsura, Nishikyo, Kyoto 615-8510,
Japan
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
The palladium catalyzed cross-coupling reaction of thiol esters with
bis(iodozincio)methane or 1,1-bis(iodozincio)ethane gave Reformatsky-type
enolates. They can react with some electrophiles to give the corresponding
adducts and were also trapped by silylation reagents to afford silyl enol ethers. As
the method applicable to the thiol ester carrying ketone moiety, it afforded zinc
enolates carrying ketone in the same molecule.
Available online
Keywords:
Zinc
Enolate
2009 Elsevier Ltd. All rights reserved
.
Palladium
Thioester
Silyl enol ether
———
Corresponding author. Tel.: +81-75-383-7130; fax: +81-75-383-2438; e-mail: matsubara.seijiro.2e@kyoto-u.ac.jp

2
Tetrahedron
1. Introduction
Table 1. Preparation and reaction with benzaldehyde of the
ACCEPTED MANUSCRIPT
zinc enolate from thiol ester 3aa-ad.a
Bis(iodozincio)methane (1) and 1,1-bis(iodozincio)ethane (2),
which are easily prepared from the corresponding gem-
diiodoalkane and zinc powder in the presence of Pb catalyst, have
been utilized in organic reactions.1,2 These reagetns work as a
nucleophile to carbonyl compounds as a dianion equivalent with
the function as
a
bidentate Lewis acid.
Especially,
bis(iodozincio)methane (1) has offered various specific and
characteristic molecular transformations, such as Wittig-type
methylenation reaction of easily enolizable ketones,3 nucleophilic
cyclopropanation reaction of 1,2-diketones,4 ring contraction via
1,4-addition to cyclic enones,5 and so on.6 It can also work as a
cross-coupling-partner with organic halides and their
equivalents;7 iodozinciomethylation of organic halides by a
transition-metal catalyzed cross-coupling reaction resulted in the
entry
R
5ab
90% <1%
5a’
Recovery
10%
21
1
2
3
4
Ph (3aa)
4-MeOC6H4 (3ab)
4-NO2C6H4 (3ac)
Et (3ad)
74
>99
<1
<1
<1
<1
<1
87
homologative organozinc reagent formation.8
Using this
a1 (1.2 mmol, 0.45 M in THF), 3aa-ad (1.0 mmol), and
benzaldehyde (1.5 mmol) were used. bIsolated yield.
strategy, we had tried to prepare a zinc enolate through the
coupling reaction of 1 with acylating reagents. We had already
reported syntheses of symmetrical 1,3-diketones by treatment of
acyl chloride with gem-dizinc 1 in the presence of Pd catalysis.9
The formation of the duplicated acylation of gem-dizinc 1 was
observed, regardless of the stoichiometric relationship. The high
reactivity of acyl chloride cannot ignore the existence of the
formed zinc enolate equivalent, which was quenched
immediately with the starting acyl chloride to give the
symmetrical 1,3-diketone. In order to use the formed zinc
enolate equivalent as a synthetic tool, the milder acylating
reagent, which is hard to react with the zinc enolate, should be
Various electrophiles can be applied as a substrate to the
obtained enolate, as shown in Table 2. A reaction with acyl
cyanides gave 1,3-diketones. A conjugate addition was not
observed in the reaction with (E)-MeCH=CHCOPh (entry 7).
Tolerance of functional groups in this enolate formation was also
appealed: Primary bromide (entry 11), silyl ether (entry 14), and
ester (entry 15) were intact during the reaction. Bromobenzene
(entry12) did not disturb the formation of the enolate, although it
often interacts with palladium catalyst.
used.
From this viewpoint, we chose a thiol ester, which had
been used for the ketone synthesis by a cross-coupling with
alklylzinc species.10 As a result, we can perform chemoselective
cross-coupling of gem-dizinc 1 or 2 with a thiol ester carrying
various functional group;11 the transformation gave a route to
obtain the zinc enolate carrying even ketone moiety, that had
been difficult to be prepared by the classical method.12 The
obtained zinc enolates 4 can be used as a C-nucleophile and also
as a precursor for silyl enol ethers (Scheme 1).
Table 2. Reaction of the enolate from thiol esters 3 with
various electrophiles.a
b
entry
R
Electrophile
PhCOCN
MeCOCN
PhCHO
R’ in 5
PhCO-
Yield %
1
2
PhCH2CH2- (3b)
89 (5ba)
70 (5bb)
99 (5bc)
99 (5bd)
86 (5be)
3b
MeCO-
3
3b
PhCH(OH)-
EtCH(OH)-
PhCMe(OH)-
Scheme 1. Preparation and reaction of the zinc enolate by Pd-
catalyzed zincioalkylation of a thiol ester.
4
3b
EtCHO
5
3b
PhCOMe
2. Results and Discussion
6
3b
Cyclohexanone 1-Hydroxycyclohexyl 99 (5bf)
(E)-MeCH=CHCOPh (E)-MeCH=CHCPh(OH)- 62 (5bg)
According to palladium catalyzed cross-coupling reaction of
S-ethy alkanethioate and ethylzinc iodide,10,13 we started the
cross-coupling reaction of bis(iodozincio)methane (1) and a thiol
ester14 using Pd/PPh3 catalyst. As shown in Table 1, arenethiol
esters of 5-hexenoic acid 3aa-ac were treated with
bis(iodozincio)methane (1) in the presence of the catalyst,
prepared from Pd2dba3 and triphenylphosphine, and reacted
subsequently with benzaldehyde. The electron density of the
benzene ring of thiols affected the yield. The aldol product 5a
was obtained quantitatively, starting from 4-nitrobenzenethiol
ester 3ac (entry 3). Regioisomeric aldol product 5a’, which may
be formed by an isomerization of the initially formed enolate,
was not observed. Use of the ethane thiol 3ad ester as a
substrate, which is a typical substrate for Fukuyama ketone
synthesis,9 resulted in the recovery of the starting material in this
case (entry 4).
7
3b
8
Ph (3c)
PhCOCN
PhCOCN
PhCOCN
PhCOCN
PhCOCN
PhCOCN
PhCOCN
PhCO-
PhCO-
PhCO-
PhCO-
PhCO-
PhCO-
PhCO-
80 (5c)
96 (5aa)
93 (5d)
80 (5e)
85 (5f)
84 (5g)
93 (5h)
9
CH2=CH(CH2)3- (3ac)
BrCH2(CH2)6- (3d)
11
12 4-BrC6H4CH2CH2- (3e)
13 PhO(CH2)10- (3f)
14 TBDMSO(CH2)11- (3g)
15 EtO2C(CH2)5- (3h)
a1 (1.2 mmol, 0.45 M in THF), 3 (1.0 mmol), and benzaldehyde (1.5
mmol) were used. bIsolated yield.
The preparation of the zinc enolate, which has ketone group in
the same molecule, is quite useful.15 Treatment of a thiol ester
carrying a keto group 3i with bis(iodozincio)methane (1) in the
presence of palladium catalyst gave a sluggish mixture， which

3
might be formed by a reaction of the ketone group and the
Table 4. Preparation of silyl enol ethers 6ba-be by a
ACCEPTED MANUSCRIPT
formed enolate. Mixing an electrophile, benzoyl cyanide, in
advance, however, prevented this homo-condensation. As shown
in Table 3, the results by the following procedure were shown: A
mixture of thiol esters with keto group 3i-m and benzoyl cyanide
was treated with the dizinc 1 in the presence of palladium
catalyst. These reactions gave triketones in excellent yields. The
initially formed zinc enolate reacted with benzoyl cyanide, which
is more electrophilic than ketone. It reacted with benzoyl
cyanide without transposing to the other methyl ketone moiety in
the same molecule. The formation and reaction of enolate from
thiol esters proceeded chemo- and regioselectively.
reaction of silylation reagents with enolates from thiol ester
3b.a
entry
1
RCH(ZnI)2
SiX
Yield (%)b
96 (6ba)
92 (6ba)
>99 (6ba)
32 (6bb)
92 (6bb)
89 (6bb)
93 (6bc)
34 (6bd)
34 (6be)
60 (6be)
72 (6be)
Z : E
–
CH2(ZnI)2 (1)
Me3SiCl
2
1
Me3SiCN
–
3
1
Me3SiOTf
–
Table 3. Preparation of triketone 5i-m by a reaction of
benzoyl cyanide with enolates from thiol esters carrying acyl
group 3i-m.a
4
1
t-BuMe2SiCl
t-BuMe2SiCN
t-BuMe2SiOTf
Me3SiCl
–
5
1
–
6
1
–
7
CH3CH(ZnI)2 (2)
79:21
70:30
96:4
93:7
93:7
8
2
2
2
2
PhMe2SiCl
t-BuMe2SiCl
t-BuMe2SiCN
t-BuMe2SiOTf
9
entry
R
Yield (%)b
92 (5i)
10
11
1
2
CH3CO(CH2)5– (3i)
aThiol ester (2.0 mmol), dizinc (0.45 M in THF, 3.0 mmol), Si-X (3.0
mmol), Pd2dba3 (0.02 mmol) and phosphine (0.84 mmol) were used.
bYields were determined by 1H NMR using bromoform as an internal
standard. The product was also isolated by bulb-to-bulb distillation in
entries 1–3, 7 and by short silica gel column chromatography in
entries 4–6, 8–11.
CH3CO(CH2)8– (3j)
72 (5j)
3
4-CH3CO-C6H4-(CH2)2– (3k)
CH3COCH(CH3)CH2– (3l)
CH3COCH2CH(CH3)– (3m)
83 (5k)
94 (5l)
4
5c
79 (5m)
a1 (1.5 mmol, 0.45 M in THF), 3 (1.0 mmol), and benzoyl cyanide
(0.5 mmol) were used. bIsolated yield. cPd2dba3 (2.0 mol%) and P(2-
furyl)3 (8.4 mol%) were used.
Table 5. Preparation of silyl enol ethers 6 by a reaction of
silylation reagents with enolates from various thiol esters 3.a
To broaden the scope of this method, the formed zinc enolates
were transformed into the silyl enol ethers. The silyl enol ethers
have been important reagents especially for cross-aldol reactions,
but the selective preparation of those compounds are still
needed.16 For example, it is not so easy to realize the
regioselective preparation from an internal ketone, such as 3-
hexanone. When we can trap the zinc enolates prepared from
thiol ester and gem-dizinc 1 or 2, it is possible to construct the
silyl enol ether of methyl- and ethyl ketones carrying functional
groups regio- and chemoselectively.
entry
R’
gem-dizinc
SiX
6 (%)b
94 (6aa)
70 (6ca)
79 (6da)
76 (6ea)
79 (6fa)
96 (6ga)
66 (6ab)
67 (6eb)
60 (6hb)
58 (6nb)
63 (6oa)
59 (6pa)
Z : E
1
2
CH2=CH(CH2)3- (3ac)
Ph (3c)
1
1
1
1
1
1
Me3SiCl
–
Me3SiCl
Me3SiCl
Me3SiCl
Me3SiCl
Me3SiCl
–
–
3
BrCH2(CH2)6- (3d)
4-BrC6H4CH2CH2- (3e)
PhO(CH2)10- (3f)
EtO2C(CH2)5- (3h)
CH2=CH(CH2)3- (3ac)
4-BrC6H4CH2CH2- (3e)
EtO2C(CH2)5- (3h)
CH3CH2CH2- (3n)
3-Furanyl (3o)
As
shown
in
Table
4,
S-(4-nitrophenyl)
3-
4
–
phenylpropanethioate (3b) was treated with gem-dizinc 1 or 2 in
the presence of palladium catalyst and the mixture were treated
with various silylation reagents. In this preparation of silyl enol
5
–
6
–
ether, the palladium catalyst prepared from Pd
2
dba and tris(2-
3
7
2
2
2
2
1
1
t-BuMe2SiOTf
t-BuMe2SiOTf
t-BuMe2SiOTf
t-BuMe2SiOTf
Me3SiCl
90:10
93:7
93:7
90:10
–
furyl)phosphine gave the good yields. Trimethylsilyl triflate gave
the best yield among the used trimethysilylation reagents (entries
1-3). The reactions of 1,1-bis(iodozincio)ethane (2) gave the
corresponding silyl enol ethers 6 as a mixture of E/Z-iomers. Use
of tert-butyldimethylsilylation gave the sterically less hindered Z-
enolate more diastereoselectively compare to trimethylsilation or
dimethylphenylsilation (entries 7-11).
8
9
10
11
12
3-Thienyl (3p)
Me3SiCl
–
aThiol ester (2.0 mmol), dizinc (0.45 M in THF, 3.0 mmol), Si-X (3.0
mmol), Pd2dba3 (0.02 mmol) and phosphine (0.84 mmol) were used.
bYields were determined by 1H NMR using bromoform as an internal
standard. The product was also isolated by bulb-to-bulb distillation in
entries 1–6, 12,13 and by short silica gel column chromatography in
entries 8–11.

4
Tetrahedron
As shown in Table 5, various thiol esters were examined for
Kieselgel 60 F254 (0.25 mm) Plates. Visualization was
ACCEPTED MANUSCRIPT
the preparation of silyl enol ethers. Thiol esters carrying primary
bromide (entry 3), aryl bromide (entries 4, 9), and ester (runs 6,
10) were transformed into the corresponding silyl enol ethers in
good yields. When 1,1-bis(iodozincio)ethane was used, the
produced silyl enol ethers had Z-configuration selectively.17
Especially, the transformation shown in entry 11 gave (Z)-tert-
butyl(hex-2-en-3-yloxy)dimethylsilane, which is hard to prepare
selectively from the corresponding ketone, 3-hexanone.18
accomplished with UV light (254 nm) and an aqueous vanillin
solution followed by heating. Flash column chromatography was
carried out using Kanto Chemical silica gel (spherical, 40–100
ꢀm). Unless otherwise noted, commercially available reagents
were used without purification. Tetrahydrofuran, Dehydrated
stabilizer free ―Super― was purchased from Kanto Chemical
Co., stored under argon, and used as it is. Zinc powder, which
does not contain lead (electrolytic zinc), was purchased from
Aldrich (>98% purity on label, <10um). Zinc powder, which
contains 0.04-0.07 mol% Pb originally (distilled zinc), was
purchased from Wako Pure Chemical Industries (>98% purity).2a
Zinc powder was used after washing with 10% HCl according to
the reported procedure.19
As shown in Table 6, treatment of a mixture of the thiol ester
carrying keto group and chlorotrimethylsilane with
bis(iodozincio)methane in the palladium catalyst gave the
corresponding silyl enol ether carrying acyl group in the same
molecule. In entries 3 and 4, two possible kinetic enolates from
3-methylhexane-2,5-dione 6k,l were prepared selectively. The
classical deprotonation method from 3-methylhexane-2,5-dione
cannot yield selectively.
3.2. Experimental Procedure and Characterization Data for
Substrates.
Preparation of bis(iodozincio)methane (1)3
A mixture of zinc powder (150 mmol), diiodomethane (1.0
mmol), and PbCl2 (0.005 mmol) in THF (5.0 mL) was sonicated
for 1 h in an ultrasonic cleaner bath under Ar. When the distilled
zinc was used instead of the electrolytic zinc, it was not
necessary to add PbCl2. Diiodomethane (50 mmol) in THF (45
mL) was added dropwise to the mixture over 30 min at 0 °C with
vigorous stirring. The mixture was then stirred for 4 h at 25 °C.
After the stirring was stopped, the reaction vessel was allowed to
stand undisturbed for several hours. Excess zinc was separated
by sedimentation. 1H NMR spectra of the obtained supernatant
showed a broad singlet at –1.2 ppm at 0 °C, which corresponded
to the methylene proton of 1. The supernatant was used in
further reactions as a solution of 1 in THF (0.4–0.5 M). The
Table 6. Preparation of silyl enol ether having acyl group in
the same molecule 6. a
entry
R
6b
1
2
3
4
5
CH3CO(CH2)5– (3i)
82 %(6i)
97 (6j)
58 (6k)
62 (6l)
65 (6q)
4-CH3CO-C6H4-(CH2)2– (3j)
CH3COCH(CH3)CH2– (3k)
CH3COCH2CH(CH3)– (3l)
CH3CO(CH2)4– (3q)
1
concentration of 1 was estimated by H NMR analysis using
2,2,3,3-tetramethylbutane
as
an
internal
standard.
Bis(iodozincio)methane in THF can be kept for at least a month
in a sealed reaction vessel.
Preparation of 1,1-bis(iodozincio)ethane (2)5b
A mixture of zinc powder (150 mmol), 1,1-diiodoethane (1.0
mmol), and PbCl2 (0.005 mmol) in THF (5.0 mL) was sonicated
for 1 h in an ultrasonic cleaner bath under Ar. Zinc When the
distilled zinc was used instead of the electrolytic zinc, it was not
necessary to add PbCl2. Both of pure zinc and pyrometallurgy
zinc are commercially available. To the mixture, 1,1-diiodoethane
(50 mmol) in THF (45 mL) was added dropwise over 30 min at 0
°C with vigorous stirring. The mixture was stirred for 4 h at 25
°C. After the stirring was stopped, the reaction vessel was
allowed to stand undisturbed for several hours. Excess zinc was
separated by sedimentation. 1H NMR (300 MHz, 20°C) δ –0.08
(q, J = 7.8 Hz, 1H), 1.45 (d, J = 7.8 Hz, 3H). 1H NMR spectra of
the obtained supernatant showed a quartet at –0.08 ppm at 0 °C,
which corresponded to the methyne proton of 2. The supernatant
was used for the further reaction as a solution of 2 in THF (0.1–
0.5 M). The concentration of 2 was estimated by 1H NMR
analysis using 2,2,3,3-tetramethylbutane as an internal standard.
1.1-bis(iodozincio)ethane in THF can be kept unchanged at least
for two days in a sealed reaction vessel.
a1 (1.5 mmol, 0.45 M in THF), 3 (1.0 mmol), and benzoyl
cyanide (0.5 mmol) were used. bIsolated yield.
.
3. Experimental
3.1. General
Nuclear magnetic resonance spectra were taken on Varian
UNITY INOVA 500 (1H, 500 MHz; 13C, 125.7 MHz)
1
spectrometer using tetramethylsilane for H NMR as an internal
standard (δ = 0 ppm), CDCl3 for 13C NMR as an internal standard
General procedure for the preparation and reaction of zinc
enolate from thiol ester (Preparation of 5)
1
(δ = 77.0 ppm). H NMR data are reported as follows: chemical
shift, multiplicity (s = singlet, d = doublet, t = triplet, q = quartet,
br = broad, m = multiplet), coupling constants (Hz), and
integration. High-resolution mass spectra were obtained with a
Thermo Fisher SCIENTIFIC EXACTIVE (ESI, APCI). Infrared
(IR) spectra were determined on a SHIMADZU FTIR-8200PC
spectrometer. Melting points were determined using a YANAKO
MP-500D. TLC analyses were performed by means of Merck
To a solution of Pd2dba3 (0.005 mmol, 4.6 mg) in THF (0.8
mL), triphenylphosphine (0.021 mmol, 5.5 mg) was added at 25
°C. The mixture was stirred for 10 min. To a solution, p-
nitrobenzene thiol ester of 5-hexenoic acid (3ac, 1.0 mmol, 0.25
g) in THF (1.0 ml) and bis(iodozincio)methane in THF (1, 0.45
M, 1.2 mmol, 2.7 mL) were added subsequently at 0 °C. The

5
resulting mixture was stirred for 5 min at the same temperature.
A solution of electrophile (1.5 mmol) in THF (1.0 mL) was added
at 0 °C. The whole was stirred for 5 min at the same
temperature. Saturated aqueous solution of ammonium chloride
(1.0 mL) was added to the reaction mixture. The mixture was
extracted with ether. The combined organic layers were washed
with sat.NaHCO3aq and brine, and dried over anhydrous sodium
sulfate. After a short silica-gel column chromatography using
hexane/ethyl acetate as an eluent, 5 was isolated.
1339.6, 1110.1, 1030.0, 982.8, 745.5, 697.3, 668.4 cm–1.
ACCEPTED MANUSCRIPT
HRMS (ESI) Calcd for C13H19O2: [M+H]+, 207.1380. Found: m/z
207.1378.
5-Hydroxy-1,5-diphenylhexan-3-one (5be): CAS RN [925421-
43-8].
1H NMR (CDCl3) δ 7.41−7.40 (m, 2H), 7.35−7.31 (m, 2H),
7.27−7.23 (m, 3H), 7.20−7.17 (m, 1H), 7.07−7.06 (m, 2H), 3.16
(d, J = 16.5 Hz, 1H), 2.80 (d, J = 16.5. Hz, 1H), 2.81−2.67 (m,
3H), 2.62−2.55 (m, 1H), 1.51 (s, 3H). 13C NMR (CDCl3) δ
211.8, 147.1, 140.4, 128.5, 128.3, 128.2, 126.7, 126.1, 124.3,
73.3, 53.4, 46.0, 30.6, 29.0.
1-Hydroxy-1-phenyloct-7-en-3-one (5a).
1H NMR (CDCl3) δ 7.25 (m, 4H), 7.18 (m, 1H), 5.65 (ddt, J =
17.0, 10.5, 7.0 Hz, 1H), 5.06 (dt, J = 9.0, 3.0 Hz, 1H), 4.90 (m,
2H), 2.76 (dd, J = 17.0, 9.0 Hz, 1H), 2.68 (dd, J = 17.0, 3.0 Hz,
1H), 2.35 (t, J = 7.5 Hz, 2H), 1.96 (m, 2H), 1.60 (quint, J = 7.5
Hz, 2H). 13C NMR (CDCl3) δ 211.3, 142.7, 137.7, 128.5, 127.6,
125.6, 115.4, 69.9, 51.1, 42.7, 32.9, 22.4. TLC: Rf 0.40
(hexane/EtOAc = 3:1). IR (KBr) 3417.0, 3073.7, 3031.3, 2931.9,
1707.1, 1640.5, 1517.1, 1452.5, 1405.2, 1371.5, 1338.7, 1089.8,
1062.8, 1001.1, 913.3, 760.0, 700.2 cm–1. HRMS (ESI) Calcd for
C14H18O2Na: [M+Na]+, 241.1199. Found: m/z 241.1194
1-(1-Hydroxycyclohexyl)-4-phenylbutan-2-one (5bf).
1H NMR (CDCl3) δ 7.30−7.26 (m, 2H), 7.21−7.17 (m, 3H), 3.55
(bs, 1H), 2.89 (t, J = 7.5 Hz, 2H), 2.76 (d, J = 7.5. Hz, 2H), 2.56
(s, 2H), 1.70−1.60 (m, 4H), 1.55−1.49 (m, 1H), 1.42−1.31 (m,
4H), 1.29−1.21 (m, 1H). 13C NMR (CDCl3) δ 212.2, 140.6,
128.5, 128.3, 126.2, 70.7, 52.3, 46.2, 37.5, 29.3, 25.6, 21.9.
TLC: Rf 0.47 (hexane/EtOAc = 3:1). IR (neat) 3491.3, 3027.4,
2931.0, 2857.7, 1701.3, 1496.8, 1453.4, 1405.2, 1363.7, 1312.6,
1267.3, 1168.9, 1095.6, 969.3, 745.5, 699.2 cm–1. HRMS (ESI)
Calcd for C16H23O2: [M+H]+, 247.1693. Found: m/z 247.1690.
1-Phenyloct-7-ene-1,3-dione (5aa): CAS RN [131223-44-4].
1H NMR (CDCl3) δ 7.90−7.87 (m, 2H), 7.54−7.51 (m, 1H),
7.47−7.43 (m, 2H), 6.18 (s, 1H), 5.82 (ddt, J = 17.0, 10.5, 6.5 Hz,
1H), 5.06 (dd, J = 17.0, 2.0 Hz, 1H), 5.01 (dd, J = 10.5, 2.0 Hz,
1H), 2.45 (t, J = 8.0. Hz, 2H), 2.14 (dt, J = 8.0, 6.5 Hz, 2H), 1.85-
1.75 (m, 2H). 13C NMR (CDCl3) δ 196.6, 183.4, 137.8, 134.0,
132.2, 128.6, 127.0, 115.4, 96.2, 38.4, 33.1, 24.8
(E)-5-Hydroxy-1,5-diphenyloct-6-en-3-one (5bg).
1H NMR (CDCl3) δ 7.40−7.38 (m, 2H), 7.34−7.31 (m, 2H),
7.28−7.22 (m, 3H), 7.20−7.17 (m, 1H), 7.10−7.08 (m, 2H), 5.69
(dq, J = 15.0, 1.5 Hz, 1H), 5.57 (ddq, J = 15.0, 6.5, 1.5 Hz, 1H),
4.76 (bs, 1H), 3.09 (d, J = 16.5. Hz, 1H), 2.95 (d, J = 16.5. Hz,
1H), 2.86−2.71 (m, 3H), 2.68−2.61 (m, 1H), 1.69 (ddd, J = 6.0,
1.5, 1.0 Hz, 3H). 13C NMR (CDCl3) δ 211.5, 145.3, 140.5, 135.9,
128.5, 128.2, 128.2, 126.9, 126.2, 125.0, 124.6, 75.3, 52.2, 46.1,
29.0, 17.7. Mp. 59.5–60.2 °C. TLC: Rf 0.40 (hexane/EtOAc =
10:1). IR (KBr) 3473.0, 2837.4, 1681.0, 1595.2, 1576.9, 1507.4,
1474.6, 1450.5, 1363.7, 1339.6, 1175.7, 1107.2, 1079.2, 979.9,
854.5, 840.0, 758.1, 737.8, 700.2, 690.6 cm–1. HRMS (ESI)
Calcd for C20H23O2: [M+H]+, 295.1693. Found: m/z 295.1691.
1,5-Diphenylpentane-1,3-dione (5ba): CAS RN [71298-03-8].
1H NMR (CDCl3) δ 7.86−7.85 (m, 2H), 7.54−7.51 (m, 1H),
7.46−7.43 (m, 2H), 7.32−7.29 (m, 2H), 7.24−7.21 (m, 3H), 6.14
(s, 1H), 3.02 (t, J = 8.0 Hz, 2H), 2.76 (t, J = 8.0 Hz, 2H). 13C
NMR (CDCl3) δ 195.8, 183.1, 140.7, 134.8, 132.3, 128.6, 128.5,
128.3, 127.0, 126.2, 96.3, 41.0, 31.6.
6-Phenylhexane-2,4-dione (5bb): CAS RN [52393-50-7].
1,3-Diphenylpropane-1,3-dione (5c): CAS RN [120-46-7].
1H NMR (CDCl3) δ 7.31−7.27 (m, 2H), 7.22−7.18 (m, 3H), 5.48
(s, 0.84H), 3.56 (s, 0.32H), 2.95−2.90 (m, 2H), 2.86−2.83 (m,
0.32H), 2.60 (t, J = 7.5 Hz, 1.68H), 2.20 (s, 0.48H), 2.04 (s,
2.52H). 13C NMR (CDCl3) δ 203.2, 202.0, 193.2, 191.0, 140.7,
140.5, 128.53, 128.47, 128.30, 128.26, 126.23, 126.19, 100.0,
58.0, 45.2, 40.0, 31.4, 30.9, 29.4, 24.8.
1H NMR (CDCl3) δ 8.01−7.99 (m, 4H), 7.58−7.55 (m, 2H),
7.52−7.48 (m, 4H), 6.87 (s, 1H). 13C NMR (CDCl3) δ 185.8,
135.5, 132.5, 128.7, 127.2, 93.1.
10-Bromo-1-phenyldecane-1,3-dione (5d).
1H NMR (CDCl3) δ 7.90−7.87 (m, 2H), 7.54−7.51 (m, 1H),
7.47−7.43 (m, 2H), 6.17 (s, 1H), 3.41 (t, J = 7.0 Hz, 2H), 2.43 (t,
J = 7.5 Hz, 2H), 1.86 (tt, J = 7.0, 6.5 Hz, 2H), 1.69 (tt, J = 7.5,
6.5 Hz, 2H), 1.48−1.35 (m, 6H). 13C NMR (CDCl3) δ 196.9,
183.4, 135.0, 132.2, 128.6, 127.0, 96.1, 39.2, 33.9, 32.7, 29.0,
28.5, 28.0, 25.7. TLC: Rf 0.70 (hexane/EtOAc = 10:1). IR (KBr)
2920.4, 2852.8, 1737.0, 1559.5, 1494.9, 1457.3, 1404.2, 1366.6,
1303.0, 1279.8, 1258.6, 1217.1, 1143.8, 1078.3, 929.7, 766.7,
691.5 cm–1. HRMS (ESI) Calcd for C16H22BrO2: [M+H]+,
325.0798. Found: m/z 325.0787.
1-Hydroxy-1,5-diphenylpentan-3-one (5bc): CAS RN [62731-45-
7].
1H NMR (CDCl3) δ 7.34−7.33 (m, 4H), 7.30−7.27 (m, 3H),
7.22−7.19 (m, 1H), 7.18−7.16 (m, 2H), 5.16 (dd, J = 9.5, 3.0 Hz,
1H), 2.92 (t, J = 7.5 Hz, 2H), 2.85 (dd, J = 17.5, 9.5 Hz, 1H),
2.77 (t, J = 7.5 Hz, 2H), 2.76 (dd, J = 17.5, 3.0 Hz, 1H). 13C
NMR (CDCl3) δ 210.3, 142.7, 140.6, 128.9, 128.5, 128.3, 127.7,
126.2, 125.6, 69.9, 51.3, 45.1, 29.4.
5-Hydroxy-1-phenylheptan-3-one (5bd).
1H NMR (CDCl3) δ 7.30−7.27 (m, 2H), 7.21−7.20 (m, 1H),
7.19−7.17 (m, 2H), 3.98−3.93 (m, 1H), 2.91 (t, J = 7.5 Hz, 2H),
2.77 (t, J = 7.5 Hz, 2H), 2.58 (dd, J = 17.5, 3.0 Hz, 1H), 2.49 (dd,
J = 17.5, 9.0 Hz, 1H), 1.55−1.38 (m, 2H), 0.93 (t, J = 7.5 Hz,
3H). 13C NMR (CDCl3) δ 211.2, 140.7, 128.5, 128.2, 126.2,
68.9, 48.8, 45.0, 29.5, 29.3, 9.8. TLC: Rf 0.30 (hexane/EtOAc =
3:1). IR (neat) 3467.2, 3026.4, 2964.7, 2918.4, 2878.9, 2850.0,
2308.9, 1710.9, 1700.3, 1654.0, 1559.5, 1540.2, 1507.4, 1457.3,
5-(4-Bromophenyl)-1-phenylpentane-1,3-dione (5e).
1H NMR (CDCl3) δ 7.86−7.84 (m, 2H), 7.54−7.51 (m, 1H),
7.47−7.43 (m, 2H), 7.43−7.34 (m, 2H), 7.12−7.10 (m, 2H), 6.12
(s, 1H), 2.97 (t, J = 7.5 Hz, 2H), 2.73 (t, J = 7.5 Hz, 2H). 13C
NMR (CDCl3) δ 195.5, 183.0, 139.6, 134.6, 132.4, 131.6, 130.1,
128.6, 127.0, 120.0, 96.4, 40.7, 30.9. Mp. 51.5–52.0 °C. TLC:
Rf 0.64 (hexane/EtOAc = 10:1). IR (KBr) 3059.2, 2930.0,
1599.1, 1533.5, 1488.2, 1298.2, 1227.7, 1102.4, 1073.4, 1000.1,

6
Tetrahedron
925.9, 821.7, 755.2, 680.9 cm–1. HRMS (ESI) Calcd for
J = 7.5 Hz, 2H), 2.14 (s, 3H), 1.70 (tt, J = 7.5, 7.5 Hz, 2H), 1.62
ACCEPTED MANUSCRIPT
C17H16BrO2: [M+H]+, 331.0328. Found: m/z 331.0355.
(tt, J = 7.5, 7.5 Hz, 2H), 1.40−1.34 (m, 2H). 13C NMR (CDCl3) δ
209.0, 196.7, 183.4, 134.9, 132.3, 128.6, 127.0, 96.1, 43.4, 39.0,
29.9, 28.7, 25.5, 23.4. Mp. 57.5–58.2 °C. TLC: Rf 0.33
(hexane/EtOAc = 3:1). IR (KBr) 2937.7, 2866.3, 1705.2, 1614.5,
1598.1, 1575.9, 1462.1, 1411.0, 1360.8, 1345.4, 1295.3, 1261.5,
1144.8, 1088.9, 1069.6, 947.1, 774.5, 695.4 cm–1. HRMS (ESI)
Calcd for C16H21O3: [M+H]+, 261.1485. Found: m/z 261.1482.
13-Phenoxy-1-phenyltridecane-1,3-dione (5f).
1H NMR (CDCl3) δ 7.89−7.88 (m, 2H), 7.53−7.50 (m, 1H),
7.46−7.43 (m, 2H), 7.29−7.25 (m, 2H), 6.94−6.89 (m, 3H), 6.17
(s, 1H), 3.94 (t, J = 6.5 Hz, 2H), 2.42 (t, J = 7.5 Hz, 2H), 1.77 (tt,
J = 6.5, 6.5 Hz, 2H), 1.68 (tt, J = 7.5, 7.5 Hz, 2H), 1.48−1.27 (m,
12H). 13C NMR (CDCl3) δ 197.0, 183.4, 159.0, 135.0, 132.2,
129.3, 128.5, 126.9, 120.4, 114.4, 96.0, 67.8, 39.2, 29.5, 29.3,
29.3, 29.2, 29.2, 26.0, 25.8. Mp. 70.5–71.0 °C. TLC: Rf 0.63
(hexane/EtOAc = 10:1). IR (KBr) 2932.9, 2916.5, 2850.9,
1602.9, 1575.9, 1497.8, 1473.7, 1337.7, 1303.0, 1274.0, 1251.9,
1172.8, 1146.7, 1080.2, 1012.7, 879.6, 749.4, 691.5 cm–1.
HRMS (ESI) Calcd for C25H33O3: [M+H]+, 381.2424. Found: m/z
381.2416.
1-Phenyltridecane-1,3,12-trione (5j).
1H NMR (CDCl3) δ 7.89−7.87 (m, 2H), 7.53−7.50 (m, 1H),
7.47−7.43 (m, 2H), 6.17 (s, 1H), 2.42 (t, J = 7.5 Hz, 2H), 2.41 (t,
J = 7.5 Hz, 2H), 2.13 (s, 3H), 1.67 (tt, J = 7.5, 7.5 Hz, 2H), 1.56
(tt, J = 7.5, 7.5 Hz, 2H), 1.37−1.26 (m, 8H). 13C NMR (CDCl3) δ
209.4, 197.0, 183.4, 135.0, 132.2, 128.6, 127.0, 96.1, 43.7, 39.2,
29.9, 29.2, 29.2, 29.2, 29.1, 25.8, 23.8. Mp. 34.8–35.5 °C. TLC:
Rf 0.60 (hexane/EtOAc = 3:1). IR (KBr) 3098.8, 2930.0, 2852.8,
2549.0, 1705.2, 1616.4, 1595.2, 1576.9, 1507.4, 1499.7, 1410.0,
1341.6, 1101.4, 950.0, 929.7, 854.5, 839.1, 740.7, 692.5 cm–1.
HRMS (ESI) Calcd for C19H27O3: [M+H]+, 303.1955. Found: m/z
303.1947.
14-((t-Butyldimethylsilyl)oxy)-1-phenyltetradecane-1,3-dione
(5g).
1H NMR (CDCl3) δ 7.89−7.87 (m, 2H), 7.54−7.50 (m, 1H),
7.47−7.44 (m, 2H), 6.17 (s, 1H), 3.59 (t, J = 6.5 Hz, 2H), 2.42 (t,
J = 7.5 Hz, 2H), 1.68 (tt, J = 7.5, 7.5 Hz, 2H), 1.52−1.47 (m, 2H),
1.38−1.25 (m, 14H), 0.89 (s, 9H), 0.04 (s, 6H). 13C NMR
(CDCl3) δ 197.0, 183.5, 135.1, 132.2, 128.6, 127.0, 96.1, 63.2,
39.3, 32.9, 29.6, 29.5, 29.5, 29.4, 29.4, 29.3, 26.0, 25.9, 25.8,
18.4, −5.3. TLC: Rf 0.57 (hexane/EtOAc = 10:1). IR (neat)
3065.0, 2927.1, 2854.8, 2648.4, 1723.5, 1603.9, 1575.9, 1463.1,
1360.8, 1300.1, 1255.7, 1182.4, 1097.5, 1028.1, 1005.9, 954.8,
835.2, 774.5, 694.4 cm–1. HRMS (ESI) Calcd for C26H45O3Si:
[M+H]+, 433.3132. Found: m/z 433.3127.
5-(4-Acetylphenyl)-1-phenylpentane-1,3-dione (5k).
1H NMR (CDCl3) δ 7.91−7.89 (m, 2H), 7.86−7.83 (m, 1H),
7.54−7.51 (m, 2H), 7.47−7.43 (m, 2H), 7.33−7.32 (m, 2H), 6.13
(s, 1H), 3.08 (t, J = 7.5 Hz, 2H), 2.78 (t, J = 7.5 Hz, 2H), 2.58 (s,
3H). 13C NMR (CDCl3) δ 197.8, 195.4, 182.9, 146.4, 135.4,
134.6, 132.4, 128.7, 128.6, 128.6, 127.0, 96.3, 40.4, 31.4, 26.6.
Mp. 50.9–51.5 °C. TLC: Rf 0.53 (hexane/EtOAc = 2:1). IR
(KBr) 3065.0, 2918.4, 1683.9, 1602.9, 1570.1, 1494.9, 1460.2,
1406.2, 1360.8, 1302.0, 1267.3, 1177.6, 1142.9, 1108.2, 1079.2,
1033.9, 1013.6, 957.7, 868.0, 824.6, 779.3, 697.3 cm–1. HRMS
(ESI) Calcd for C19H19O3: [M+H]+, 295.1329. Found: m/z
295.1322.
Ethyl 7,9-dioxo-9-phenylnonanoate (5h).
1H NMR (CDCl3) δ 7.90−7.87 (m, 2H), 7.54−7.50 (m, 1H),
7.47−7.43 (m, 2H), 6.17 (s, 1H), 4.12 (q, J = 7.0 Hz, 2H), 2.43 (t,
J = 7.5 Hz, 2H), 2.31 (t, J = 7.5 Hz, 2H), 1.74−1.64 (m, 4H),
1.44−1.38 (m, 2H), 1.25 (t, J = 7.0 Hz, 3H). 13C NMR (CDCl3) δ
196.6, 183.4, 173.6, 134.9, 132.2, 128.6, 127.0, 96.1, 62.2, 39.0,
34.1, 28.7, 25.4, 24.6, 14.2. TLC: Rf 0.40 (hexane/EtOAc = 5:1).
IR (neat) 3082.4, 2918.4, 2850.9, 2369.7, 1735.0, 1599.1, 1570.1,
1459.2, 1412.9, 1369.5, 1340.6, 1291.4, 1260.5, 1181.5, 1087.9,
1028.1, 853.5, 767.7, 697.3 cm–1. HRMS (ESI) Calcd for
C17H23O4: [M+H]+, 291.1591. Found: m/z 291.1586.
5-Methyl-1-phenylheptane-1,3,6-trione (5l).
1H NMR (CDCl3) δ 7.86−7.85 (m, 2H), 7.53−7.50 (m, 1H),
7.46−7.43 (m, 2H), 6.17 (s, 1H), 3.13 (ddq, J = 8.0, 7.0, 6.0 Hz,
1H), 2.94 (dd, J = 16.0, 8.0 Hz, 1H), 2.44 (dd, J = 16.0, 6.0 Hz,
1H), 2.25 (s, 3H), 1.18 (d, J = 7.0 Hz, 3H). 13C NMR (CDCl3) δ
211.1, 196.6, 181.0, 134.3, 132.3, 128.6, 126.9, 96.7, 42.8, 42.3,
28.5, 16.6. Mp. 35.1–36.0 °C. TLC: Rf 0.60 (hexane/EtOAc =
2:1). IR (KBr) 3403.5, 3095.9, 2973.4, 2877.9, 1712.9, 1598.1,
1560.5, 1462.1, 1427.4, 1396.5, 1371.5, 1336.7, 1281.8, 1213.3,
1174.7, 1150.6, 1082.1, 1068.6, 951.9, 932.6, 834.4, 770.6, 692.5
cm–1. HRMS (ESI) Calcd for C14H17O3: [M+H]+, 233.1172.
Found: m/z 233.1171.
Preparation of 1-phenyldecane-1,3,9-trione (5i).
To a solution of Pd2dba3 (0.01 mmol, 9.2 mg) in THF (1.0
mL), triphenylphosphine (0.042 mmol, 11.3 mg) was added at 25
°C. The mixture was stirred for 10 min. To a solution, benzoyl
cyanide (0.5 mmol, 0.066 g) in THF (0.5 mL) and p-nitrobenzene
thiol ester of 7-oxooctanoic acid (1.0 mmol, 0.29 g) in THF (1.0
mL), bis(iodozincio)methane in THF (1, 0.45 M, 1.5 mmol, 3.3
mL) was added dropwise at 0 °C. The resulting mixture was
stirred for 1 h at the same temperature. Saturated aqueous
solution of ammonium chloride (2.0 mL) was added to the
reaction mixture. The mixture was extracted with ether. The
combined organic layers were washed with sat.NaHCO3aq and
brine, and dried over anhydrous sodium sulfate. After a short
silica-gel column chromatography using hexane/ethyl acetate as
an eluent, the title compound 3 was obtained in 92% yield.
Triketone, 5k-m were obtained by the same procedure. P(2-
furyl)3 was used instead of PPh3 in the preparation of 5m.
4-Methyl-1-phenylheptane-1,3,6-trione (5m).
1H NMR (CDCl3) δ 7.88−7.86 (m, 2H), 7.53−7.50 (m, 1H),
7.46−7.43 (m, 2H), 6.23 (s, 1H), 3.08 (ddq, J = 7.5, 7.5, 5.0 Hz,
1H), 3.02 (dd, J = 17.5, 7.5 Hz, 1H), 2.51 (dd, J = 17.5, 5.0 Hz,
1H), 2.18 (s, 3H), 1.22 (d, J = 7.5 Hz, 3H). 13C NMR (CDCl3) δ
206.9, 201.2, 181.3, 134.4, 132.2, 128.6, 126.9, 95.4, 46.5, 38.7,
30.3, 17.9. Mp. 30.5–31.0 °C. TLC: Rf 0.63 (hexane/EtOAc =
2:1). IR (KBr) 2968.6, 1781.3, 1710.9, 1612.6, 1576.9, 1516.1,
1464.0, 1392.7, 1373.4, 1339.6, 1275.0, 1153.5, 1122.6, 1067.7,
942.3, 853.5, 802.8, 781.2, 693.4 cm–1. HRMS (ESI) Calcd for
C14H17O3: [M+H]+, 233.1172. Found: m/z 233.1169.
1H NMR (CDCl3) δ 7.89−7.87 (m, 2H), 7.54−7.51 (m, 1H),
7.47−7.43 (m, 2H), 6.17 (s, 1H), 2.45 (t, J = 7.5 Hz, 2H), 2.30 (t,
Preparation of 6 except 6i-l,o:

7
Tri(2-furyl)phosphine (0.082 mmol) in THF (1.0 mL)
was added at 25 °C to a solution of Pd2dba3 (0.02 mmol)
in THF (1.0 mL) and the mixture was stirred for 15 min.
gem-dizinc in THF (1 or 2, 0.45M, 3.0mmol) and p-
nitrobenzene thiol ester of carboxylic acid (3, 2.0 mmol)
in THF (1.0 ml) were added subsequently at 0 °C. The
resulting mixture was stirred for 15 min at the same
temperature. Silylation reagent (3.0 mmol) was added to
the reaction mixture. The resulting mixture was stirred
for 6 h at 25 °C. Et3N (1.0 mL) was added to the mixture.
A saturated aqueous solution of sodium bicarbonate (5.0
mL) was added to the reaction mixture and the mixture
extracted with diethyl ether. The combined organic
layers were washed with sat. aq. NaHCO3 and brine,
and dried over anhydrous sodium sulfate. After rapid
column chromatography on silica gel with hexane–ethyl
acetate as the eluent, 6 was obtained.
Hz, 2H), 4.65 (q, J = 7.0 Hz, 0.30H), 4.59 (q, J = 6.5 Hz,
ACCEPTED MANUSCRIPT
0.70H), 2.79 (t, J = 8.0 Hz, 0.60H), 2.71 (t, J = 8.0 Hz, 1.40H),
2.37 (t, J = 8.0 Hz, 0.60H), 2.23 (t, J = 8.0 Hz, 1.40H), 1.54 (dt, J
= 6.5, 1.0 Hz, 2.10H), 1.42 (d, J = 6.5 Hz, 0.90H), 0.51 (s,
4.20H), 0.47 (s, 1.80H). 13C NMR (for Z isomer, CDCl3) δ 150.4,
141.9, 137.9, 133.3, 129.8, 128.3, 128.2, 127.9, 125.7, 103.1,
38.7, 33.8, 10.8, −0.9. IR (neat) 3068.9, 2958.0, 2917.5, 2861.5,
1678.1, 1496.8, 1454.4, 1428.4, 1381.1, 1327.1, 1252.8, 1191.1,
1118.8, 1041.6, 998.2, 898.9, 832.3, 787.0, 743.6, 698.3 cm–1.
HRMS (EI) Calcd for C19H24OSi: [M]+, 296.1596. Found: m/z
296.1588.
t-Butyldimethyl((5-phenylpent-2-en-3-yl)oxy)silane (Z/E mixture,
93/7) (6be).
1H NMR (CDCl3) δ 7.29 (t, J = 7.5 Hz, 2H), 7.19 (m, 3H), 4.64
(q, J = 7.0 Hz, 0.07H), 4.56 (q, J = 7.0 Hz, 0.93H), 2.80 (t, J =
8.5 Hz, 2H), 2.31 (t, J = 8.5 Hz, 2H), 1.55 (d, J = 7.0 Hz, 2.79H),
1.45 (d, J = 7.0 Hz, 0.21H), 1.01 (s, 8.37H), 0.97 (s, 0.63H), 0.17
(s, 5.58H), 0.09 (s, 0.42H). 13C NMR (for Z isomer, CDCl3) δ
150.5, 142.0, 128.3, 128.3, 125.8, 102.4, 38.8, 33.9, 25.8, 10.8,
1.0, −4.0. IR (neat) 3027.4, 2958.9, 2921.3, 2862.5, 2360.0,
2342.7, 1676.2, 1604.8, 1496.8, 1454.4, 1382.1, 1331.9, 1220.0,
1192.1, 1105.3, 1041.6, 993.4, 912.4, 844.9, 751.3, 698.3 cm–1.
HRMS (EI) Calcd for C17H28OSi: [M]+, 276.1909. Found: m/z
276.1906.
(Hepta-1,6-dien-2-yloxy)trimethylsilane (6aa).
1H NMR (CDCl3) δ 5.81 (ddt, J = 17.0, 10.0, 2.0 Hz, 1H), 5.01
(dd, J = 17.0, 2.0 Hz, 1H), 4.96 (dd, J = 10.0, 2.0 Hz, 1H), 4.05
(s, 2H), 2.06 (dt, J = 7.5, 6.5 Hz, 2H), 2.02 (dd, J = 7.5, 7.5 Hz,
2H), 1.55 (tt, J = 7.5, 7.5 Hz, 2H), 0.20 (s, 9H). 13C NMR
(CDCl3) δ 159.4, 138.9, 114.8, 90.2, 36.1, 33.3, 26.3, 0.3. TLC:
Rf 0.30 (hexane/EtOAc = 1:1). IR (neat) 3077.6, 2957.0, 2863.5,
1638.6, 1458.3, 1437.0, 1251.9, 1225.8, 1172.8, 1100.4, 1035.8,
958.7, 911.4, 841.0, 752.3, 694.4 cm–1. HRMS (ESI) Calcd for
C10H20OSi: [M+K]+, 223.0915. Found: m/z 223.0943.
Trimethyl((1-phenylvinyl)oxy)silane (6ca) : CAS RN [13735-81-
4].
1H NMR (CDCl3) δ 7.62−7.52 (m, 2H), 7.25−7.35 (m, 3H), 4.92
(d, J = 2.0 Hz, 1H), 4.43 (d, J = 2.0 Hz, 1H), 0.27 (s, 9H). 13C
NMR (CDCl3) δ 155.9, 137.7, 128.4, 128.2, 125.4, 91.3, 0.3.
Trimethyl((4-phenylbut-1-en-2-yl)oxy)silane (6ba) : CAS RN
[59417-89-9].
1H NMR (CDCl3) δ 7.30−7.26 (m, 2H), 7.21−7.17 (m, 3H), 4.07
(d, J = 0.5 Hz, 1H), 4.06 (d, J = 0.5 Hz, 1H), 2.79 (dd, J = 8.0,
8.0 Hz, 2H), 2.34 (dd, J = 8.0, 8.0 Hz, 2H), 0.22 (s, 9H). 13C
NMR (CDCl3) δ 158.9, 142.1, 128.6, 128.5, 125.9, 90.4, 38.5,
33.6, 0.3.
((9-Bromonon-1-en-2-yl)oxy)trimethylsilane (6da).
1H NMR (CDCl3) δ 4.03 (bs, 2H), 3.40 (t, J = 7.0 Hz, 2H), 2.00
(dd, J = 7.5, 7.5 Hz, 2H), 1.85 (ddt, J = 7.5, 7.5, 7.0 Hz, 2H),
1.48−1.38 (m, 4H), 1.36−1.26 (m, 4H), 0.20 (s, 9H). 13C NMR
(CDCl3) δ 159.7, 90.0, 36.6, 34.1, 33.0, 29.0, 28.8, 28.3, 26.9,
0.3. IR (neat) 2960.9, 2932.9, 2857.7, 2360.0, 2331.1, 1654.0,
1635.7, 1628.0, 1459.2, 1433.2, 1251.9, 1216.2, 1117.8, 1016.5,
844.9, 752.3, 666.4 cm–1. HRMS (EI) Calcd for C12H25BrOSi:
[M]+, 292.0858. Found: m/z 292.0851.
t-Butyldimethyl((4-phenylbut-1-en-2-yl)oxy)silane (6bb)
.
1H NMR (CDCl3) δ 7.30 (t, J = 7.5 Hz, 2H), 7.21 (m, 2H), 4.07
(bs, 2H), 2.83 (t, J = 8.0 Hz, 2H), 2.36 (t, J = 8.0 Hz, 2H), 0.98
(s, 9H), 0.20 (s, 6H). 13C NMR (CDCl3) δ 158.8, 141.9, 128.4,
128.3, 125.8, 90.1, 38.6, 3[3.4, 25.7, 18.1, −4.7. IR (neat)
3112.3, 3028.4, 2957.0, 2930.0, 2858.6, 2361.9, 1654.0, 1635.7,
1496.8, 1472.7, 1361.8, 1292.4, 1257.6, 1221.0, 1160.2, 1149.6,
1077.3, 1031.0, 1005.0, 838.1, 810.1, 780.2, 697.3 cm–1. HRMS
(EI) Calcd for C14H22OSi: [M]+, 234.1440. Found: m/z 234.1431.
((4-(4-Bromophenyl)but-1-en-2-yl)oxy)trimethylsilane (6ea).
1H NMR (CDCl3) δ 7.39 (d, J = 8.5 Hz, 2H), 7.06 (d, J = 8.5 Hz,
2H), 4.04 (d, J = 1.0 Hz, 1H), 4.02 (d, J = 1.0 Hz, 1H), 2.73 (dd,
J = 8.0, 6.5 Hz, 2H), 2.30 (dd, J = 8.0, 6.5 Hz, 2H), 0.21 (s, 9H).
13C NMR (CDCl3) δ 158.4, 141.0, 131.5, 130.4, 119.7, 90.6, 38.3,
33.0, 0.3. IR (neat) 2958.9, 1654.0, 1631.9, 1617.4, 1488.2,
1349.3, 1340.6, 1292.4, 1252.8, 1219.1, 1152.5, 1100.4, 1072.5,
1031.0, 1011.7, 921.1, 846.8, 753.2, 684.8 cm–1. HRMS (EI)
Calcd for C13H18OBrSi: [M−H]+, 297.0313. Found: m/z
297.0312.
Trimethyl((5-phenylpent-2-en-3-yl)oxy)silane (Z/E mixture,
79/21) (6bc).
1H NMR (CDCl3) δ 7.29 (t, J = 7.5 Hz, 2H), 7.20 (m, 3H), 4.65
(q, J = 7.0 Hz, 0.21H), 4.59 (q, J = 7.0 Hz, 0.79H), 2.79 (t, J =
8.0 Hz, 2H), 2.37 (t, J = 8.0 Hz, 0.42H), 2.30 (t, J = 8.0 Hz,
1.58H), 1.53 (dt, J = 7.0, 1.0 Hz, 2.37H), 1.46 (d, J = 7.0 Hz,
0.63H), 0.23 (s, 7.11H), 0.20 (s, 1.89H). 13C NMR (for Z isomer,
CDCl3) δ 150.4, 142.0, 128.3, 128.3, 125.8, 102.7, 38.8, 33.7,
10.7, 0.6. IR (neat) 2929.0, 1676.2, 1454.4, 1331.9, 1252.8,
1192.1, 1105.3, 1092.7, 1041.6, 995.3, 912.4, 898.9, 843.9,
750.3, 698.3 cm–1. HRMS (EI) Calcd for C16H26OSi: [M]+,
262.1753. Found: m/z 262.1748.
Trimethyl((12-phenoxydodec-1-en-2-yl)oxy)silane (6fa).
1H NMR (CDCl3) δ 7.30−7.25 (m, 2H), 6.95−6.85 (m, 3H), 4.04
(bs, 2H), 3.95 (t, J = 6.5 Hz, 2H), 2.00 (dd, J = 7.0, 7.0 Hz, 2H),
1.78 (ddt, J = 7.0, 7.0, 6.5 Hz, 2H), 1.50−1.40 (m, 4H),
1.40−1.26 (m, 10H), 0.21 (s, 9H). 13C NMR (CDCl3) δ 159.8,
159.3, 129.6, 120.1, 114.7, 89.9, 68.0, 36.7, 29.7, 29.7, 29.6,
29.6, 29.5, 29.3, 27.0, 26.3, 0.3. IR (neat) 3109.4, 3040.9, 2927.1,
2854.8, 1632.8, 1602.0, 1497.8, 1468.9, 1387.8, 1301.0, 1251.9,
1171.8, 1107.2, 1014.6, 846.8, 814.0, 752.3, 690.6 cm–1. HRMS
(EI) Calcd for C21H36OSi: [M]+, 348.2485. Found: m/z 348.2480.
Dimethyl(phenyl)((5-phenylpent-2-en-3-yl)oxy)silane (6bd) (Z/E
mixture, 70/30)
.
1H NMR (CDCl3) δ 7.68 (dd, J = 4.0, 2.0 Hz, 2H), 7.43 (m, 3H),
Ethyl 7-((trimethylsilyl)oxy)oct-7-enoate (6ga).
7.24 (t, J = 7.5 Hz, 2H), 7.18 (t, J = 7.5 Hz, 1H), 7.03 (d, J = 7.5

8
Tetrahedron
1H NMR (CDCl ) δ 4.12 (q, J = 7.5 Hz, 2H), 4.03 (bs, 2H),
1H NMR (CDCl ) δ 7.49 (bs, 1H), 7.33 (t, J = 2.0 Hz, 1H), 6.45
ACCEPTED MANUSCRIP3T
3
2.29 (t, J = 7.5 Hz, 2H), 2.00 (t, J = 7.5 Hz, 2H), 1.63 (tt, J = 7.5,
7.5 Hz, 2H), 1.47 (tt, J = 7.5, 7.5 Hz, 2H), 1.33 (tt, J = 7.5, 7.5
Hz, 2H), 1.25 (t, J = 7.5 Hz, 3H), 0.20 (s, 9H). 13C NMR
(CDCl3) δ 159.5, 90.1, 60.4, 36.5, 34.5, 28.8, 26.7, 25.0, 14.6,
0.3. IR (neat) 2938.7, 2863.5, 2360.0, 2331.1, 1739.9, 1735.0,
1252.8, 1181.5, 1139.0, 1087.9, 1014.6, 916.2, 845.8, 752.3,
685.7, 673.2 cm–1. HRMS (ESI) Calcd for C13H27O3Si: [M+H]+,
259.1724. Found: m/z 259.1722.
(dd, J = 1.0, 1.0 Hz, 1H), 4.56 (d, J = 1.5 Hz, 1H), 4.30 (d, J =
1.5 Hz, 1H), 0.25 (s, 9H). 13C NMR (CDCl3) δ 150.0, 143.2,
140.2, 125.3, 108.0, 90.8, 0.1. IR (neat) 2959.9, 2917.5, 2904.0,
2850.0, 2377.4, 1319.4, 1253.8, 1168.0, 1100.4, 1070.5, 1009.8,
956.7, 843.9, 795.7 cm–1. HRMS (EI) Calcd for C9H14O2Si:
[M]+, 182.0763. Found: m/z 182.0762.
Trimethyl((1-(thiophen-3-yl)vinyl)oxy)silane (6pa): CAS RN
[101306-15-4]
t-Butyldimethyl(octa-2,7-dien-3-yloxy)silane (Z/E mixture, 90/10)
(6ab).
1H NMR (CDCl3) δ 7.36 (dd, J = 3.0, 1.0 Hz, 1H), 7.24 (dd, J =
5.0, 3.0 Hz, 1H), 7.20 (dd, J = 5.0, 1.5 Hz, 1H), 4.76 (d, J = 1.5
Hz, 1H), 4.37 (d, J = 1.5 Hz, 1H), 0.27 (s, 9H). 13C NMR
(CDCl3) δ 152.1, 140.3, 125.6, 125.2, 121.8, 90.8, 0.1. HRMS
(ESI) Calcd for C9H14OSSi: [M+H]+, 198.0535. Found: m/z
198.0533.
1H NMR (CDCl3) δ 5.80 (ddt, J = 17.0, 10.5, 6.5 Hz, 1H), 5.01
(dd, J = 17.0, 2.0 Hz, 1H), 4.95 (dd, J = 17.0, 2.0 Hz, 1H), 4.63
(q, J = 7.0 Hz, 0.10H), 4.49 (q, J = 7.0 Hz, 0.90H), 2.05 (dt, J =
7.5, 6.5 Hz, 2H), 2.00 (dd, J = 7.5, 7.5 Hz, 2H), 1.55 (tt, J = 7.5,
7.5 Hz, 2H), 1.52 (d, J = 7.0 Hz, 3H), 0.95 (s, 8.10H), 0.94 (s,
0.90H), 0.12 (s, 6H). 13C NMR (CDCl3) δ 151.1, 138.9, 114.7,
102.1, 36.2, 33.4, 26.5, 26.0, 18.5, 11.0, -3.8. IR (neat) 3067.0,
2956.0, 2858.6, 1642.5, 1472.7, 1383.0, 1361.8, 1330.9, 1254.8,
1193.0, 1045.5, 910.4, 837.1, 777.4 cm–1. HRMS (EI) Calcd for
C14H28OSi: [M]+, 240.1909. Found: m/z 240.1906.
Preparation of 6i-l,q:
To a solution of Pd2dba3 (0.02 mmol) in THF (1.0 mL), tri(2-
furyl)phosphine (0.082 mmol) in THF (1.0 mL) was added at 25
°C. The mixture was stirred for 10 min. To this solution,
chlorotrimethylsilane (3.0 mmol, 0.4 mL) and p-nitrobenzene
thiol ester of keto acid (3i-l,o 2.0 mmol) in THF (2.0 mL) were
((5-(4-Bromophenyl)pent-2-en-3-yl)oxy)(t-butyl)dimethylsilane
(Z/E mixture, 93/7) (6eb).
added subsequently at
0
°C and
a
solution of
bis(iodozincio)methane in THF (1, 0.45 M, 3.0 mmol) was added
dropwise at 0 °C. The resulting mixture was stirred for 5 min at
the same temperature and then stirred for an additional 15 min at
25 °C. Et3N (1.0 mL) was added to the mixture. A saturated
aqueous solution of sodium bicarbonate (5.0 mL) was added to
the reaction mixture and the mixture extracted with diethyl ether.
The combined organic layers were washed with brine, and dried
over anhydrous sodium sulfate. The product was isolated by
bulb-to-bulb distillation.
1H NMR (CDCl3) δ 7.38 (d, J = 8.5 Hz, 2H), 7.04 (d, J = 8.5 Hz,
2H), 4.61 (q, J = 7.0 Hz, 0.07H), 4.48 (q, J = 6.5 Hz, 0.93H),
2.77−2.67 (m, 2H), 2.32 (dd, J = 8.0, 7.5 Hz, 1.86H), 2.25 (dd, J
= 8.0, 7.5 Hz, 0.14H), 1.51 (d, J = 6.5 Hz, 2.79H), 1.41 (d, J =
6.5 Hz, 0.21H), 0.98 (s, 8.37H), 0.94 (s, 0.63H), 0.14 (s, 5.58H),
0.13 (s, 0.42H). 13C NMR (for Z isomer, CDCl3) δ 150.1, 141.1,
131.5, 130.3, 119.7, 103.0, 38.7, 33.3, 26.0, 18.5, 11.0, −3.7. IR
(neat) 3024.5, 2955.1, 2930.0, 2857.7, 1489.1, 1471.8, 1404.2,
1388.8, 1331.9, 1253.8, 1193.0, 1100.4, 1043.5, 1012.7, 904.7,
838.1, 806.3, 778.3, 697.3 cm–1. HRMS (EI) Calcd for
C17H26BrOSi: [M−H]+, 353.0936. Found: m/z 353.0935.
8-((Trimethylsilyl)oxy)non-8-en-2-one (6i).
1H NMR (CDCl3) δ 4.03 (bs, 2H), 2.42 (t, J = 7.5 Hz, 2H), 2.13
(s, 3H), 2.00 (t, J = 7.5 Hz, 2H), 1.58 (tt, J = 7.5, 7.5 Hz, 2H),
1.46 (tt, J = 7.5, 7.5 Hz, 2H), 1.30 (tt, J = 7.5, 7.5 Hz, 2H), 0.20
(s, 9H). 13C NMR (CDCl3) δ 209.3, 159.2, 89.9, 47.7, 36.2, 29.9,
28.5, 26.5, 23.6, 0.1. IR (neat) 3111.3, 2940.6, 2860.6, 2361.9,
2321.4, 1718.7, 1430.3, 1358.9, 1252.8, 1222.9, 1168.9, 1145.8,
1092.7, 1016.5, 895.0, 845.8, 755.2, 684.8 cm–1. HRMS (ESI)
Calcd for C12H25O2Si: [M+H]+, 229.1618. Found: m/z 229.1617.
Ethyl 7-((t-butyldimethylsilyl)oxy)non-7-enoate (Z/E mixture,
93/7) (6hb).
1H NMR (CDCl3) δ 4.61 (q, J = 7.0 Hz, 0.07H), 4.48 (q, J = 7.0
Hz, 0.93H), 4.12 (q, J = 7.0 Hz, 2H), 2.29 (t, J = 8.0 Hz, 2H),
1.98 (t, J = 8.0 Hz, 2H), 1.62 (tt, J = 8.0, 7.5 Hz, 2H), 1.51 (d, J =
7.0 Hz, 3H), 1.47 (tt, J = 8.0, 8.0 Hz, 2H), 1.31 (tt, J = 8.0, 7.5
Hz, 2H), 1.25 (t, J = 7.0 Hz, 3H), 0.95 (s, 9H), 0.11 (s, 6H). 13C
NMR (for Z isomer, CDCl3) δ 159.5, 151.2, 102.0, 60.4, 36.6,
34.5, 28.9, 26.9, 26.0, 25.1, 18.5, 14.4, 11.0, −3.8. IR (neat)
2951.2, 2930.0, 2858.6, 2361.9, 1739.9, 1676.2, 1601.0, 1472.7,
1465.0, 1462.1, 1330.9, 1302.0, 1252.8, 1193.0, 1181.5, 1099.5,
1036.8, 1005.9, 939.4, 894.0, 838.1, 806.3, 777.4, 692.5 cm–1.
HRMS (EI) Calcd for C17H33O3Si: [M−H]+, 313.2199. Found:
m/z 313.2191.
1-(4-(3-((Trimethylsilyl)oxy)but-3-en-1-yl)phenyl)ethan-1-one
(6j).
1H NMR (CDCl3) δ 7.88 (d, J = 8.5 Hz, 2H), 7.28 (d, J = 8.5 Hz,
2H), 4.04 (d, J = 1.0 Hz, 1H), 4.03 (d, J = 1.0 Hz, 1H), 2.84 (dd,
J = 8.0, 6.5 Hz, 2H), 2.58 (s, 3H), 2.34 (dd, J = 8.0, 6.5 Hz, 2H),
0.21 (s, 9H). 13C NMR (CDCl3) δ 198.0, 158.2, 147.9, 135.3,
128.8, 128.6, 90.6, 38.0, 33.0, 26.7, 0.3. IR (neat) 2958.9,
2931.9, 1685.9, 1635.7, 1607.7, 1430.3, 1412.9, 1338.7, 1290.4,
1268.3, 1252.8, 1221.0, 1182.4, 1154.5, 1112.0, 1032.0, 1005.9,
954.8, 923.9, 847.8, 755.2, 685.7 cm–1. HRMS (EI) Calcd for
C15H22O2Si: [M]+, 262.1389. Found: m/z 262.1388.
t-Butyl(hex-2-en-3-yloxy)dimethylsilane (Z/E mixture, 95/5)
(6nb).
1H NMR (CDCl3) δ 4.63 (q, J = 6.5 Hz, 0.05H), 4.48 (q, J = 6.5
Hz, 0.95H), 2.03 (t, J = 7.0 Hz, 0.10H), 1.96 (t, J = 7.5 Hz,
1.90H), 1.52 (d, J = 6.5 Hz, 3H), 1.47 (tq, J = 7.5, 7.5 Hz, 2H),
0.95 (s, 9H), 0.89 (t, J = 7.5 Hz, 3H), 0.12 (s, 5.70H), 0.11 (s,
0.30H). 13C NMR (for Z isomer, CDCl3) δ 151.3, 101.8, 38.9,
26.0, 20.5, 18.5, 13.9, 11.0, −3.8. IR (neat) 2958.9, 2930.0,
2859.6, 2808.5, 2360.0, 2331.1, 1672.4, 1465.0, 1253.8, 1194.0,
1110.1, 914.3, 837.1, 777.4, 665.5 cm–1. HRMS (EI) Calcd for
C12H26OSi: [M]+, 214.1753. Found: m/z 214.1752.
3-Methyl-5-((trimethylsilyl)oxy)hex-5-en-2-one (6k).
1H NMR (CDCl3) δ 4.05 (bs, 1H), 4.04 (bs, 1H), 2.74 (dd, J =
13.5, 6.5 Hz, 1H), 2.40 (dd, J = 13.5, 6.5 Hz, 1H), 2.16 (s, 3H),
2.06 (ddq, J = 13.5, 6.5, 6.5 Hz, 1H), 1.08 (d, J = 6.5 Hz, 3H),
0.20 (s, 9H). 13C NMR (CDCl3) δ 212.0, 156.5, 91.3, 44.5, 39.8,
28.3, 15.7, −0.1. IR (neat) 2963.8, 2920.4, 2360.0, 2312.8,
1714.8, 1635.7, 1576.9, 1510.3, 1457.3, 1338.7, 1287.5, 1251.9,
1091.8, 1012.7, 842.9, 742.6, 668.4 cm–1. HRMS (ESI) Calcd for
C10H20O2Si: [M+H]+, 201.1305. Found: m/z 201.1302.
((1-(Furan-3-yl)vinyl)oxy)trimethylsilane (6oa)

9
10. Tokuyama, H.; Yokoshima, S.; Yamashita, T.; Fukuyama, T.
4-Methyl-5-((trimethylsilyl)oxy)hex-5-en-2-one (6l).
ACCEPTED MANUSCRIPT
Tetrahedron Lett. 1998, 39, 3189-3192.
1H NMR (CDCl3) δ 4.06 (bs, 1H), 3.99 (bs, 1H), 2.67 (dd, J =
13.5, 6.5 Hz, 1H), 2.36 (dd, J = 13.5, 6.5 Hz, 1H), 2.16 (s, 3H),
2.07 (ddq, J = 13.5, 6.5, 6.5 Hz, 1H), 1.04 (d, J = 6.5 Hz, 3H),
0.20 (s, 9H). 13C NMR (CDCl3) δ 208.3, 162.0, 88.3, 48.5, 36.0,
30.4, 18.4, 0.0. IR (neat) 2965.7, 2917.5, 2850.0, 2598.2, 2375.4,
2310.8, 1717.7, 1539.3, 1253.8, 1010.7, 844.9, 665.5 cm–1.
HRMS (ESI) Calcd for C10H20O2Si: [M+H]+, 201.1305. Found:
m/z 201.1305.
11. Ooguri, A.; Ikeda, Z.; Matsubara, S. Chem. Commun. 2007, 45, 4761-
4763. (b) Ikeda. Z.; Hirayama, T.; Matsubara, S. Angew. Chem. Int. Ed.
2006, 45, 8200-8203.
12. (a) Lombard, M.; Trombini, C. in The Chemistry of Organozinc
Compounds (Eds.: Z. Rappoport; I. Marek), John Wiley & Sons, Ltd,
West Sussex, 2006, pp797-862. (b) Vedejes, E.; Ahmand, S.
Tetrahedron Lett. 1988, 29, 2291-2294. (c) Matsubara, S.; Tsubonia,
N.; Morizawa, Y.; Oshima, K.; Nozaki, H. Bull. Chem. Soc. Jpn. 1984,
57, 3242-3247. (d) Rieke, R. D.; Uhm, S. J. Synthesis 1975, 452-453.
(e) Rathke, M. W. Org. React. 1975, 22, 423-460.
13.
(a) Fausett, B. W.; Liebeskind L. S. J. Org. Chem. 2005, 70, 4851-
4853. (b) Srogl, J.; Liu, W.; Marshall, D.; Liebeskind, L. S. J. Am.
Chem. Soc. 1999, 121, 9449-9450. (c) Roberts, W. P.; Ghosh, I.;
Jacobi, P. A. Can. J. Chem. 2004, 82, 279-284. (d) Lengar, A.; Kappe,
C. O. Org. Lett. 2004, 6, 771-774.
7-((Trimethylsilyl)oxy)oct-7-en-2-one (6q).
1H NMR (CDCl3) δ 4.03 (bs, 2H), 2.43 (t, J = 7.5 Hz, 2H), 2.13
(s, 3H), 2.01 (t, J = 7.5 Hz, 2H), 1.58 (m, 2H), 1.45 (m, 2H), 0.19
(s, 9H). 13C NMR (CDCl3) δ 209.2, 158.9, 90.1, 43.6, 36.2, 29.9,
26.3, 23.2, 0.1. IR (neat) 2942.5, 2859.6, 1718.7, 1715.8, 1672.4,
1635.7, 1433.2, 1412.0, 1357.9, 1252.8, 1222.9, 1169.9, 1145.8,
1016.5, 846.8, 755.2, 683.8 cm–1. HRMS (EI) Calcd for
C11H22O2Si: [M]+, 214.1389. Found: m/z 214.1386.
14. Prepared from mixed anhydride and thiol; see, Neises, B.; Steglich, W.
Angew. Chem. Int. Ed. 1978, 17, 522-524
15. Alkylzinc reagent carrying carbonyl group. (a) Jones, P.; Reddy, K.C.;
Knochel, P. Tetrahedron 1998, 54, 1471. (b) Nakamura, E.; Aoki, S.;
Sekiya, K.; Oshino, H.; Kuwajima, I. J. Am. Chem. Soc. 1987, 109,
8056. (c) Tamaru, Y.; Tanigawa, H.; Yamamoto, T.; Yoshida, Z. Angew.
Chem. Int. Ed. 1989, 28, 351. (d) Lipshutz, B. H.; Wood, M. R.;
Tirano, R. J. Am. Chem. Soc. 1995, 117, 6126.
4. Conclusion
16. (a) Chan, D. G.; Winternheimer, D. J.; Merlic, C. A. Org. Lett. 2011,
13, 2778-2781. (b) Ho, C.-Y.; Ohmiya, H.; Jamison, T. F. Angew.
Chem. Int. Ed. 2008, 47, 1893. (c) Aggarwal, V. K.; Sheldon, C. G.;
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This zinciomethylation of thiol esters offers an efficient
method to give zinc enolates carrying additional ketone regio-,
chemo-, and stereoselectively. The enolates can be isolated as
the corresponding silyl enol ethers, which are important
nucleophilic reagents for organic synthesis. The preparation of
the silyl enol ether, which carries ketone moiety in the same
molecule, is one of the most useful applications of this method.
18. Braun, M. Helv. Chim. Acta 2015, 98, 1-31.
Acknowledgments
19. Fieser. L. F.; Fieser, M. Reagents for Organic Synthesis; Vol 1; Wiley:
New York, 1967, 1276.
This work was supported by Grants-in-Aid from the
Ministry of Education, Culture, Sports, Science and
Technology, Japan.
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