1-(Trimethylsilyl)vinyl MIDA Boronate: A Trifunctional C 2 Building Block

Article abstract of DOI:10.1055/s-0036-1591926

1-(Trimethylsilyl)vinyl MIDA boronate - a trifunctional C ₂ building block - is prepared in only two laboratory steps and 54% overall yield starting from readily available trimethyl(vinyl)silane. The title compound undergoes orthogonal functionalization at either of the groups present in its structure, for example, iodination at the trimethylsilyl moiety, epoxidation at the double bond, and Suzuki-Miyaura coupling at the MIDA boronate.

Full text of DOI:10.1055/s-0036-1591926

SYNTHESIS
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Georg Thieme Verlag Stuttgart · New York
2018, 50, A–E
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Synthesis
Y. M. Ivon et al.
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1
-(Trimethylsilyl)vinyl MIDA Boronate: A Trifunctional C Building
2
Block
Yevhen M. Ivona,b
Zoya V. Voitenkob
Oleksandr O. Grygorenko*a,b
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2
6-
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a
Enamine Ltd., Chervonotkatska Street 78, Kyiv 02094,
Ukraine
National Taras Shevchenko University of Kyiv,
Volodymyrska Street, 60, Kyiv 01601, Ukraine
gregor@univ.kiev.ua
b
Received: 06.12.2017
Accepted after revision: 12.01.2018
Published online: 05.02.2018
reactions has been demonstrated.26 To date, only a few α-
heteroatom-substituted MIDA boronates have been de-
scribed in the literature. In particular, bromide 1 (Figure 1)
was prepared in two steps: borylation and bromination–
DOI: 10.1055/s-0036-1591926; Art ID: ss-2017-t0790-op
Abstract 1-(Trimethylsilyl)vinyl MIDA boronate — a trifunctional C2
building block — is prepared in only two laboratory steps and 54% over-
all yield starting from readily available trimethyl(vinyl)silane. The title
compound undergoes orthogonal functionalization at either of the
groups present in its structure, for example, iodination at the trimethyl-
silyl moiety, epoxidation at the double bond, and Suzuki–Miyaura cou-
pling at the MIDA boronate.
14
elimination starting from vinyl magnesium bromide.
2
-Perfluoroalkyl-1-iodo derivatives 2 were obtained by
Ru-catalyzed photoredox reactions of ethynyl MIDA boro-
nate and perfluoroalkyl iodides.27 Silyl enol ethers 3 were
prepared by multistep synthesis via the corresponding acyl
9
boronates. Finally, α,α-diboryl derivatives 4 were synthe-
sized via diborylation of alkynyl MIDA boronates and sub-
sequent Suzuki–Miyaura reactions of intermediates 5.
Key words organosilicon compounds, organoboron compounds,
alkenes, Suzuki–Miyaura coupling, orthogonal reactions
23
R1
R2
Br
O
I
TMSO
O
Vinyl boronic acids and their derivatives are versatile
–
O
O
–
O
–
O
building blocks that are widely used in organic synthesis,
initially as the coupling partners for Suzuki–Miyaura reac-
B
B
B
O
O
O
O
O
O
N+
N+
N+
1
tions. α-Heteroatom-substituted vinyl boronic acid deriva-
2, R1 = n-CnF2n+1
3, R2 = Ph, i-Pr
1
tives are of special interest since after coupling, functional-
ized alkenes are obtained in a regioselective manner; more-
over, iterative chemoselective cross-coupling to form
+
R3
R4
O
N
O
O
–
O R3
O
B
O
O
O
O
–
–
O
O
B–
2–4
+
N
B
B
+
N
O
polysubstituted alkenes is possible.
Examples of these
–B
O O
O O
+
N
5–8
+
O
organoboron compounds include α- and β-(sulfon)amido,
N
O
9–11
12–14
α-alkoxy,
α-halogenoboronates,
α-boryl vinyl sila-
O
O
4, R3 = Alkyl, Aryl;
7
,15–20
21–23
nes
and α,α-diboryl alkenes.
Most of these com-
5
R4 = Aryl
pounds have a boronic acid ester as the boryl moiety, which
is prone to oxidation, protodeborylation and polycondensa-
tion, and therefore provides limited possibilities for chemi-
cal manipulations at other functional groups. Trifluorobo-
rates are widely recognized alternatives to boronate
Figure 1 Known α-heteroatom-substituted vinyl MIDA boronates
In this work, we describe a short and convenient syn-
thesis, as well as some reactions of 1-(trimethylsilyl)vinyl
MIDA boronate 6, a promising building block possessing
three functional groups per two main chain carbon atoms.
It should be noted that to date, several boronic acid esters of
general formula 7 have been described in the literature;
24,25
esters;
however, they have poor solubility in several
typical organic solvents, which complicates their use in
many routine transformations. On the contrary, N-methyl-
iminodiacetic acid (MIDA) boronates have good chemical
stability and solubility, and their utility for the synthesis of
complex boronic acid derivatives and subsequent coupling
they were prepared by alkylidene-type lithium carbenoid
insertion into B–Si bonds (Scheme 1).1
9,20
Compounds 7
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Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–E

B
Synthesis
Y. M. Ivon et al.
Paper
were also observed as minor by-products in the hydrobora-
tion of trimethylsilylacetylene.28 Very recently, the synthe-
sis of pinacol derivative 7a via lithiation of bromide 8 [avail-
able in one step and 67% yield starting from trimethyl-
Having in hand gram amounts of the compound 6, we
were interested in the possibility of its orthogonal func-
tionalization at any of the groups present in the molecule
(Scheme 3). It was found that:
(1) The reaction with iodine proceeded smoothly to give
the corresponding vinyl iodide 11 in 78% yield.
29
(
vinyl)silane ], followed by transmetalation with pinaco-
30
late 9, was reported on gram scale.
(
2) Both the trimethylsilyl and MIDA boronate groups
SiR1
3
Me3Si
R13Si–B
were stable toward deuterium exchange; the compound did
not react with CF COOD or CF COOD/TBAF at ambient tem-
perature.
(3) Reaction with m-chloroperbenzoic acid (MCPBA)
gave epoxide 12 quantitatively. Surprisingly, the product 12
was stable toward the action of acids (aq H SO , HClO ,
HCOOH, CF COOH) and nucleophiles (NaN /NH Cl,
EtSH/Et N, EtSH/BF ·Et O, Me CuLi and n-Bu CuLi, Me Cu-
Li/BF ·Et O, PhMgBr/CuI, and Me Al).
Li
O
–
O
B
B
3
3
Br
O
O
N+
7
, R1 = Me, Ph
H
H
6
= pinacol,
pinanediol
O
O
1
.
B Oi-Pr
2
4
4
O
O
SiMe3
Br
t-BuLi
Li
9
3
3
4
B
SiMe3 2. HCl
SiMe3
3 3 2 2 2 2
8
7a
3
2
3
Scheme 1 Synthesis of boronic acid esters 7
(4) Cyclopropanations under Simmons–Smith reaction
conditions (Et Zn/CH I or ClCH I) and with ethyl diazoace-
2
2 2
2
tate/Rh (OAc) or Pd(OAc) , as well as cross-metathesis re-
2
4
2
nd
Our approach to 6 started with a similar (but not identi-
cal) reaction sequence (Scheme 2). To install the boron
functionality, lithiation with t-BuLi was used, followed by
actions (allyltrimethylsilane, Grubbs’ 2 generation cata-
lyst, various temperatures, CH Cl , benzene or toluene as
2
2
the solvent) were unfruitful.
transmetalation with B(OMe) . It was found that the lithia-
(5) Suzuki–Miyaura coupling under slow-release condi-
tions was very efficient with either electron-rich or elec-
tron-poor aryl, hetaryl, and vinyl bromides, affording vinyl
silanes 13a–e in 64–97% yields. No desilylation was ob-
served.
3
tion should be performed in Et O as the solvent, while the
2
transmetalation proceeded smoothly only after addition of
better solvating THF. The next step — ligand interchange
from the ate-complex 10 to give MIDA boronate 6 — was
challenging, probably due to protodeborylation. It was
found that the method of Burke and co-workers, which re-
lied on slow addition of the ate-complex to a hot solution of
N-methyliminodiacetic acid in DMSO (110–160 °C), was
O
O
SiMe3
MCPBA
100%
+
N
–
B
O
O
O
14,31,32
O
beneficial.
showed that the addition should be performed at 120–
40 °C, with simultaneous removal of volatiles by distilla-
In our case, optimization of the procedure
O
I
O
SiMe3
I2
+
–
+
–
O
12
N
B
N
B
1
78%
O
O
RBr, Pd(OAc)2
SPhos, K3PO4
SiMe3
tion (see Figure S1 in the Supporting Information). In this
way, the target compound 6 was obtained in good yield
R
O
11
O
6
1
1
3a, R = Ph, 64%
3b, R = pyrid-3-yl, 85%
3
1
(
81% from 8) on 11 g scale. It should be noted that the
+
2+
counterion of the preformed ate-complex 10 (Li vs Mg )
had a strong influence on the solubility of this salt. In par-
ticular, the magnesium salt (used in some of the previous
13c, R = 4-AcC6H4, 65%
1
1
3d, R = 4-HOC6H4, 95%
3e, R = inden-2-yl, 97%
14,32
Scheme 3 Reactions of 1-(trimethylsilyl)vinyl MIDA boronate 6 (SPhos:
work
) had limited solubility in THF (used for the meta-
2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl)
lation), while the lithium salt was well soluble, which was
crucial for the addition step upon scale-up.
In conclusion, a convenient approach to 1-(trimethyl-
O
silyl)vinyl MIDA boronate 6—a small, trifunctional C build-
NH+
2
O
ing block—has been developed. It was shown that efficient
orthogonal functionalization at either of the groups present
in boronate 6 was possible. Compound 6, as well as prod-
ucts 11 and 12 are shelf-stable at room temperature for at
least six months, hence they are promising reagents for the
construction of small molecules.
O
SiMe3
Br
t-BuLi
Li
B(OMe)3
THF
O
–
O
CO H CO2–
B
2
+
–
Li+
N B
Et2O
DMSO
81%
SiMe3
SiMe3
O
SiMe3
8
10
O
6
Scheme 2 Synthesis of 1-(trimethylsilyl)vinyl MIDA boronate 6
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Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–E

C
Synthesis
Y. M. Ivon et al.
Paper
The solvents were purified according to standard procedures.33 (1-
was extracted with EtOAc (2 × 30 mL). The combined organic extracts
were dried over Na SO and evaporated. The residue was recrystal-
Bromovinyl)trimethylsilane (8) was prepared according to the litera-
2
4
29
lized from CHCl /EtOAc to give iodide 11.
ture method. All other starting materials were purchased from com-
mercial sources. Analytical TLC was performed using Polychrom SI
F254 plates. Column chromatography was performed using Kieselgel
Merck 60 (230–400 mesh) as the stationary phase. Melting points
were measured on a MPA100 OptiMelt automated melting point sys-
3
Yield: 565 mg (78%); colorless crystals; mp 183–184 °C.
1
H NMR (400 MHz, DMSO-d ): δ = 6.84 (s, 1 H), 6.56 (s, 1 H), 4.36 (d,
6
J = 17.1 Hz, 2 H), 4.07 (d, J = 17.1 Hz, 2 H), 2.89 (s, 3 H).
13C NMR (100 MHz, DMSO-d
): δ = 168.4 (C=O), 150.8 (br s, C), 137.8
1
13
6
tem. H and C NMR spectra were recorded on a Bruker 170 Avance
1
13
(CH ), 62.5 (CH ), 46.7 (CH ).
2 2 3
5
00 spectrometer [499.9 MHz ( H) and 124.9 MHz ( C)] and on a
1
11
Varian Unity Plus 400 spectrometer [400.4 MHz ( H) and 100.7 MHz
C)]. Chemical shifts are reported in ppm downfield from TMS as an
B NMR: (128 MHz, DMSO-d ): δ = 8.4.
6
1
3
(
MS (CI): m/z = 310 [M + H]+.
internal standard. Mass spectra were recorded on an Agilent 1100
LCMSD SL instrument [chemical ionization (APCI), electrospray ion-
ization (ESI)] and an Agilent 5890 Series II 5972 GCMS instrument
Anal. Calcd for C H BINO : C, 27.22; H, 2.94; N, 4.53. Found: C, 27.45;
7
9
4
H, 3.02; N, 4.67.
[
electron impact ionization (EI)]. Elemental analyses were performed
2
-(Trimethylsilyl)oxiran-2-yl MIDA Boronate 12
at the Laboratory of Organic Analysis, Department of Chemistry, Na-
tional Taras Shevchenko University of Kyiv.
MCPBA (70%, 2.24 g, 9.1 mmol) was added to a stirred solution of
MIDA boronate 6 (1.16 g, 4.55 mmol) in CH Cl (90 mL) at 0 °C, and
2
2
the resulting mixture was stirred overnight at r.t. A second portion of
MCPBA (70%, 0.60 g, 2.43 mmol) was added and the mixture was
stirred at r.t. overnight, then quenched with 10% aq Na S O (30 mL)
1
-(Trimethylsilyl)vinyl MIDA Boronate 6
All operations were carried out under an argon atmosphere. A solu-
tion of (1-bromovinyl)trimethylsilane (8) (10.0 g, 55.8 mmol) in Et O
2
2
3
2
and saturated aq NaHCO3 (20 mL). The organic layer was separated,
and the aqueous layer extracted with EtOAc (2 × 60 mL). The com-
bined organic extracts were washed with 10% aq Na S O (20 mL) and
(
110 mL) was cooled to –90 °C, after which a solution of t-BuLi in
pentane (62 mL, 1.7 M, 0.105 mol) was added dropwise at –90 to
80 °C. The resulting mixture was stirred at this temperature for 30
2
2
3
–
saturated aq NaHCO3 (20 mL), dried over Na SO and evaporated in
2
4
min. Trimethyl borate (6.85 mL, 61.4 mmol) was added at –80 °C, fol-
lowed by THF (110 mL) below –60 °C. The solution was stirred at
vacuo. The residue was triturated with CH Cl to give epoxide 12.
2
2
–60 °C for an additional 40 min and allowed to warm to r.t. over 1 h.
Yield: 1.22 g (quant.); colorless crystals; mp 137–139 °C.
At this point, the solution was transferred via cannula to a dropping
funnel connected to a second reaction vessel.
1
H NMR (500 MHz, DMSO-d ): δ = 4.31 (d, J = 17.3 Hz, 1 H), 4.13 (d, J =
6.7 Hz, 1 H), 4.06 (d, J = 17.3 Hz, 1 H), 3.85 (d, J = 17.0 Hz, 1 H), 2.95
6
1
In another three-necked flask (fitted with a short distillation column,
a thermometer and a dropping funnel with an argon inlet, see Figure
S1 in the Supporting Information), a solution of N-methyliminodia-
cetic acid (26.3 g, 0.179 mmol) in DMSO (90 mL) was heated to
(s, 3 H), 2.75 (d, J = 5.8 Hz, 1 H), 2.62 (d, J = 5.8 Hz, 1 H), 0.00 (s, 9 H).
13
C NMR (125 MHz, DMSO-d ): δ = 169.4 (C=O), 168.1 (C=O), 62.2
6
(
CH ), 62.1 (CH ), 51.5 (br s, C), 48.9 (CH ), 46.3 (CH ), –2.3 (CH ).
2 2 2 3 3
11
B NMR (128 MHz, DMSO-d ): δ = 10.4.
6
120 °C. Hexane (100 mL) was added dropwise with distillation, and
MS (CI): m/z = 272 [M + H]+.
the temperature in the flask was increased to 120–140 °C. The solu-
tion of ate complex 10 from the above-mentioned dropping funnel
was added dropwise with simultaneous distilling of the ethereal sol-
vents under vigorous stirring (the temperature in the reaction flask
should be kept above 120 °C). After the addition was complete, the
mixture was heated for an additional 20 min and then allowed to cool
Anal. Calcd for C10H18BNO Si: C, 44.30; H, 6.69; N, 5.17. Found: C,
5
44.26; H, 6.72; N, 5.46.
Suzuki–Miyaura Coupling; General Procedure
The corresponding (het)aryl bromide (2.44 mmol) or 2-bromoindene
to r.t. The mixture was diluted with H O (400 mL) and extracted with
2
(
191 mg, 0.98 mmol), MIDA boronate 6 (500 mg, 1.96 mmol), K PO4
3
EtOAc (2 × 200 mL). The combined extracts were washed with
brine/H O (1:1) (2 × 200 mL), dried over Na SO and evaporated in
(3.12 g, 14.7 mmol) and Pd(OAc)2 (22 mg, 0.1 mmol) were mixed in
2
2
4
dioxane/H O (6:1, 20 mL) under an argon atmosphere. SPhos (80 mg,
2
vacuo. The residue was recrystallized from CHCl /EtOAc to give MIDA
3
0.2 mmol) was added, and the solution was stirred at 60 °C overnight
boronate 6.
(
ca.16 h), then cooled to r.t., diluted with H O (5 mL) (for 13a–c and
2
Yield: 10.9 g (81%); colorless powder; mp 200–201 °C.
13e) or 0.5 M aq NaHSO4 to pH = 3 (for 13d), and extracted with t-
1
H NMR (400 MHz, DMSO-d ): δ = 6.14 (s, 2 H), 4.24 (d, J = 17.3 Hz, 2
BuOMe (for 13a–c), EtOAc (for 13d) or hexanes (for 13e) (2 × 30 mL).
6
H), 4.00 (d, J = 17.3 Hz, 2 H), 2.65 (s, 3 H), 0.06 (s, 9 H).
The combined organic extracts were washed with brine (20 mL),
13
dried over Na SO and evaporated in vacuo.
2 4
C NMR (125 MHz, DMSO-d ): δ = 169.1 (C=O), 139.3 (CH ), 61.8
6
2
(
1
CH ), 47.5 (CH ), –0.4 (CH ).
2
3
3
Trimethyl(1-phenylvinyl)silane (13a)
1
B NMR: (128 MHz, DMSO-d ): δ = 11.1.
6
Purified by column chromatography on silica gel using hexanes/CH Cl2
2
MS (CI): m/z = 256 [M + H]+.
(20:1) as eluent.
Anal. Calcd for C10H18BNO Si: C, 47.07; H, 7.11; N, 5.49. Found: C,
Yield: 220 mg (64%); colorless liquid [Lit.32 bp 70–72 °C (10 mmHg)].
4
47.23; H, 6.89; N, 5.65.
1
H NMR (400 MHz, CDCl ): δ = 7.33–7.16 (m, 5 H), 5.83 (d, J = 3.0 Hz, 1
3
H), 5.61 (d, J = 3.0 Hz, 1 H), 0.17 (s, 9 H).
1
-Iodovinyl MIDA Boronate 11
13
C NMR (125 MHz, CDCl ): δ = 153.7 (C), 144.9 (C), 128.3 (CH), 127.3
3
Iodine (716 mg, 2.82 mmol) was added to a stirred solution of MIDA
boronate 6 (600 mg, 2.35 mmol) in CH Cl (25 mL) in one portion. The
mixture was stirred at r.t. for 3 d and then quenched with 10% aq
Na S O (20 mL). The layers were separated and the aqueous phase
(
CH ), 126.8 (CH), 126.4 (CH), –0.74 (CH ).
2
3
2
2
+
]+, 135, 73 [Me Si]+.
MS (EI): m/z = 176 [M] , 161 [M – CH
3
3
2
2
3
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Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–E

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Synthesis
Y. M. Ivon et al.
Paper
+
+
Anal. Calcd for C11H16Si: C, 74.93; H, 9.15. Found: C, 75.10; H, 9.39.
-[1-(Trimethylsilyl)vinyl]pyridine (13b)
MS (EI): m/z = 214 [M] , 199 [M – CH ] , 183, 141, 140, 139, 115, 73
3
+
[
Me Si] .
3
3
Anal. Calcd for C14H18Si: C, 78.44; H, 8.46. Found: C, 78.75; H, 8.08.
Purified by column chromatography on silica gel using hexanes/t-
BuOMe (4:1) as eluent.
Funding Information
Yield: 295 mg (85%); colorless liquid; R = 0.35 (hexanes/t-BuOMe,
f
4
:1).
This work was supported by Enamine Ltd.
)(
1
H NMR (400 MHz, CDCl ): δ = 8.47 (d, J = 4.8 Hz, 1 H), 8.43 (s, 1 H),
3
7.47 (d, J = 7.8 Hz, 1 H), 7.22 (dd, J = 7.8 Hz, 5.0 Hz, 1 H), 5.85 (d, J = 2.5
Hz, 1 H), 5.70 (d, J = 2.5 Hz, 1 H), 0.17 (s, 9 H).
Acknowledgment
13
C NMR (125 MHz, CDCl ): δ = 150.3 (C), 147.9 (CH), 147.7 (CH),
3
The authors thank Dr. Andriy V. Tymtsunik for helpful discussions,
Andriy V. Kozitsky for NMR measurements and Prof. Andrey A. Tol-
machev for his encouragement and support.
1
40.4 (C), 134.0 (CH), 129.2 (CH ), 123.1 (CH), –1.0 (CH ).
2
3
+
+
+
MS (EI): m/z = 177 [M] , 176, 162 [M – CH ] , 136, 73 [Me Si] .
3
3
Anal. Calcd for C10H15NSi: C, 67.74; H, 8.53; N, 7.90. Found: C, 67.71;
H, 8.47; N, 7.87.
Supporting Information
1
-{4-[1-(Trimethylsilyl)vinyl]phenyl}ethanone (13c)
Supporting information for this article is available online at
https://doi.org/10.1055/s-0036-1591926.
Purified by column chromatography on silica gel using hexanes/t-
BuOMe (10:1) as eluent.
S
u
p
p
o
nrtogI
i
f
rm oaitn
S
u
p
p
ortioIgnfmr oaitn
Yield: 280 mg (65%); yellowish liquid; R = 0.50 (hexanes/t-BuOMe,
f
1
0:1).
References
1
H NMR (400 MHz, CDCl ): δ = 7.90 (d, J = 8.0 Hz, 2 H), 7.24 (d, J = 8.0
3
(1) Hall, D. G. In Boronic Acids: Preparation and Applications in
Hz, 2 H), 5.85 (d, J = 2.5 Hz, 1 H), 5.67 (d, J = 2.5 Hz, 1 H), 2.59 (s, 3 H),
Organic Synthesis, Medicine and Materials; Hall, D. G., Ed.;
Wiley-VCH: Weinheim, 2011, 1–133.
0.17 (s, 9 H).
13
C NMR (100 MHz, CDCl ): δ = 197.9 (C=O), 153.2 (C), 150.3 (C), 135.3
3
(
(
2) Woerly, E. M.; Roy, J.; Burke, M. D. Nature 2014, 6, 484.
3) Lee, S. J.; Anderson, T. M.; Burke, M. D. Angew. Chem. Int. Ed.
2010, 49, 8860.
(
C), 128.50 (CH ), 128.48 (CH), 127.0 (CH), 26.7 (CH ), –0.9 (CH ).
2
3
3
+
+
+
MS (EI): m/z = 218 [M] , 203 [M – CH ] , 177, 73 [Me Si] .
3
3
(
(
4) He, Z.; Zajdlik, A.; Yudin, A. K. Acc. Chem. Res. 2014, 47, 1029.
5) He, G.; Chen, S.; Wang, Q.; Huang, H.; Zhang, Q.; Zhang, D.;
Zhang, R.; Zhu, H. Org. Biomol. Chem. 2014, 12, 5945.
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Zhang, R.; Zhu, H. Eur. J. Org. Chem. 2013, 6979.
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853.
Anal. Calcd for C13H18OSi: C, 71.50; H, 8.31. Found: C, 71.86; H, 8.37.
-[1-(Trimethylsilyl)vinyl]phenol (13d)
4
(
(
Purified by column chromatography on silica gel using hexanes/t-
BuOMe (4:1) as eluent.
Yield: 360 mg (95%); colorless solid; mp 66–67 °C; R = 0.42 (hex-
f
anes/t-BuOMe, 4:1).
(8) St. Denis, J. D.; Zajdlik, A.; Tan, J.; Trinchera, P.; Lee, C. F.; He, Z.;
1
Adachi, S.; Yudin, A. K. J. Am. Chem. Soc. 2014, 136, 17669.
9) He, Z.; Trinchera, P.; Adachi, S.; St. Denis, J. D.; Yudin, A. K.
H NMR (500 MHz, CDCl ): δ = 7.10 (d, J = 8.7 Hz, 2 H), 6.79 (d, J = 8.7
3
(
Hz, 2 H), 5.80 (d, J = 2.9 Hz, 1 H), 5.55 (d, J = 2.9 Hz, 1 H), 4.89 (s, 1 H),
0
Angew. Chem. Int. Ed. 2012, 51, 11092.
.17 (s, 9 H).
(
10) Katz, J. D.; Lapointe, B. T.; Dinsmore, C. J. J. Org. Chem. 2009, 74,
866.
13
C NMR (125 MHz, CDCl ): δ = 154.2 (C), 152.6 (C), 137.5 (C), 128.1
3
8
(
CH), 126.4 (CH ), 115.2 (CH), –0.7 (CH ).
2
3
(
11) Percy, J. M.; Emerson, H.; Fyfe, J. W. B.; Kennedy, A. R.; Maciuk,
S.; Orr, D.; Rathouská, L.; Redmond, J. M.; Wilson, P. G. Chem.
Eur. J. 2016, 22, 12166.
+
+
+
MS (EI): m/z = 192 [M] , 177 [M – CH ] , 161, 151, 119, 91, 73 [Me Si] .
3
3
Anal. Calcd for C11H16OSi: C, 68.69; H, 8.39. Found: C, 68.95; H, 8.39.
(
(
(
(
12) Tatsuya, W.; Yuto, S.; Azusa, K.; Hideki, Y.; Koichiro, O. Bull.
Chem. Soc. Jpn. 2009, 82, 1433.
13) Xu, S.; Lee, C.-T.; Rao, H.; Negishi, E. Adv. Synth. Catal. 2011, 353,
[
1-(1H-Inden-2-yl)vinyl]trimethylsilane (13e)
Purified by column chromatography on silica gel using hexanes as
eluent. Nearly a two-fold excess of 6 over 2-bromoindene should be
used to ensure complete conversion of the bromide; otherwise, the
product is not separable from unreacted 2-bromoindene.
2
981.
14) Woerly, E. M.; Miller, J. E.; Burke, M. D. Tetrahedron 2013, 69,
732.
7
15) Jiao, J.; Hyodo, K.; Hu, H.; Nakajima, K.; Nishihara, Y. J. Org.
Chem. 2014, 79, 285.
Yield: 221 mg (97%); colorless liquid; R = 0.75 (hexanes).
f
1
H NMR (400 MHz, CDCl ): δ = 7.44 (d, J = 7.3 Hz, 1 H), 7.37 (d, J = 7.3
(16) Chae, Y. M.; Bae, J. S.; Moon, J. H.; Lee, J. Y.; Yun, J. Adv. Synth.
Catal. 2014, 356, 843.
3
Hz, 1 H), 7.27 (t, J = 7.3 Hz, 1 H), 7.19 (t, J = 7.3 Hz, 1 H), 6.82 (s, 1 H),
6
H).
.01 (d, J = 2.5 Hz, 1 H), 5.56 (d, J = 2.5 Hz, 1 H), 3.62 (s, 2 H), 0.31 (s, 9
(17) La Cascia, E.; Cuenca, A. B.; Fernández, E. Chem. Eur. J. 2016, 22,
18737.
1
3
(18) Bhat, N. G.; Aguirre, C. P. Tetrahedron Lett. 2000, 41, 8027.
C NMR (100 MHz, CDCl ): δ = 149.6 (C), 146.3 (C), 145.7 (C), 142.4
3
(19) Kurahashi, T.; Hata, T.; Masai, H.; Kitagawa, H.; Shimizu, M.;
(C), 129.5 (CH), 126.6 (CH), 125.4 (CH ), 124.9 (CH), 123.6 (CH), 121.0
2
Hiyama, T. Tetrahedron 2002, 58, 6381.
(
CH), 39.0 (CH ), –0.4 (CH ).
2
3
©
Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–E

E
Synthesis
Y. M. Ivon et al.
Paper
(
(
(
20) Hata, T.; Kitagawa, H.; Masai, H.; Kurahashi, T.; Shimizu, M.;
(28) Kalinin, A. V.; Scherer, S.; Snieckus, V. Angew. Chem. Int. Ed.
2003, 42, 3399.
(29) Boeckman, R. K. Jr.; Blum, D. M.; Ganem, B.; Halvey, N. Org.
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2017, 139, 5027.
Hiyama, T. Angew. Chem. Int. Ed. 2001, 40, 790.
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P. A. Angew. Chem. Int. Ed. 2016, 55, 5834.
22) Ferrand, L.; Lyu, Y.; Rivera-Hernández, A.; Fallon, B. J.; Amatore,
M.; Aubert, C.; Petit, M. Synthesis 2017, 49, 3895.
(23) Hyodo, K.; Suetsugu, M.; Nishihara, Y. Org. Lett. 2014, 16, 440.
(24) Darses, S.; Genet, J.-P. Chem. Rev. 2008, 108, 288.
(25) Molander, G. A.; Ellis, N. Acc. Chem. Res. 2007, 40, 275.
(26) Gillis, E. P.; Burke, M. D. Aldrichimica Acta 2009, 42, 17.
(27) Kublicki, M.; Dąbrowski, M.; Durka, K.; Kliś, T.; Serwatowski, J.;
Woźniak, K. Tetrahedron Lett. 2017, 58, 2162.
(31) Dick, G. R.; Knapp, D. M.; Gillis, E. P.; Burke, M. D. Org. Lett.
2010, 12, 2314.
(32) Struble, J. R.; Lee, S. J.; Burke, M. D. Tetrahedron 2010, 66, 4710.
(33) Armarego, W. L. F.; Chai, C. Purification of Laboratory Chemicals,
5th ed.; Elsevier: Oxford, 2003.
(34) Oliva, A.; Molinari, A. Synth. Commun. 1985, 15, 707.
©
Georg Thieme Verlag Stuttgart · New York — Synthesis 2018, 50, A–E