of 77
Supplementary Information for
Toutov, Betz, Haibach, Romine, and Grubbs
Sodium hydroxide
catalyzed dehydrocoupling of alcohols with
hydrosilanes
Anton A. Toutov,
1
Kerry N. Betz,
1
Michael
C.
Haibach,
Andrew M. Romine
,
1
& Robert H. Grubbs
1
*
rhg@caltech.edu
1
Division of Chemistry and Chemical Engineering, California Institute of Technology
Pasadena, California 91125, United States
Table of Contents
General information.
................................
................................
................................
........
2
Part I.
General observations
.
.
.
................................
................................
........................
4
Part II. Experimental and analytics.
................................
................................
...............
4
1. General procedure for
Na
OH
catalyzed silylation and characterization data.
...................
4
2.
Synthesis of
2,2,4,4,6,6
-
Hexaethyl
-
1,3,5,2,4,6
-
trioxatrisilinane
2j
................................
..
2
5
3.
Procedure for cross
-
coupling using
2,4,4,5,5
-
pentamethyl
-
2
-
phenyl
-
1,3,2
-
dioxasilolane
11
................................
.......................
2
6
Part III.
1
H NMR and
13
C NMR spectra
.
................................
................................
.....
2
7
Supplementary Information for Toutov,
Betz, Haibach, Romine, and
Grubbs
SI
-
2
General information.
Unless otherwise stated, reactions were performed in
oven
-
dried brand
-
new Fisherbrand
scintillation vials
flushed with argon
or in flame
-
dried Schlenk flasks under argon
connected on a
Schlenk line using dry, degassed solvents and
brand
-
new stirring bars
.
Solvents were dried by passage through an activated alumina column under argon.
1
Reaction progress was monitored by thin
-
layer chromatography (TLC)
, GC
-
MS,
or
GC
-
FID analyses
.
TLC was
performed using E. Merck silica gel 60 F254 precoated glass plates
(0.25 mm) and visualized by UV fluorescence quenching,
p
hosphomolybdic acid, or
KMnO
4
staining.
Silicycle SiliaFlash P60 Academic Silica gel (particle size 40
63 nm)
was
used for flash chr
omatography.
1
H NMR spectra were recorded on
a
Varian Inova 500
MHz
spectrometer
in CDCl
3
,
THF
-
d
8
, or Benzene
-
d
6
and are reported relative to residual
solvent peak at
δ
7.26 ppm
,
δ
3.58
ppm
, or
δ
7.16
ppm
respectively.
13
C NMR spectra were
recorded on a Varian Inova 500 MHz spectrometer (126 MHz) in
CDCl
3
, THF
-
d
8
, or
Benzene
-
d
6
and are reported relative to residual solvent peak at
δ
77.16 ppm
,
δ
67.21
ppm
,
or
δ
128.06
ppm
respectively. Data for
1
H NMR are reported as follo
ws: chemical shift (
δ
ppm) (multiplicity, coupli
ng constant (Hz), integration).
Multiplicities are reported as
follows: s = singlet, d = doublet, t = triplet, q = quartet, p = pentet, sept = septet, m =
multiplet, br s = broad singlet, br d =
broad doublet
, app = apparent.
Data for
13
C NMR are
reported in terms of chemical shifts (
δ
ppm). IR spectra were obtained on a
Perkin Elmer
Spectrum BXII
spectrometer using thin films deposited on NaCl plates and reported in
frequency of absorption (cm
1
). GC
-
FID anal
yses were obtained on an Agilent 6890N gas
chromatograph equipped with a HP
-
5 (5%
-
phenyl)
-
methylpolysilox
ane capillary column
(Agilent).
GC
-
MS analyses were obtained on an Agilent 6850 gas chromatograph equipped
with a HP
-
5 (5%
-
phenyl)
-
methylpolysiloxane c
apillary column (Agilent). High resolution
mass spectra (HRMS) were acquired from the California Institute of Technology Mass
Spectrometry Facility.
Silanes were purchased from Aldrich and distil
led before use.
NaOH
was purchased from
Aldrich (semiconductor grade, pellets, 99.99% trace metals basis)
and was pulverized
1
Pangborn, A. M.; Giardello, M. A.; Grubbs, R. H.; Rosen, R. K.; Timmers, F. J.
Organometallics
1996
,
15
,
1518.
Supplementary Information for Toutov,
Betz, Haibach, Romine, and
Grubbs
SI
-
3
(mortar and pestle) and heated (150 °C) under vacuum prior to use.
Powdered and vacuum
-
dried (as above) ACS grade
97% NaOH from Aldrich gives identica
l results.
Alcohol and
phenol
substrates were purchased from Aldrich, TCI, or Acros.
Supplementary Information for Toutov,
Betz, Haibach, Romine, and
Grubbs
SI
-
4
Part I.
General observations
.
THF
and DME
proved to be suitable solvents
. The addition of DMF to
reaction mixtures
enabled the silylation in challenging cases
; several
substrates failed to silylate without the
addition of DMF. See characterization data (Part II) for a comprehensive view of all
substrates that required addition of DMF.
No product was obser
ved in the absence of
catalyst.
Part II. Experimental and analytics
.
1. General proced
ure for cross
-
dehydrogenative O
H silylation
and
characterization data.
To a hot, oven
-
dried
2 dram scintillation
vial
equipped with a magnetic stirring bar
, NaOH
(0.05 mmol, 10 mol
%) was added and the vial was purged with argon until cool.
Alcohol
(0.5 mmol, 1 equiv) was then added under a steady stream of argon, followed by solvent
(0.5 mL) and silane (0.75 mmol, 1.5 equiv).
The vial was then sealed and the mixture was
stirred at t
he indicated temp
erature for the indicated time.
After the reaction was complete,
the
reaction mixture was
diluted with diethyl ether (2 mL), filtered through a short pad of
silica gel
,
and conce
ntrated under reduced pressure.
Volatiles were removed under
high
vacuum and the resultant material was purified by silica gel flash chromatography if
necessary to give the desired O
Si product.
Note that since this silylation protocol produces
stoichiometric H
2
, the reaction
especially when performed on a reasona
ble scale as in the
case of
11
(page 24)
should be conducted in a well vented system and under conditions
that are appropriately suitable and safe.
R
eactions were carried out behind protective
shielding when performed in closed vials. In cases where this
was not possible, the
reactions were carried out in septum
-
capped vials connected via a needle to an argon
manifold
and a bubbler if necessary.
Supplementary Information for Toutov,
Betz, Haibach, Romine, and
Grubbs
SI
-
5
(
B
enzyloxy)dimethyl(phenyl)silane
2a:
The
general procedure was followed. The
reaction was performed with
NaOH (2.0 mg, 0.05 mmol, 10
mol %
)
,
benzyl alcohol
(
54
mg, 0.5 mmol, 1.0 equiv),
PhMe
2
SiH (
102
mg,
115
μL,
0.75
mmol,
1.5
equiv), and 0.5 mL
of
tetrahydrofuran
(THF
) at
2
5 °C for
1
8 h. The des
ired product
2a
(
113.9
mg, 9
4
% yield)
was obtained
as a colorless
oil by
silica gel flash chromatography (
5
%
EtOAc in
hexanes).
R
f
=
0.53
(
5
%
EtOAc in
hexanes);
1
H NMR (500 MHz,
CDCl
3
)
δ
7.70
7.66
(m, 2H), 7.48
7.42 (m, 3H),
7.40
7.35 (m, 4H), 7.30
(dddd, J = 6.7, 6.2, 3
.1, 1.7 Hz, 1H), 4.77 (s, 2H),
0.49 (s, 6H).
This compound has been previously characterized.
2
(
B
enzyloxy)
triethylsilane
2b:
The general procedure was followed. The
reaction was
performed with
NaOH (2.0 mg, 0.05 mmol, 10
mol %
)
,
benzyl alcohol (54 mg, 0.5 mmol,
1.0 equiv), Et
3
SiH (
87
mg,
120
μL, 0.75 mmol, 1.5 equiv), and 0.5 mL of tetrahydrofuran
(THF) at 45 °C for 18 h. The desired product
2
b
(
101.2
mg, 9
1
% yield) w
as obtained
as a
colorless oil by
silica gel flash chromatography (
5
%
EtOAc in
hexanes).
R
f
=
0.27
(
5
%
EtOAc in
hexanes);
1
H NMR (500 MHz,
CDCl
3
)
δ
7.36
7.31 (m, 4H), 7.27
7.23 (m,
1H), 4.75 (s, 2H), 1.00 (t, J = 8.0 Hz, 9H), 0.67 (q, J = 7.9 Hz,
6
H).
This compound has
been previously characterized.
3
2
Mitsudome, T
.
; Yamamoto, Y
.
; Noujima, A
.
; Mizugaki, T
.
; Jitsukawa, K
.
; Kaneda, K.
Chem
.
Eur
.
J
.
2013
,
19
, 14398
14402.
3
Abri, A
.
; Assadi, M
.
G
.
; Pourreza, S
.
J
.
Chin
.
Chem
.
So
c.
2012
,
59
,
1449
1454.
Supplementary Information for Toutov,
Betz, Haibach, Romine, and
Grubbs
SI
-
6
(
B
enzyloxy)(methyl)diphenylsilane
2c:
The general procedure was followed. The
reaction was performed with
NaOH (2.0 mg, 0.05 mmol, 10
mol %
)
,
benzyl alcohol (54
mg, 0.5 mmol, 1.0 equiv), Ph
2
MeSiH (149 mg, 150 μL, 0.75 mmol, 1.5 equiv), and 0.5 mL
of tetrahydrofuran (THF) at 25 °C for 18 h. The desired product
2c
(
129.4
mg,
85
% yield)
was obtained
as a colorless oil by
silica gel flash ch
romatography (
5
%
EtOAc in
hexanes).
R
f
=
0.50
(
5
%
EtOAc in
hexanes);
1
H NMR (500 MHz,
CDCl
3
)
δ
7.65
7.62 (m,
4
H), 7.44
7.37 (m,
6
H), 7.36
7.32 (m,
4
H), 7.29
7.26 (m,
`
H), 4.82 (d, J = 0.9 Hz,
2
H), 0.68 (s,
3
H).
This compound has been previously
characterized.
4
(
B
enzyloxy)(tert
-
butyl)dimethylsilane
2d:
The general procedure was followed. The
reaction was performed with
NaOH (4.0 mg, 0.1 mmol, 20
mol %
)
,
benzyl alcohol (54 mg,
0.5
mmol, 1.0 equiv), (
t
-
Bu)Me
2
SiH (87 mg, 124 μL, 1.5 mmol, 3.0 equiv), 0.25 mL
dimethylformamide (DMF) and 0.25 mL of tetrahydrofuran (THF) at 65 °C for 24 h. The
desired product
2d
(
66.2
mg,
60
% yield) was obtained
as a colorless oil by
silica gel flash
chromatography (
5
%
EtOAc in
hexanes).
R
f
=
0.42
(
5
%
EtOAc in
hexanes);
1
H NMR (500
MHz,
CDCl
3
)
δ
7.35 (d, J = 4.6 Hz, 4H), 7.28
7.24 (m, 1H), 4.78 (d, J = 0.6 Hz, 2H),
0.98 (s, 9H), 0.14 (s, 6H).
This compound has been previously characterized.
5
4
Igarashi, M
.
; Matsumoto, T
.
; Sato, K
.
; Ando, W
.
; Shimada, S.
Chem
.
Lett
.
2014
,
43
,
429
431.
5
Yamamoto, K
.
; Takemae, M.
Bull
. Chem. Soc. Jp
n
.
1989
,
62
,
2111
2113.
Supplementary Information for Toutov,
Betz, Haibach, Romine, and
Grubbs
SI
-
7
(
B
enzyloxy)di
-
tert
-
butylsilane
2
e
:
The general procedure was followed. The reaction was
performed with
NaOH (2.0 mg, 0.05 mmol, 10
mol %
)
,
benzyl alcohol (54 mg, 0.5 mmol,
1.0 equiv),
(
t
-
Bu)
2
SiH
2
(108 mg, 148 μL, 0.75 mmol, 1.5 equiv),
and 0.5 mL of
tetrahydrofuran (THF) at
2
5 °C for 18 h. The desired product
2
e
(
120.2
mg, 9
6
% yield)
was obtained
as a colorless oil
after removal of volatiles under high vacuum (45 mtorr) for
2 hours.
1
H NMR (500 MHz,
CDCl
3
)
δ
7.39
7.34
(m, 4H), 7.29
7.25 (m, 1H),
4.88 (d,
J = 0.7 Hz, 2H), 4.12 (s, 1H), 1.05 (s, 18H).
This compound has been previously
characterized.
6
(
B
enzyloxy)triisopropylsilane
2
f
:
The general procedure was followed. The reaction was
performed with
NaOH (2.0 mg, 0.05 mmol, 10
mol %
)
,
benzyl alcohol (54 mg, 0.5 mmol,
1.0 equiv),
(
i
-
Pr)
3
SiH (
119
mg,
154
μL, 0.75 mmol, 1.5 equiv
), 0.25 mL
dimethylformamid
e (
DMF
)
, and 0.25
mL of tetrahydrofuran (THF) at
6
5 °C for 18 h. The
desired product
2
f
(
112.4
mg,
85
% yield) was obtained
as a colorless oil by
silica gel flash
chromatography (
5
%
EtOAc in
hexanes).
R
f
=
0.52
(
5
%
EtOAc in
hexanes);
1
H NMR (500
MHz,
CDCl
3
)
δ
7.40
7.32 (m, 4H), 7.27
7.23 (m, 1H), 4.87 (d, J = 1.5 Hz, 2H), 1.26
1.17 (m, 3H), 1.
12
(
d,
J
= 7.0 Hz
, 18H).
This compound has been previously characterized.
7
6
Curran, D
.
P.; Xu,
J
.
; Lazzarini, E.
J. Chem. Soc., Perkin Trans. 1
1995
,
24
,
3049
3060.
7
Khalafi
-
Nezhad, A
.
; Fareghi Alamdari, R
.
; Zekri, N.
Tetrahedron
2000
,
56
,
7503
7506.
Supplementary Information for Toutov,
Betz, Haibach, Romine, and
Grubbs
SI
-
8
1
-
(
B
enzyloxy)
-
1,1,2,2,2
-
pentamethyldisilan
e
2
g
:
The general procedure was followed.
The reaction was performed with
NaOH (2.0 mg, 0.05 mmol, 10
mol %
)
,
benzyl alcohol
(54 mg, 0.5 mmol, 1.0 equiv),
Me
5
Si
2
H (
99
mg,
137
μL, 0.75 mmol, 1.5 equiv), and 0.5
mL of te
trahydrofuran (THF) at
2
5 °C for
24
h.
Concentration of the reaction mixture and
purification of the resulting residue via Kugelrohr distillation (120 mTorr, 60 °C) gave 79.9
mg (67% yield) of
2g
as a colorless oil.
1
H NMR (500 MHz,
THF
-
d
8
)
δ
7.31
7.24 (m,
4H), 7.21
7.15 (m, 1H), 4.68
(q, J = 0.7 Hz, 2H), 0.23 (s, 6H), 0.10 (s, 9H);
13
C NMR
(126 MHz,
THF
-
d
8
)
δ
1
42.61, 128.96, 127.71, 127.01,
66.02,
-
0.52,
-
1.79.
IR (Neat Film
NaCl)
3363, 3088, 3065, 3030, 2952, 2893, 1595, 1495, 1453, 1376,
1259, 1246, 1207,
1091, 1067, 1026, 835, 803, 766, 729, 695, 655, 617
cm
-
1
;
HRMS (EI+) calc’d for
C
1
2
H
2
3
O
Si
2
[M+H
]:
239.1288
, found
239.1295.
B
is(benzyloxy)diethylsilane
2h:
The general
procedure was followed. The reaction was
performed with
NaOH (2.0 mg, 0.05 mmol, 10
mol %
)
,
benzyl alcohol (108 mg, 1.0 mmol,
1.0 equiv), Et
2
SiH
2
(49 mg, 71 μL, 0.55 mmol, 0.55 equiv), and 1.0 mL of tetrahydrofuran
(THF) at 25 °C for 18 h. The desired product
2h
(
120.8
mg,
80
% yield) was obtained
as a
colorless oil by
silica gel flash chromatography (
5
%
EtOAc in
hexanes).
R
f
=
0.43
(
5
%
EtOAc in
hexa
nes);
1
H NMR (500 MHz,
CDCl
3
)
δ
7.35 (d
, J = 4.4 Hz, 8H), 7.31
7.26
Supplementary Information for Toutov,
Betz, Haibach, Romine, and
Grubbs
SI
-
9
(m, 2H), 4.82 (s, 4H), 1.05 (t, J = 7.9 Hz
, 6H), 0.76 (q, J = 8.0 Hz, 4H)
.
This compound
has been previously characterized.
8
B
is(benzyloxy)(methyl)(phenyl)silane
2i:
The general procedure was followed. The
reaction was performed with
NaOH (2.0 mg, 0.05 mmol, 10
mol %
)
,
benzyl alcohol (108
mg, 1.0 mmol, 1.0 equiv), MePhSiH
2
(67 mg, 76 μL, 0.55 mmo
l, 0.55 equiv), and 1.0 mL
of tetrahydrofuran (THF) at 25 °C for 18 h. The desired product
2i
(
158.8
mg,
95
% yield)
was obtained
as a colorless oil by
silica gel flash chromatography (
5
%
EtOAc in
hexanes).
R
f
=
0.44
(
5
%
EtOAc in
hexanes);
1
H NMR (500 MHz,
CDCl
3
)
δ
7.76 (dd, J =
7.9, 1.5 Hz,
2H), 7.49
7.43
(m, 3H), 7.39
7.37 (m, 8H), 7.33
7.28 (m, 2H), 4.91
4.82 (m, 4H),
0.50 (s, 3H).
This compound has been previously characterized.
9
((4
-
F
luorobenzyl)oxy)dimethyl(phenyl)silane
4a:
The general procedure was followed.
The reaction was performed with
NaOH (2.0 mg, 0.05 mmol, 10
mol %
)
,
4
-
fluorobenzyl
alcohol (63 mg, 0.5 mmol, 1.0 equiv), PhMe
2
SiH (102 mg, 115 μL, 0.75 mmol, 1.5 equiv),
8
Chatterjee, B
.
; Gunanathan, C.
Chem
.
Commun
.
2014
,
50
,
888
890.
9
Kita, Y
.
; Yasuda, H
.
; Sugiyama,
Y
.
; Fukata, F
.; Haruta, J.
; Yasumitsu, T.
Tetrahedron
Lett.
1983
,
24
,
1273
1276.
Supplementary Information for Toutov,
Betz, Haibach, Romine, and
Grubbs
SI
-
10
0.2 mL dimethylformamide (DMF) and 0.3 mL of tetrahydrofuran (THF) at 25 °C for 18
h. The desired product
4a
(
146.0
mg,
7
9% yield) was obtained
as a colorless oil by
silica
gel flash
chromatography
(
5
%
EtOAc in
hexanes).
R
f
= 0.
48
(
5
%
EtOAc in
hexanes);
1
H
NMR (500 MHz,
CDCl
3
)
δ
7.65
7.59
(m, 2H), 7.46
7.37 (m, 3H),
7.31
7.25 (m, 2H),
7.06
6.97 (m, 2H), 4.67 (q
, J = 0.8 Hz, 2H), 0.45 (s, 6H);
13
C NMR (126 MHz,
CDCl
3
)
δ
162.14 (d, J = 244.4 Hz), 137.50, 136.53
(d, J = 2.9 Hz), 133.64
, 129.90
, 128.37
(d
, J = 8.3
Hz), 128.06, 115.19 (d, J = 21.1 Hz), 64.48,
-
1.60
.
IR (Neat Film NaCl)
3440, 3070, 3050,
3022, 2958, 2866, 1605, 1509, 1463, 1427, 1417, 1375, 1294, 1253, 1221, 1155, 1117,
1082, 1014, 826, 789, 741, 700, 645
cm
1
; HRMS (EI+) calc’d for C
15
H
16
O
Si
F
[
(
M+H
)
-
H
2
]:
259.0955
, found
259.0951
.
((4
-
B
romobenzyl)oxy)dimethyl(phenyl)silane
4b:
The general procedure was followed.
The reaction was performed with
NaOH (2.0 mg, 0.05 mmol, 10
mol %
)
,
4
-
bromobenzyl
alcohol (94 mg, 0.5 mmol, 1.0 equiv), PhMe
2
SiH (102 mg, 115 μL, 0.75 mmol, 1.5 equiv),
0.2 mL dimethylformamide (DMF) and 0.3 mL of tetrahydrofuran (THF) at 65 °C for 24
h. The desired product
4b
(
146.2
mg,
91
% yield) was obtained
as
a colorless oil by
silica
gel flash chromatography (
5
%
EtOAc in
hexanes).
R
f
=
0.48
(
5
%
EtOAc in
hexanes);
1
H
NMR (500 MHz,
CDCl
3
)
δ
7.61 (dd, J = 7.7,
1.8 Hz, 2H), 7.47
7.34
(m, 5H), 7.19 (dt, J
= 8.7, 0.7 Hz, 2H), 4.66 (d, J = 0.8 Hz, 2H), 0.44 (s, 6H).
This compound has been
previously characterized.
10
10
Kennedy
-
Smith, J
.
J.; Nolin, K
.
A.; Gunterman, H
. P.; Toste, D. F
.
J. Am. Chem. Soc.
2003
,
125
,
4056
4057.
Supplementary Information for Toutov,
Betz, Haibach, Romine, and
Grubbs
SI
-
11
D
imethyl((4
-
nitrobenzyl)oxy)(phenyl)silane
4c:
The gene
ral procedure was followed.
The reaction was performed with
NaOH (2.0 mg, 0.05 mmol, 10
mol %
)
,
4
-
nitrobenzyl
alcohol (77 mg, 0.5 mmol, 1.0 equiv), PhMe
2
SiH (102 mg,
115 μL, 0.75 mmol, 1.5 equiv),
0.2 mL dimethylformamide (DMF) and 0.3 mL of tetrahydrofuran (THF) at 65 °C for 18
h. The desired product
4c
(
102.2
mg, 7
1
% yield) was obtained
as a colorless oil
by silica
gel flash chromatography (
5
% EtOAc in hexanes).
R
f
= 0
.
38
(
5
% EtOAc in hexanes);
1
H
NMR (500 MHz,
CDCl
3
)
δ
8.21
8.15 (m,
2H), 7.60 (dd, J = 7.8, 1.7
Hz, 2H), 7.47 (dt, J
= 8.8, 0.8 Hz, 2H), 7.44
7.38 (m, 3H), 4.79 (t, J = 0.8 Hz, 2H), 0.47 (s, 6H)
;
13
C NMR
(126 MHz,
CDCl
3
)
δ
1
48.51, 147.18, 136.92, 133.59,
130.13, 128.1
8, 126.77, 12
3.68,
64.03,
-
1.73
.
IR (Neat Film NaCl)
3423, 2958, 1641, 1608, 1519, 1527, 1253, 1117, 1094,
856, 830, 786, 735, 700
cm
1
; HRMS (EI+) calc’d for
C
15
H
18
SiO
3
N
[M+H]:
288.1056
,
found
288.1058
.
Methyl 4
-
(((dimethyl(phenyl)silyl)oxy)methyl)benzoate
4d:
The general procedure was
followed. The reaction was performed with
NaOH (2.0 mg, 0.05 mmol, 10
mol %
)
,
methyl
4
-
(hydroxymethyl)benzoate (83 mg, 0.5 mmol, 1.0 equiv), PhMe
2
SiH (102 mg, 115 μL,
Supplementary Information for Toutov,
Betz, Haibach, Romine, and
Grubbs
SI
-
12
0
.75 mmol, 1.5 equiv), 0.2 mL dimethylformamide (DMF) and 0.3 mL of tetrahydrofuran
(THF) at 65 °C for 24 h. The desired product
4d
(
100.6
mg,
67
% yield) was obtained
as a
colorless oil by
silica gel flash chromatography (
gradient 1
5
%
EtOAc to 30% EtOAc in
hexanes).
R
f
=
0.62
(
15
%
EtOAc in
hexanes);
1
H NMR (500 MHz,
CDCl
3
)
δ
8.01 (
d, J =
8.3 Hz, 2H), 7.63
7.60 (m, 2H),
7.45
7.36 (m, 5H), 4.76 (d, J = 0.8 Hz, 2H), 3.92 (s,
3H), 0.46 (s, 6H).
This compound has been previously characterized.
11
4
-
(
M
ethoxycarbonyl)benzyl 4
-
(((dimethyl(phenyl)silyl)oxy)methyl)benzoate
4d
-
SI:
Also isolated from the column was
4d
-
SI
(
36.9
mg,
34
%
silylation
yield
/ 17% yield based
on methyl 4
-
(hydroxymethyl)benzoate stoichiometry
)
as a colorless solid.
R
f
= 0.
43
(
15
%
EtOAc in hexanes
);
1
H NMR (500 MHz,
CDCl
3
)
δ
8.08
8.03 (m,
4H), 7.62
7.58 (m,
2H), 7.51
(dt, J = 8.6, 0.7 Hz, 2H), 7.43
7.37 (m, 5H), 5.42 (s,
2H), 4.76 (d, J = 0.8 Hz,
2H), 3.93 (s, 3H), 0.44 (s, 6H);
13
C NMR (12
6 MHz,
CDCl
3
)
δ
166.88, 1
66.31, 146.62,
141.30, 137.26,
133.61, 130.02, 129.97, 129.90, 128.63,
128.09, 127.72, 126.27, 65.94,
64.53, 52.32,
-
1.64.
((4
-
M
ethoxybenzyl)oxy)dimethyl(phenyl)silane
4e
:
T
he general procedure was
followed. The reaction was performed with
NaOH (
2.0
mg, 0.
05
mmol,
1
0
mol %
)
,
4
-
methoxy
benzyl alcohol
(69
mg, 0.5 mmol, 1.0 equiv),
PhMe
2
SiH (102 mg, 115 μL, 0.75
mmol, 1.5 equiv),
and 0
.
5
mL of tetrahydrofuran (THF) at
2
5 °C for
18
h. The desired
product
4e
(
117.9
mg,
87
% yield) was obtained
as a colorless oil by
silica gel flash
chromatography (
5
%
EtOAc in
hexanes).
R
f
=
0.29
(
5
%
EtOAc in
hexanes);
1
H NMR (500
11
Fernandez, A
.
C.; Fernandez, R
.
; Romao, C
.
C.; Royo, B.
Chem.
Commun.
2005
,
2
,
213
214.
Supplementary Information for Toutov,
Betz, Haibach, Romine, and
Grubbs
SI
-
13
MHz,
CDCl
3
)
δ
7.62 (dd, J
=
7.5, 2.0 Hz, 2H), 7.44
7.37
(m, 3H), 7.25
7.20 (m, 2H),
6.87 (d, J = 8.6 Hz,
2H), 4.64 (d, J = 0.6 Hz, 2H),
3.81 (s, 3H), 0.42 (s, 6H).
This compound
has been previously characterized.
12
3
-
(((
D
imethyl(phenyl)silyl)oxy)methyl)pyridine
silane
4f:
The general procedure was
followed. The reaction was performed with
NaOH (2.0 mg, 0.05 mmol, 10
mol %
)
,
pyridin
-
3
-
ylmethanol (55 mg, 0.5 mmol, 1.0 equiv), PhMe
2
SiH (102 mg, 115 μL, 0.75 mmol, 1.
5
equiv), and 0.5 mL of tetrahydrofuran (THF) at 25 °C for 18 h. The desired product
4f
(
118.1
mg,
97
% yield) was obtained
as a colorless oil by removal of volatiles at 80
°
C at
60mTorr.
1
H NMR (500 MHz,
CDCl
3
)
δ
8.52 (
dt, J = 2.3, 0.8 Hz, 1H), 8.49
(dd, J
= 4.8,
1.6 Hz, 1H), 7.65 (dtd, J = 7.8, 1.7, 0.9 Hz, 1H), 7.61
7.57
(m, 2H), 7.43
7.37 (m, 3H),
7.26 (ddd, J
= 7.9, 4.8, 0.9 Hz, 1H), 4.70
(dt, J = 0.6 Hz, 2H), 0.44 (s, 6H).
This compound
has been previously characterized.
13
D
imethyl(phenyl)(thiophen
-
2
-
ylmethoxy)silane
4g:
The general procedure was
followed. The reaction was performed with
NaOH (2.0 mg, 0.05 mmol, 10
mol %
)
,
thiophen
-
2
-
ylmethanol (57 mg, 0.5 mmol, 1.0 equiv), PhMe
2
SiH
(102 mg, 115 μL, 0.75
mmol, 1.5 equiv), and 0.5 mL of tetrahydrofuran (THF) at 25 °C for 18 h. The desired
product
4g
(
119.2
mg,
96
% yield) was obtained
as a colorless oil by removal of volatiles
12
Bideau, F
.
L
.
; Coradin, T
.; Henique,
J
.
; Samuel, E.
Chem. Commun.
2001
,
15
,
1408
1409.
13
Goldberg, Y
.
; Rubina, K.; Shymanska, M.; Lukevics, E.
Synth. Commun.
1990
,
20
,
2439
2446.
Supplementary Information for Toutov,
Betz, Haibach, Romine, and
Grubbs
SI
-
14
at 80
°
C at 60mTorr.
1
H NMR (500 MHz,
CDCl
3
)
δ
7.63
7.58 (m,
2
H), 7.44
7.37 (m,
3
H), 7.28 (dd, J = 4.4, 1.9 Hz,
1
H), 7.00 (d, J = 4.4 Hz,
2
H), 4.76 (d,
J = 0.8 Hz
,
2
H), 0.41
(s,
6
H).
This compound has been previously characterized.
14
(
F
uran
-
2
-
ylmethoxy)dimethyl(phenyl)sila
ne 4h:
The general procedure was followed.
The reaction was performed with
NaOH (2.0 mg, 0.05 mmol, 10
mol %
)
,
furfuryl alcohol
(49 mg, 0.5 mmol, 1.0 equiv), PhMe
2
SiH (102 mg, 115 μL, 0.75 mmol, 1.5 equiv), and 0.5
mL of tetrahydrofuran (THF) at 45 °C for 18 h. The desired product
4h
(101.1 mg, 87%
yield) was obtained as a colorless oil by removal of volatiles at 80 °C at 60mTorr.
1
H NMR
(500 MHz, CDCl
3
)
δ
7.62 (ddd, J = 7.5, 2.4, 1.3 Hz, 2H), 7.46
7.33 (m, 4H), 6
.32 (dt, J
= 3.4, 1.8 Hz, 1H), 6.21 (t, J = 2.5 Hz, 1H), 4.62 (d, J = 2.0 Hz, 2H), 0.
43
(
d, J = 1.9 Hz
,
6H). This compound has been previously characterized.
15
D
imethyl(phenyl)((2,4,6
-
trimethylbenzyl)oxy)silane
4
i
:
The general procedure was
followed. The reaction was performed with
NaOH (2.0 mg, 0.05 mmol, 10
mol %
)
,
mesitylmethanol
(
75
mg, 0.5 mmol, 1.0 equiv), PhMe
2
SiH (102 mg, 115 μL, 0.75 mmol,
1.5 equiv),
0.2
mL dimethylformamide (DMF) and 0.3 mL of tetrahydrofuran (THF)
at 65
°C for
1
8 h.
Concentration of the reaction mixture and purification of the resulting residue
14
Goldberg, Y
.; Abele, E.; Shymanska, M.;
Lukevics, E.
J. Organomet. Chem.
1991
,
410
,
127
133.
15
Goldberg, Y
.; Abele, E.; Shymanska, M.; Lukevics, E.
J. Organomet. Chem.
1991
,
410
,
127
133.
Supplementary Information for Toutov,
Betz, Haibach, Romine, and
Grubbs
SI
-
15
via
Kugelrohr distillation (100 mTorr, 210 °C) gave
118.7
mg (
84
%
yield
) of
4
i
as a
colorless oil. (Note: the purified material obtained by Kugelrohr distillation was
accompanied by ca. 5% unidentified by
-
products; however, further purification by
chromatography was precluded by the instability of
4
i
on SiO
2
as well as its decomposit
ion
under prolonged heating
)
.
1
H NMR (500 MHz, THF
-
d
8
)
δ
7.59
7.55
(m, 2H), 7.36
7.30
(m, 3H),
6.79
6.73 (m, 2H), 4.66 (s, 2H), 2.24 (t,
J = 0.6 Hz, 6H), 2.20 (s, 3H), 0.35 (s,
6H)
;
13
C NMR (126 MHz, THF
-
d
8
)
δ
139.02, 1
37.93, 137.61, 134.72, 134.46,
130.42,
129.65, 128
.68, 59.98, 21.23, 19.79,
-
1.48
.
IR (Neat Film NaCl)
3421, 3069, 3048, 3008,
2957, 2918, 1614, 1583, 1427, 1373, 1253, 1147, 1118, 1046, 848, 829, 784, 740, 699, 644
cm
1
; HRMS (EI+) calc’d for C
16
H
16
FSi
[
(
M+H
)
-
H
2
]:
283.1518
, found
283.1526
.
2
-
(2
-
((
D
imethyl(phenyl)silyl)oxy)ethyl)isoindoline
-
1,3
-
dione
4j:
The general procedure
was followed. The reaction was performed with
NaOH (2.0 mg, 0.05 mmol, 10
mol %
)
,
2
-
(2
-
hydroxyethyl)isoindoline
-
1,3
-
dione (96 mg, 0.5 mmol, 1.0 equiv), PhMe
2
SiH (102 mg,
115 μL, 0.75 mmol, 1.5 equiv), 0.2 mL dimethylformamide (DMF) and 0.3 mL of
tetrahydrofuran (THF) at 65 °C for 24 h. The desired product
4j
(
101.6
mg,
62
% yield)
was o
btained
as a colorless oil
by silica gel flash chromatography (
20
%
EtOAc in
hexanes).
R
f
= 0.
45
(
20
%
EtOAc in
hexanes);
1
H NMR (500 MHz,
Benzene
-
d
6
)
δ
7.52
7.50 (
m,
1H), 7.50 (dd, J = 2.4, 0.6
Hz, 1H), 7.43 (dd, J = 5.4, 3.0 Hz, 2H), 7.16
7.15
(m, 1H),
7.15
7.14 (m, 1H),
7.14 (d, J = 2.3 Hz, 1H), 6.87 (ddd, J = 5.5, 3.0, 0.5
Hz, 2H), 3.74
3.67 (m, 2H),
3.
68
3.62 (m, 2H), 0.26 (s, 6H)
;
13
C NMR (126 MHz,
Benzene
-
d
6
)
δ
167.96,
1
37.77, 133.81, 133.39, 132.66,
129.84, 128.13, 122.95, 60.16, 40.23,
-
1.81.
IR (Neat Film
NaCl)
2956, 1773, 1713, 1615, 1467, 1427, 1392, 1362, 1319, 1252, 1189, 1116, 1022,
929, 859, 829, 788, 718, 700
cm
1
; HRMS (EI+) calc’d for C
1
8
H
2
0
O
3
Si
N
[M+H]:
326.1213
,
found
326.1223
.
Supplementary Information for Toutov,
Betz, Haibach, Romine, and
Grubbs
SI
-
16
D
imethyl(phenyl)((5
-
phenylpentyl)oxy)silane
4
k
:
The general procedure was followed.
The reaction was performed with
NaOH (2.0 mg, 0.05 mmol, 10
mol %
)
,
5
-
phenylpentan
-
1
-
ol (82 mg, 0.5 mmol, 1.0 equiv), PhMe
2
SiH (102 mg, 115 μL, 0.75 mmol, 1.5 equiv),
and 0.5 mL of tetrahydrofuran (THF) at 45 °C for 18 h. The desired product
4
k
(
146.3
mg,
98
% yield) was obtained
as a colorless oil by
silica gel flash chromatography (
5% EtOAc
in hexanes).
R
f
= 0.
46
(
5
%
EtOAc in
hexanes);
1
H NMR (500 MHz,
CDCl
3
)
δ
7.63 (ddq, J
=
6.2, 1.9, 0.9 Hz, 2H), 7.46
7.41 (m, 3H), 7.32 (tt, J = 7.5, 0.9 Hz, 2H), 7.22 (d
dt, J =
9.9, 7.3, 1.3 Hz, 3H),
3.65 (td, J = 6.7, 1.1 Hz, 2H), 2.67
2.63 (m, 2H
), 1.74
1.58 (m,
4H), 1.47
1.38 (m
,
2H), 0.44 (t, J = 1.0 Hz, 6H);
13
C NMR (126 MHz,
CDCl
3
)
δ
142.79,
138.10, 133.58, 129.66, 128.51, 128.34, 127.93, 125.71, 63.15, 36.04, 32.57, 31.41, 25.59,
-
1.65.
IR (Neat Film NaCl)
3385, 3067, 3025, 2933, 2857, 1603, 1495, 1452, 1427, 1341,
1254, 1119, 1055, 831, 791, 726, 698
cm
1
; HRMS (EI+) calc’d for C
1
9
H
27
O
Si [M+H]:
299.1831
, found
299.1840
.
D
imethyl((3
-
methylcyclohex
-
2
-
en
-
1
-
yl)oxy)(phenyl)silane
4l:
The general procedure
was followed. The reaction was performed with
NaOH (2.0 mg, 0.05 mmol, 10
mol %
)
,
3
-
methylcyclohex
-
2
-
en
-
1
-
ol (56 mg, 0.5 mmol, 1.0 equiv), PhMe
2
SiH (102 mg, 115 μL, 0.75
Supplementary Information for Toutov,
Betz, Haibach, Romine, and
Grubbs
SI
-
17
mmol,
1.5 equiv), and 0.5 mL of tetrahydrofuran (THF) at 45 °C for 48 h. The desired
product
4l
(
113.4
mg,
92
% yield) was obtained
as a colorless oil
by silica gel flash
chromatography (
5
% EtOAc
in hexanes
).
R
f
= 0.4
3
(
5% EtOAc in hexanes
);
1
H NMR (500
MHz,
CDC
l
3
)
δ
7.64
7.56 (m, 2H)
, 7.38 (dd, J =
5.0, 1.9 Hz, 3H), 5.34 (dd, J = 3.1, 1.6
Hz, 1
H), 4.20 (dt, J = 5.0, 1.6 Hz,
1H), 1.99
1.69 (m, 4H), 1.64 (tt, J = 1.6
, 0.9 Hz, 3H),
1.55
1.42 (m, 2H), 0.40 (d, J = 1.1 Hz, 6H);
13
C NMR (126 MHz,
CDCl
3
)
δ
138.64,
1
37.78, 133.69, 129.59, 127.89,
125.14, 67.41, 32.13, 30.08, 23.80, 19.83,
-
0.80,
-
0.91.
IR
(Neat Film NaCl)
3423, 3069, 2935, 2862, 1645, 1427, 1251
, 1116
, 1074, 1024, 992, 894,
880, 828, 786, 738, 700
cm
1
; HRMS (EI+) calc’d for C
1
5
H
21
O
Si [
(
M+H
)
-
H
2
]:
245.1362
,
found
245.1368
.
(
H
ex
-
2
-
yn
-
1
-
yloxy)dimethyl(phenyl)silane
4
m
:
The general procedure was followed.
The reaction was performed with
NaOH (2.0 mg, 0.05 mmol, 10
mol %
)
,
hex
-
2
-
yn
-
1
-
ol
(
49
mg, 0.5 mmol, 1.0 equiv), PhMe
2
SiH (102 mg, 115 μL, 0.75 mmol, 1.5 equiv),
and 0.5
mL of 1
tetrahydrofuran (THF)
at 45 °C for
18
h. The desired product
4
m
(
99.9
mg,
86
%
yield) was obtained
as a colorless oil
by silica gel flash chromatography
(
5% EtOAc in
hexanes).
R
f
= 0.
43
(
5
%
EtOAc in
hexanes);
1
H NMR (500 MHz,
CDCl
3
)
δ
7.62
7.59
(m, 2H), 7.42
7.36 (m, 3H),
4.27 (t, J = 2.2 Hz, 2H), 2.16 (tt, J = 7.1, 2.2 Hz,
2H), 1.51
(h, J = 7.3 Hz, 2H),
0.97 (t
, J =
7.3 Hz, 3H), 0.45 (s, 6H)
;
13
C NMR (126 MHz,
CDCl
3
)
δ
137.36,
133.71, 129.84, 127.97, 85.99,
78.37, 51
.93, 22.11, 20.92, 13.66,
-
1.46
.
Note: this
product decomposes slowly in CDCl
3
.
IR (Neat Film NaCl)
3420, 2956, 1646, 1254, 1118,
1067, 1026, 830, 789, 7
26, 698
cm
1
; HRMS (EI+) calc’d for C
1
4
H
1
9
O
Si [M+H]:
231.1205
,
found
231.1207
.
Supplementary Information for Toutov,
Betz, Haibach, Romine, and
Grubbs
SI
-
18
(
C
yclopropylmethoxy)dimethyl(phenyl)silane
4
n
:
The general procedure was followed.
The reaction was
performed with
NaOH (2.0 mg, 0.05 mmol, 10
mol %
)
,
cyclopropanemethanol (36 mg, 0.5 mmol, 1.0 equiv), PhMe
2
SiH (102 mg, 115 μL, 0.75
mmol, 1.5 equiv),
0.2 mL dimethylformamide (DMF) and 0.3 mL of tetrahydrofuran (THF)
at
65
°C for 18 h. Concentration of th
e reaction mixture and purification of the resulting
residue
via
Kugelrohr distillation (120 mTorr, 65 °C) gave
65.4
mg (
63
%
yield
) of
4
n
as a
colorless oil.
Note: product is volatile under high vacuum.
(Note: the purified material
obtained by Kugelrohr di
stillation was accompanied by ca. 5% unidentified by
-
products;
however, further purification by chromatography was precluded by the instability of
4
n
on
SiO
2
).
1
H NMR (500 MHz,
Benzene
-
d
6
)
δ
7.63
7.58 (m, 2H), 7.27
7.19 (m, 3H),
3.40
(d, J = 6.4 Hz,
2H), 0.95 (ttt, J = 8.0, 6
.4, 4.9 Hz, 1H), 0.34 (s, 6H),
0.32
0.28 (m, 2H),
0.12
0.05 (m, 2H)
;
13
C NMR (126 MHz, Benzene
-
d
6
)
δ
138.63,
133.92, 129.80, 128.15,
67.54, 13.68, 3.23,
-
1.38
.
IR (Neat Film NaCl)
3070, 3006, 2958, 2862, 1470, 1427, 1403,
1251
, 1177, 1116, 1073, 851, 826, 785, 740, 699
cm
1
; HRMS (EI+) calc’d for
C
12
H
18
OSi
[M+•]: 206.1127, found 206.1148.
D
imethyl(oxiran
-
2
-
ylmethoxy)(phenyl)silane
4
o
:
The general procedure was
followed.
The reaction was performed with
NaOH (2.0 mg, 0.05 mmol, 10
mol %
)
,
glycidol
(
37
mg,
0.5 mmol, 1.0 equiv), PhMe
2
SiH (102 mg, 115 μL, 0.75 mmol, 1.5 equiv),
and 0.5
mL of
tetrahydrofuran (THF) at
2
5 °C for
18
h. The desired product
4
o
(
74.8
mg,
72
% yield) was
obtained
as a colorless oil by
silica gel flash chromatography (
10
%
EtOAc in
hexanes).
R
f
Supplementary Information for Toutov,
Betz, Haibach, Romine, and
Grubbs
SI
-
19
=
0.60
(
10
%
EtOAc in
hexanes);
1
H NMR (500 MHz,
Benzene
-
d
6
)
δ
7.63
7.53 (m, 2H),
7
.22 (dd, J = 5.5, 1.8 Hz, 3H),
3.58 (dd, J = 11.9, 2.9 Hz, 1H), 3.3
3 (dd, J = 11.9, 5.3 Hz,
1H), 2.78 (ddt, J = 5.4, 3.9,
2.7 Hz, 1H), 2.24 (dd, J = 5.3, 4.0 Hz, 1H), 2.16 (dd, J = 5.3,
2.6 Hz, 1H), 0.33 (s, 6H).
This compound has been previously characterized.
16
(((3s,5s,7s)
-
A
damantan
-
1
-
yl)oxy)dimethyl(phenyl)sil
ane
4
p
:
The general procedure
was followed. The reaction was performed with
NaOH (2.0 mg, 0.05 mmol, 10
mol %
)
,
1
-
adamantol (76 mg, 0.5 mmol, 1.0 equiv), PhMe
2
SiH (102 mg,
115 μL, 0.75 mmol, 1.5
equiv), and 0.5 mL of tetrahydrofuran (THF) at 65 °C for 18 h. The desired product
4
p
(66.2 mg, 60% yield) was obtained as a colorless oil by removal of volatiles at 80 °C at
60mTorr.
1
H NMR (500 MHz, CDCl
3
)
δ
7.68
7.62 (m, 2H), 7.
40
7.38 (m, 3H), 2.13
2.08 (m, 3H), 1.80 (dt, J = 3.3, 0.8 Hz, 6H), 1.64
1.55 (m, 6H), 0.43 (s, 6H). This
compound has been previously characterized.
17
D
imethyl(octyloxy)(phenyl)silane
4
q
:
The general procedure was followed. The reaction
was performed with
NaOH (2.0 mg, 0.05 mmol, 10
mol %
)
,
1
-
octanol (65 mg, 0.5 mmol,
1.0 equiv), PhMe
2
SiH (102 mg, 115 μL, 0.75 mmol, 1.5 equiv), and 0.5 mL of
tetrahydrofur
an (THF) at 25 °C for 18 h. The desired product
4
q
(
111.1
mg,
84
% yield)
16
Bideau, F
.
L
.
; Coradin, T
.; Henique,
J
.
; Samuel, E.
Chem. Commun.
2001
,
15
,
1408
1409.
17
Park, J
.
-
W
.
; Jun,
C
.
-
H.
Org. Lett.
2007
,
9
,
4073
4076.
Supplementary Information for Toutov,
Betz, Haibach, Romine, and
Grubbs
SI
-
20
was obtained
as a colorless oil by
silica gel flash chromatography (
100%
hexanes).
R
f
=
0.49
(
100%
hexanes);
1
H NMR (500 MHz,
CDCl
3
)
δ
7.64
7.58 (m, 2H), 7.41 (dd,
J =
5.0, 1.9 Hz, 3H),
3.62 (t, J = 6.7 Hz, 2H), 1.60
1.51 (m, 2H), 1.32
1.24
(m, 10H), 0.97
0.85 (m, 3H),
0.41 (s, 6H).
This compound has been previously characterized.
18
Dimethyl(phenyl)(3,3,3
-
trifluoropropoxy)silane 4r:
The general procedure was
followed. The reaction was performed with 3,3,3
-
trifluoropropanol (114 mg, 1.00 mmol.
1.0 equiv), Me
2
PhSiH
(204 mg, 230
μ
L, 1.5 mmol, 1.5 equiv), NaOH (4.0 mg, 0.10 mmol,
10 mol%)
and THF (1.0 mL). The reaction was heated to 60°C for 24 hours, then
concentrated in vacuo and purified by
silica gel
column chromatography
(
5% EtOAc in
hexanes) to afford
4r
(
220 mg
, 89% yield
)
as a
colorless
oil.
R
f
= 0.48 (
5% EtOAc
in
hexanes
)
;
1
H NMR (500 MHz,
CDCl
3
)
δ
7.76
7.55 (m, 2H), 7.55
7.41 (m, 3H), 3.91 (t,
J
= 6.7 Hz, 2H), 2.43 (qt,
J
= 10.7, 6.7 Hz, 2H), 0.49 (s, 6H).
13
C NMR (126 MHz,
CDCl
3
)
δ
137.
18, 133.54, 130.00, 128.11,
56.
34
(q,
J
= 3.9 Hz), 36.
96
(q,
J
= 27.4 Hz),
-
1.96
;
19
F
NMR (282 MHz,
CDCl
3
)
δ
-
64.60
(t,
J
= 10.7 Hz)
.
IR (Neat Film NaCl) 3051, 3070, 3022,
3012, 2959, 3002, 2892, 1591, 1410, 1382, 1347, 1255, 1152, 1137, 1119, 1094, 1050,
1025, 1006, 917, 830, 728, 699 cm
1
; HRMS (EI+) calc’d for C
15
H
18
O
2
Si [M+•]:
248.0844
,
found
248.0836
.
(3
-
chloropropoxy)dimethyl(phenyl)silane
4s:
The general procedure was followed. The
reaction was performed with 3
-
chloropropanol (94 mg, 1.00 mmol. 1.0 equiv), Me
2
PhSiH
18
Itagaki, S
.
; Sunaba, H
.
; Kamata, K
.
; Yamaguchi, K
.
; Mizuno, N.
Chem. Lett.
2013
,
42
,
980
982.
Supplementary Information for Toutov,
Betz, Haibach, Romine, and
Grubbs
SI
-
21
(204 mg, 230
μ
L, 1.5 mmol, 1.5 equiv), NaOH (4.0 mg, 0.10 mmol, 10 mol%) and THF
(1.0 mL). The reaction was heated to 60°C for 24 hours, then concentrated in vacuo and
purified by
silica gel flash chromatography
(
5% EtOAc in
hexanes) to afford
4s
(
178 mg
,
78% yield) as a
colorless
oil.
R
f
= 0.43 (5% EtOAc in
hexanes
);
1
H NMR (500 MHz,
CDCl
3
)
δ
7.80
7.60 (m, 2H), 7.57
7.38 (m, 3H), 3.84 (t,
J
= 5.8 Hz, 2H), 3.73 (q,
J
=
6.5 Hz, 2H), 3.58 (q,
J
= 7.0 Hz, 1H), 2.17
1.96 (m, 2H), 1.31 (t,
J
= 7.0 Hz, 1H
), 0.50
(d,
J
= 4.3 Hz, 6H)
;
13
C NMR (126 MHz,
CDCl
3
)
δ
137.61, 133.47, 129.75, 127.96, 59.44,
41.71, 35.21,
-
1.87.
Note the high volatility of the product
,
which prevents quantitative
solvent removal by high vacuum (i.e., that some residual solvent signal
s remain).
IR (Neat
Film NaCl) 3069, 3050, 3011, 2958, 2874, 2361, 2343, 1427, 1253, 1118, 1097, 1068, 830,
788, 699 cm
1
; HRMS (FAB+) calc’d for C
11
H
17
ClOSi [M+H]: 229.0816, found 229.0797.
(4
-
M
ethoxyphenoxy)dimethyl(phenyl)silane
4
t
:
The general procedure was followed.
The reaction was performed with
NaOH (2.0 mg, 0.05 mmol, 10
mol %
)
,
4
-
methoxyphenol
(62 mg, 0.5 mmol, 1.0 equiv), PhMe
2
SiH (102 mg, 115 μL, 0.75 mmol, 1.5 equiv), 0.2 mL
dimethylformamide (DMF) and 0.3 mL of tetrahydrofuran (THF) at 65 °C for 18 h. The
desired product
4
t
(
106.0
mg,
82
% yield) was obtained
as a colorless oil
by silica gel flash
chromatography (
5
%
EtOAc in
h
exanes).
R
f
= 0.
45
(
5
%
EtOAc in
hexanes);
1
H NMR (500
MHz,
CDCl
3
)
δ
7.63 (dd, J =
7.8, 1.7 Hz, 2H), 7.45
7.36
(m, 3H), 6.74 (s,
4H), 3.74 (s,
3H), 0.50 (s, 6H);
13
C NMR (126 MHz,
CDCl
3
)
δ
1
54.32, 148.85, 137.40, 133.61,
130.00,
128.06, 120.73, 114.57, 55
.70,
-
1.11.
IR (Neat Film NaCl)
3420, 2958, 2833,1638, 1505,
1465, 1441, 1427, 1253, 1233, 1118, 1037, 911, 831,787, 729, 700
cm
1
; HRMS (EI+)
calc’d for C
15
H
18
O
2
Si [M+•
]:
258.1076
, found
258.1083
.