of 128
Supplementary Information for Toutov,
Betz,
Schuman,
Liu
,
Fedorov
,
Stoltz, and
Grubbs
Alkali metal hydroxide
catalyzed C(
sp
)
H bond silylation
Anton A. Toutov,
1
Kerry N. Betz,
1
David P. Schuman,
1
Wen
-
Bo Liu,
1
Alexey Fedorov,
1
Brian M. Stoltz
1
&
Robert H. Grubbs
1
*
stoltz@caltech.edu,
r
h
g
@caltech.edu
1
Division of Chemistry and Chemical Engineering, California Institute of Technology
Pasadena, California 91125, United States
Present A
ddress: D
epartment of Chemistry and Applied Biosciences, ETH Zürich,
Vladimir Prelog Weg 2, CH
-
8093, Zürich, Switzerland.
Table of Contents
General information
.
................................
................................
................................
...
SI
-
2
Part I.
Reaction optimizations, trace metal analysis, and prelimi
nary mechanistic
investigations
.
................................
................................
................................
...............
SI
-
4
1. Reaction optimization
................................
................................
................................
.....
SI
-
4
2.
T
race metal analysis
by ICP
-
MS
................................
................................
....................
SI
-
6
3
.
Evidence
of H
2
production
................................
................................
............................
SI
-
8
Part II.
Experimental and analytics
.
................................
................................
........
SI
-
1
1
1. General procedure for
MOH
catalyzed silyl
ation and characterization data
...............
SI
-
1
1
2. Multi
-
gram scale synthesi
s of
4s
................................
................................
..................
SI
-
37
3.
Optimization and s
ynthesis
of
mono
-
and
bis
-
silylated diynes
................................
.....
SI
-
38
4.
Geminal
one
-
pot silaboration of alkynes
.
................................
................................
.....
SI
-
4
3
5.
L
ate
-
stage silylation of pharmaceuticals
................................
................................
.......
SI
-
48
6
.
Synthesis of symmetric and unsymmetric diethynylsilanes
................................
.........
SI
-
5
1
Part
III
.
1
H NMR and
13
C NMR spectra of new compounds.
................................
SI
-
5
8
Supplementary Information for Toutov,
Betz, Schuman, Liu
,
Fedorov,
Stoltz, and
Grubbs
SI
-
2
General information.
Unless otherwise stated, reactions were performed in
oven
-
dried brand
-
new Fisherbrand
scintillation vials
in a nitrog
en filled glove box or in flame
-
dried Schlenk flasks under
argon connected on a Schlenk line using dry, degassed solvents and
brand
-
new sti
rring
bars
. Solvents were dried by passage through an activated alumina column under argon.
1
Reaction progress was monitored by thin
-
layer chromatography (TLC)
or
GC
-
FID
analyses
.
TLC was performed using E. Merck silica gel 60 F254 precoated glass plate
s
(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 chromatography.
1
H NMR spectra were recorded on
a
Varian Inova 500
MHz
in CDCl
3
or
THF
-
d
8
and are reported relative to residual solvent peak at
δ
7.26 ppm
or
δ
3.58
ppm respectively.
13
C NMR spectra were recorded on a Varian Inova 500 MHz
spectrometer (
126 MHz
) in CDCl
3
or
THF
-
d
8
and are reported relative to residual solvent
peak at
δ
77.16 ppm or
δ
67.21
ppm respectively. Data for
1
H NMR are reported as follows:
chemical shift (
δ
ppm) (multiplicity, coupling 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)
. GC
-
FID analyses were obtained
on an A
gilent 6890N gas chromatograph equipped with a HP
-
5 (5%
-
phenyl)
-
methylpolysiloxane capillary column (Agilent).
GC
-
MS analyses were obtained on an
Agilent 6850 gas chromatograph equipped with a HP
-
5 (5%
-
phenyl)
-
methylpolysiloxane
capillary column (Agilent)
.
High
resolution mass spectra (HRMS) were acquired from the
California Institute of Technology Mass Spectrometry Facility.
Note that the calculated
mass of the quasi
-
molecular ion does not take into account the loss of the electron mass.
ICP
-
MS analysis w
as conducted at the California Institute of Technology Mass
Spectrometry Facility.
Silanes were purchased from Aldrich and distilled before use. KO
t
-
Bu was purchased from
Aldrich (
sublimed grade, 99.99% trace metals basis
) and used directly.
KOH
was
pur
chased from Aldrich (
semiconductor grade, pellets, 99.99% trace metals basis
)
and was
pulverized (mortar and pestle) and heated (150 °C) under vacuum
for 24 h
prior to use
.
Supplementary Information for Toutov,
Betz, Schuman, Liu
,
Fedorov,
Stoltz, and
Grubbs
SI
-
3
NaOH was purchased from Aldrich (
semiconductor grade, pellets, 99.99% trace metals
basis
)
and was pulverized (mortar and pestle) and heated (150 °C) under vacuum prior to
use
. Alkyne
substrates were purchased from Aldrich, TCI, or Acros
and
used as received
(unless noted
)
.