Iridium-Catalyzed Hydrosilylation of Unactivated Alkenes: Scope and Application to Late-Stage Functionalization

Article abstract of DOI:10.1021/acs.joc.8b02838

Highly efficient and general Ir-catalyzed hydrosilylation of unactivated alkenes with excellent anti-Markovnikov regioselectivity was described. A broad scope of hydrosilylated products were synthesized economically and conveniently from commercially or n

Full text of DOI:10.1021/acs.joc.8b02838

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Note
Iridium-Catalyzed Hydrosilylation of Unactivated Alkenes:
Scope, and Application to Late-Stage Functionalization
Xingze Xie, Xueyan Zhang, Haoyu Yang, Xin Ji, Jianing Li, and Shengtao Ding
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b02838 • Publication Date (Web): 18 Dec 2018
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The Journal of Organic Chemistry
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Iridium-Catalyzed Hydrosilylation of Unactivated Alkenes: Scope,
and Application to Late-Stage Functionalization
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Xingze Xie,† Xueyan Zhang,† Haoyu Yang,† Xin Ji,† Jianing Li,† Shengtao Ding*,†
†State Key Laboratory of Organic-Inorganic Composites, College of Chemical Engineering, Beijing University of
Chemical Technology, Beijing, 100029, China
KEYWORDS: Iridium, hydrosilylation, alkene, late-stage, catalysis
ABSTRACT: Highly efficient and general Ir-catalyzed hydrosilylation of unactivated alkenes with excellent anti-Markovni-
kov regioselectivity was described. A broad scope of hydrosilylated products were synthesized economically and conven-
iently from commercially or naturally available compounds, which provides versatile valuable precursors for organic and
medicinal studies.
Organosilicon compounds are intriguing reagents in or-
ganic transformations because of their great advantages in
stability, solubility, non-toxicity, easy-handling, accessibil-
ity, and selectivity (Figure 1, a).1 Moreover, benefiting from
the unique atomic properties of silicon, silicon analogues
play important roles in drug discovery (Figure 1, b).2 Al-
kene hydrosilylation is one major approach widely used in
industry to provide commodity silicones after the Direct
Process.3 However, application of this atom-economic
strategy in fine chemical synthesis, such as the above-men-
tioned areas, is much less common (Scheme 1, a). Mild and
efficient methods for construction of organosilicons with
Iridium complexes are powerful tools in silylation of a wide
broad substrate scope and high selectivity are still in ur-
variety of functional groups.4 Surprisingly, despite usually
gent desire.
recognized as one main kind of precious metal catalysts in
Figure 1. Selected examples of organosilicon compounds’
applications in organic transformations and pharmaceuti-
cals.
alkene hydrosilylation, reports on exploitation of iridium
complexes for this process are rare. Till now, most of re-
lated works were published as patents, which mainly fo-
cused on simple terminal alkenes.5,6 Inspired by this re-
search vacancy, a few works were released recently.7-10 Shi-
mada reported the iridium-catalyzed hydrosilylation of al-
lyl acetates8 and sulfur-containing olefins10. Kühn gave a
mechanistic study on the iridium-catalyzed hydrosilyla-
tion of allyl compounds.9 Recently, one of us, together with
Sun and Wu, developed iridium-catalyzed hydrosilylation
of internal thioalkynes with excellent regio- and stereose-
lectivity.11 Generation of intermediate Ir(I) hydride A (in
Scheme 1, b) is presumptively crucial in this process, which
we envisioned is probably one key factor in other iridium-
catalyzed hydrosilylation processes as well.10, 11 Meanwhile,
existence of heteroatoms or functional groups that can co-
ordinate to iridium center might facilitate these catalytic
conversions. Herein, we demonstrate our research on the
Ir-catalyzed hydrosilylation of unactivated alkenes with
Scheme 1. Hydrosilylation of alkenes.
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excellent anti-Markovnikov regioselectivity and high effi-
Page 2 of 10
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ciency, which provides complementary examples and ad-
ditional insight to previous reports.5-10, 12 This catalytic sys-
tem is suitable for a broad substrate scope, especially for
those containing heteroatoms. More importantly, it works
effectively on late-stage hydrosilylation, which is rarely re-
ported before.
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8
9
We initiated this study with phenyl allyl sulfide 1a as the
model substrate and triethoxysilane 2a as the silylation re-
agent (Table 1). Several iridium complexes were investi-
gated by using deuterated chloroform as the solvent,
among which [Ir(COD)Cl]2 was identified as the most effi-
cient catalyst, affording linear product 3a in 82% NMR
yield with excellent regioselectivity (Entry 1-4). Chlorin-
ated solvents, such as dichloromethane and dichloro-
ethane, gave better results in this process (Entry 5-13). A
slightly decreased yield of 82% was observed when the
loading amount of the catalyst was reduced to 0.5 mol %
(Entry 14). Furthermore, this reaction could be carried out
in neat status as most industrial productions do, though
providing a moderate yield (Entry 15).
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Table 1. Optimization of Reaction Conditions.
aReaction conditions: The mixture of 1 (0.50 mmol, 1.0
equiv.), 2 (0.75 mmol, 1.5 equiv.) and catalyst (0.01 mmol, 2
mol %) in solvent (2.0 mL) was stirred for 6 h under room
b
b
Entry Cat.
Solvent
CDCl3
Yieldb 3a/3a’
c
temperature. Isolated yield. 3.0 Equivalent of silane was
d
1
[Ir(COD)Cl]2
82
48
17
>99:1
>99:1
--
e
used. 4.5 Equivalent of silane was used. Ratio of allylic
sulfide and silane is 3:1.
2
[Ir(COD)(OMe)]2 CDCl3
3
[Ir(COE)2Cl]2
[Cp*IrCl2]2
CDCl3
CDCl3
DCM
DCE
With the optimized condition in hand, a variety of alkenes
containing sulfur atom were tested to react with different
silanes (Table 2). Good to excellent yields were observed in
the reactions of aryl allyl sulfides bearing diverse func-
tional groups (3a to 3d). As Shimada has reported one sim-
ilar work mainly covering simple aryl and aliphatic sulfur-
containing olefins,10 we turned our attention to more com-
plexed substrates. N-Heterocycles are common structures
in drugs. To probe the efficiency of this catalytic system,
several substrates containing different types of N-hetero-
cycles, including pyridine, pyrimidine, triazine, tetrazole,
and benzo[d]thiazole, were investigated (3e to 3j). Related
products were afforded in moderate to high yields with ex-
cellent regioselectivity in all cases. This system is also ap-
plicable to various alkyl allyl sulfides (3k to 3o). Both
homoallylic and vinylic sulfides performed well under the
mild condition (3p & 3q). Next, we evaluated the silane
scope in this process, and found that several familiar
silanes, including (MeO)3SiH, (EtO)2MeSiH, PhMe2SiH,
and BnMe2SiH, could react with the allylic sulfides
smoothly, providing the desired products 3r-3u with high
efficiency and selectivity. Only a trace amount of product
3v was detected while Et3SiH was used. The success of us-
ing disilane as reaction partner permits the potential appli-
cation of this new developed catalytic system in linear pol-
ymer and porous organic polymer synthesis (3w).
4
<5
93
89
55
47
10
--
5
[Ir(COD)Cl]2
[Ir(COD)Cl]2
[Ir(COD)Cl]2
[Ir(COD)Cl]2
[Ir(COD)Cl]2
[Ir(COD)Cl]2
[Ir(COD)Cl]2
[Ir(COD)Cl]2
[Ir(COD)Cl]2
[Ir(COD)Cl]2
[Ir(COD)Cl]2
>99:1
>99:1
--
6
7
THF
8
MeCN
DMF
--
9
--
10
11
12
13
14c
15
1,4-Dioxane 52
--
Toluene
EtOH
H2O
36
45
--
--
n.d.
82
61
--
DCM
>99:1
neat
>99:1
aReaction conditions: The mixture of 1a (0.10 mmol, 1.0
equiv.), 2a (0.15 mmol, 1.5 equiv.) and catalyst (0.002 mmol,
2 mol %) in solvent (0.50 mL) was stirred for 6 h under
room temperature. bYield and ratio were determined by 1H
NMR spectroscopy using dimethyl sulfone as internal
standard. c0.5 mol % of catalyst was used.
Table 2. Scope of alkenyl sulfides and silanes.
We then turned our attention to oxygen-containing olefins
(Table 3). This catalytic system was proved to be effective
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with numerous catalysts, we just listed several examples
in hydrosilylation of several selected representative aryl/al-
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kyl allyl ethers, including bis(allyl) ethers derived from hy-
droquinone and BINOL (5a to 5f). Vinyl ether could be hy-
drosilylated efficiently as well (5g). Encouraged by these
positive results, more efforts were put on exploring late-
stage hydrosilylation of nature molecule analogues. Inspir-
ingly, allylic ether derivatives from proline, menthol, glu-
cose, and glucofuranose were tolerated well, giving corre-
sponding anti-Markovnikov addition products in good to
excellent yields (5h to 5k). Allyl ether analogues of estrone,
testosterone, and vitamin E were also successfully modi-
fied by using this hydrosilylation protocol (5l to 5n).
here (7j to 7l).
Table 4. Hydrosilylation of other olefins.
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Table 3. Scope of olefins containing oxygen atom.
aReaction conditions: The mixture of 6 (0.50 mmol, 1.0
equiv.), 2 (0.75 mmol, 1.5 equiv.) and catalyst (0.01 mmol, 2
mol %) in solvent (2.0 mL) was stirred for 6 h under room
temperature. Isolated yield. 3.0 Equivalent of silane was
used.
b
c
Sterically hindered disubstituted terminal alkenes were in-
vestigated as well (Scheme 2). No desired product was ob-
served from 8a or 8b (Eq. 1). 8c could be hydrosilylated to
afford 3x in 74% yield, while isomerization of 8d to 9 was
the major phenomenon under the same condition (Eq. 2).
Notably, both of the terminal alkenyl groups in myrcene
(8e) were hydrosilylated (7m, Eq. 3).
Scheme 2. Hydrosilylation of disubstituted terminal al-
kenes.
aReaction conditions: The mixture of 4 (0.50 mmol, 1.0
equiv.), 2 (0.75 mmol, 1.5 equiv.) and catalyst (0.01 mmol, 2
mol %) in solvent (2.0 mL) was stirred for 6 h under room
b
c
temperature. Isolated yield. 3.0 Equivalent of silane was
used.
Based on previous reports and our observation,10, 11 a plau-
sible mechanism is given in Scheme 3. Heteroatoms or
functional groups in the substrates is presumed to coordi-
nate to iridium center and could help to stabilize possible
intermediates C and D, which would facilitate the catalytic
cycle. This coordination effect might be more critical to-
wards disubstituted terminal alkenes. More detailed mech-
anism studies are underway.
Having examined alkenes containing chalcogens, we took
a further step to check the capacity of the Ir-catalyzed hy-
drosilylation processes for functional groups or other ele-
ments (Table 4). Allylic sulfone and ester were compatible
with this method (7a & 7b). The reactions of allylic tertiary
and secondary amines provided desired hydrosilylated
product (7c & 7d). Allyl phosphine showed poor reactivity,
which might be due to the coordination of phosphine atom
with iridium which obstructs the formation of active cata-
lyst intermediate A, as the reaction of allylic phosphonate
with (EtO)3SiH proceeded smoothly under this condition
(7e). The investigation of this protocol for allyl bromide
and allyl Bpin gave satisfied results with excellent yields (7f
& 7g). Sterically bulky allylsilane and vinylsilane were con-
verted into related products in good yields (7h & 7i). As
hydrosilylation of alkyl/aryl olefins has been addressed
Scheme 3. Proposed mechanism.
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Page 4 of 10
(3-((4-Chlorophenyl)thio)propyl)triethoxysilane (3b) was
prepared as pale yellow oil from 1b (0.50 mmol, 92.4 mg) and
1
2
3
(EtO)3SiH (0.75 mmol, 125.8 mg), according to the General
1
Procedure in 86% yield (150.1 mg, l/b > 99:1): H NMR (400
MHz, CDCl3) δ 7.26-7.20 (m, 4 H), 3.80 (q, J = 6.8 Hz, 6 H),
2.92 (t, J = 7.2 Hz, 2 H), 1.79-1.70 (m, 2 H), 1.20 (t, J = 6.8 Hz, 9
H), 0.79-0.74 (m, 2 H); 13C {1H} NMR (100 MHz, CDCl3) δ 135.3,
131.5, 130.3, 128.8, 58.3, 36.5, 22.6, 18.2, 9.7; HRMS m/z (CI)
calcd. for C15H25ClO3SSiNa (M+Na)+ 371.0880, found 371.0898.
Triethoxy(3-(p-tolylthio)propyl)silane (3c) was prepared as
pale yellow oil from 1c (0.50 mmol, 82.1 mg) and (EtO)3SiH
(0.75 mmol, 125.8 mg), according to the General Procedure in
84% yield (138.0 mg, l/b > 99:1): 1H NMR (400 MHz, CDCl3) δ
7.24 (d, J = 8.0 Hz, 2 H), 7.06 (d, J = 8.0 Hz, 2 H), 3.79 (q, J =
6.8 Hz, 6 H), 2.90 (t, J = 7.2 Hz, 2 H), 2.30 (s, 3 H), 1.77-1.69 (m,
2 H), 1.20 (t, J = 6.8 Hz, 9 H), 0.79-0.75 (m, 2 H); 13C {1H} NMR
(100 MHz, CDCl3) δ 135.7, 132.8, 129.9, 129.5, 58.3, 37.1, 22.7, 20.8,
18.2, 9.7; HRMS m/z (CI) calcd. for C16H28O3SSiNa (M+Na)+
351.1426, found 351.1419.
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In summary, we demonstrated the efficiency and compati-
bility of one simple, mild iridium catalytic system in hy-
drosilylation of unactivated alkenes. A wide scope of anti-
Markovnikov hydrosilylated products with excellent regi-
oselectivity were afforded conveniently from commercially
or naturally available compounds, providing versatile val-
uable blocks for organic and medicinal studies.
Triethoxy(3-((4-methoxyphenyl)thio)propyl)silane (3d) was
prepared as pale yellow oil from 1d (0.50 mmol, 90.1 mg) and
(EtO)3SiH (0.75 mmol, 125.8 mg), according to the General
1
Procedure in 76% yield (130.9 mg, l/b > 99:1): H NMR (400
EXPERIMENTAL SECTION
MHz, CDCl3) δ 7.28-7.24 (m, 2 H), 6.78-6.74 (m, 2 H), 3.72 (q,
J = 6.8 Hz, 6 H), 3.71 (s, 3 H), 2.77 (t, J = 7.2 Hz, 2 H), 1.66-1.58
(m, 2 H), 1.13 (t, J = 6.8 Hz, 9 H), 0.70-0.66 (m, 2 H); 13C {1H}
NMR (100 MHz, CDCl3) δ 158.7, 133.0, 126.6, 114.4, 58.3, 55.3,
38.7, 22.8, 18.2, 9.6; HRMS m/z (CI) calcd. for C16H28O4SSiNa
(M+Na)+ 367.1375, found 367.1365.
General Information. All air or moisture sensitive reac-
tions were conducted in oven-dried glassware under nitrogen
atmosphere using dry solvents. Flash column chromatography
was performed over silica gel (200-300 mesh) purchased from
Qingdao Puke Co., China. Silanes and common organic chem-
icals were purchased from commercial suppliers, such as
Sigma-Aldrich® and J&K® Scientific Ltd., and used as received.
Iridium complexes were purchased from Strem® Chemicals,
2-((3-(Triethoxysilyl)propyl)thio)pyridine (3e) was prepared
as pale yellow oil from 1e (0.50 mmol, 75.6 mg) and (EtO)3SiH
(0.75 mmol, 125.8 mg), according to the General Procedure in
1
1
53% yield (83.6 mg, l/b > 99:1): H NMR (400 MHz, CDCl3) δ
Inc. H and 13C NMR spectra were collected on a Bruker AV
8.44-8.42 (m, 1 H), 7.50-7.45 (m, 1 H), 7.19 (d, J = 8.4 Hz, 1 H),
7.00-6.95 (m, 1 H), 3.83 (q, J = 7.2 Hz, 6 H), 3.21 (t, J = 7.2 Hz, 2
H), 1.90-1.81 (m, 2 H), 1.23 (t, J = 7.2 Hz, 9 H), 0.84 (t, J = 8.0
Hz, 2 H); 13C {1H} NMR (100 MHz, CDCl3) δ 159.4, 149.4, 135.8,
122.1, 119.1, 58.4, 33.1, 23.0, 18.3, 10.0; MS (ESI) m/z (relative in-
tensity) 315.4 (5), 55.1 (100) [M]+.
400 MHz NMR spectrometer using residue solvent peaks as
an internal standard (1H NMR: CDCl3 at 7.26 ppm, 13C NMR:
CDCl3 at 77.0 ppm). Mass spectra were collected on an
Thermo Scientific GC/MS ISQ7000 system, or a Xevo G2 Qtof
mass spectrometer.
Safety Note. Triethoxysilane is a corrosive and flammable
liquid. Methyldiethoxysilane is advised to be used for large-
scale (> 1.0 g) reactions instead.
2-((3-(Triethoxysilyl)propyl)thio)pyrimidine (3f) was pre-
pared as pale yellow oil from 1f (0.50 mmol, 76.1 mg) and
(EtO)3SiH (0.75 mmol, 125.8 mg), according to the General
General Procedure for Hydrosilylation. In a glove box,
to an oven-dried 5-mL vial was added the alkene (0.50 mmol),
the silane (0.75 mmol), [Ir (COD)Cl]2 (0.008 mmol), and DCM
(2.0 mL). The vial was capped and removed from the glove box.
The reaction mixture was stirred at room temperature for 4 h,
and then concentrated under reduced pressure. The residue
was purified by silica gel flash column chromatography (elu-
ent: 0-50% EtOAc in petroleum ether) to give the desired
product. Compounds 3a,10 3e,13 3i,14 3j,13 3k,15 3l,16 3o,17 3q,18 3r,10
3s,10 5a,19 5c,20 5e,21 5f,22 5g,23 5i,24 5n,25 7a,26 7b,27 7d,28 7f,29 7g,30
7h,28 7j,31 7k,28 7l31 are known compounds. Result of MS was
given for known compounds, and result of HRMS was given
for unknown compounds.
Triethoxy(3-(phenylthio)propyl)silane (3a) was prepared as
pale yellow oil from 1a (0.50 mmol, 75.1 mg) and (EtO)3SiH
(0.75 mmol, 125.8 mg), according to the General Procedure in
93% yield (146.2 mg, l/b > 99:1): 1H NMR (400 MHz, CDCl3) δ
7.37-7.33 (m, 2 H), 7.31-7.25 (m, 2 H), 7.20-7.14 (m, 1 H), 3.82 (q,
J = 8.0 Hz, 6 H), 2.98 (t, J = 7.2 Hz, 2 H), 1.84-1.75 (m, 2 H), 1.23
(t, J = 8.0 Hz, 9 H), 0.81 (t, J = 8.0 Hz, 2 H); 13C {1H} NMR (100
MHz, CDCl3) δ 136.7, 129.0, 128.7, 125.6, 58.3, 36.4, 22.7, 18.2,
9.7; MS (ESI) m/z (relative intensity) 314.1 (5), 163.1 (100) [M]+.
1
Procedure in 80% yield (126.6 mg, l/b > 99:1): H NMR (400
MHz, CDCl3) δ 8.47 (d, J = 5.2 Hz, 2 H), 6.92 (dd, J1 = J2 = 5.2
Hz, 1 H), 3.80 (q, J = 6.8 Hz, 6 H), 3.16 (t, J = 7.6 Hz, 2 H), 1.89-
1.80 (m, 2 H), 1.20 (t, J = 6.8 Hz, 9 H), 0.80 (t, J = 8.0 Hz, 2 H);
13C {1H} NMR (100 MHz, CDCl3) δ 172.6, 157.0, 116.1, 58.2, 33.6,
22.7, 18.1, 9.8; HRMS m/z (CI) calcd. for C13H24N2O3SSiNa
(M+Na)+ 339.1175, found 339.1179.
2, 4-Bis((3-(triethoxysilyl)propyl)thio)pyrimidine (3g) was
prepared as pale yellow oil from 1g (0.50 mmol, 112.17 mg) and
(EtO)3SiH (1.50 mmol, 251.6 mg), according to the General
1
Procedure in 85% yield (235.0 mg, l/b > 99:1): H NMR (400
MHz, CDCl3) δ 8.07 (d, J = 5.2 Hz, 1 H), 6.78 (d, J = 5.2 Hz, 1 H),
3.85-3.79 (m, 12 H), 3.20-3.14 (m, 4 H), 1.91-1.80 (m, 4 H), 1.24-
1.20 (m, 18 H), 0.83-0.76 (m, 4 H); 13C {1H} NMR (100 MHz,
CDCl3) δ 171.6, 170.0, 154.1, 114.0, 58.23, 58.19, 33.6, 31.9, 22.8,
22.7, 18.1, 9.9; HRMS m/z (CI) calcd. for C22H45N2O6S2Si2
(M+H)+ 553.2258, found 553.2272.
2, 4, 6-Tris((3-(triethoxysilyl)propyl)thio)-1, 3, 5-triazine (3h)
was prepared as pale yellow oil from 3h (0.50 mmol, 148.7 mg)
and (EtO)3SiH (2.25 mmol, 377.4 mg), according to the Gen-
1
eral Procedure in 65% yield (256.8 mg, l/b > 99:1): H NMR
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(400 MHz, CDCl3) δ 3.81 (q, J = 6.8 Hz, 18 H), 3.10 (t, J = 7.2 Hz,
(0.75 mmol, 125.8 mg), according to the General Procedure in
99% yield (158.7 mg, l/b > 99:1): 1H NMR (400 MHz, CDCl3) δ
3.82 (q, J = 6.8 Hz, 6 H), 2.65-2.59 (m, 1 H), 2.55 (t, J = 7.2 Hz,
2 H), 1.98-1.95 (m, 2 H), 1.78-1.75 (m, 2 H), 1.73-1.65 (m, 2 H),
1.33-1.25 (m, 6 H), 1.23 (t, J = 6.8 Hz, 9 H), 0.77-0.72 (m, 2 H);
13C {1H} NMR (100 MHz, CDCl3) δ 58.3, 43.2, 33.7, 33.1, 26.1, 25.8,
23.6, 18.2, 9.9; MS (ESI) m/z (relative intensity) 320.1 (6), 163.1
(100) [M]+.
1
2
3
4
5
6
7
8
6 H), 1.87-1.78 (m, 6 H), 1.21 (t, J = 6.8 Hz, 27 H), 0.79-0.74 (m,
6 H); 13C {1H} NMR (100 MHz, CDCl3) δ 179.4, 58.3, 33.1, 22.7,
18.2, 9.9; HRMS m/z (CI) calcd. for C30H63N3O9S3Si3Na
(M+Na)+ 812.2932, found 812.2925.
1-Methyl-5-((3-(triethoxysilyl)propyl)thio)-1H-tetrazole (3i)
was prepared as pale yellow oil from 1i (0.50 mmol, 78.1 mg)
and (EtO)3SiH (0.75 mmol, 125.8 mg), according to the Gen-
eral Procedure in 90% yield (144.2 mg, l/b > 99:1): 1H NMR (400
MHz, CDCl3) δ 3.90 (s, 3 H), 3.79 (q, J = 7.2 Hz, 6 H), 3.35 (t, J
= 7.2 Hz, 2 H), 1.94-1.85 (m, 2 H), 1.19 (t, J = 7.2 Hz, 9 H), 0.76
(t, J = 8.0 Hz, 2 H); 13C {1H} NMR (100 MHz, CDCl3) δ 154.2, 58.3,
35.9, 33.2, 23.1, 18.1, 9.7; MS (ESI) m/z (relative intensity) 320.1
(5), 163.1 (100) [M]+.
Triethoxy(4-(p-tolylthio)butyl)silane (3p) was prepared as
pale yellow oil from 1p (0.50 mmol, 89.1 mg) and (EtO)3SiH
(0.75 mmol, 125.8 mg), according to the General Procedure in
80% yield (137.0 mg, l/b > 99:1): 1H NMR (400 MHz, CDCl3) δ
7.25-7.22 (m, 2 H), 7.09-7.05 (m, 2 H), 3.80 (q, J = 6.8 Hz, 6 H),
2.87 (t, J = 7.2 Hz, 2 H), 2.30 (s, 3 H), 1.70-1.62 (m, 2 H), 1.58-
1.50 (m, 2 H), 1.20 (t, J = 6.8 Hz, 9 H), 0.65-0.61 (m, 2 H); 13C
{1H} NMR (100 MHz, CDCl3) δ 135.7, 133.1, 129.7, 129.5, 58.2, 33.8,
32.4, 22.0, 20.8, 18.2, 9.9; HRMS m/z (CI) calcd. for
C17H30O3SSiNa (M+Na)+ 365.1583, found 365.1580.
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2-((3-(Triethoxysilyl)propyl)thio)benzo[d]thiazole (3j) was
prepared as pale yellow oil from 1j (0.50 mmol, 103.7 mg) and
(EtO)3SiH (0.75 mmol, 125.8 mg), according to the General
1
Procedure in 96% yield (178.4 mg, l/b > 99:1): H NMR (400
MHz, CDCl3) δ 7.87 (d, J = 8.4 Hz, 1 H), 7.77 (d, J = 8.4 Hz, 1 H),
7.45-7.40 (m, 1 H), 7.33-7.28 (m, 1 H), 3.85 (q, J = 7.2 Hz, 6 H),
3.40 (t, J = 7.2 Hz, 2 H), 2.03-1.94 (m, 2 H), 1.24 (t, J = 7.2 Hz, 9
H), 0.88-0.83 (m, 2 H); 13C {1H} NMR (100 MHz, CDCl3) δ 167.2,
153.4, 135.2, 125.9, 124.0, 121.4, 120.8, 58.4, 36.4, 23.0, 18.2, 9.9;
MS (ESI) m/z (relative intensity) 371.1 (5), 167.0 (100) [M]+.
Triethoxy(3-(methylthio)propyl)silane (3k) was prepared as
pale yellow oil from 1k (0.50 mmol, 44.1 mg) and (EtO)3SiH
(0.75 mmol, 125.8 mg), according to the General Procedure in
Triethoxy(2-(phenylthio)ethyl)silane (3q) was prepared as
pale yellow oil from 1q (0.50 mmol, 68.1 mg) and (EtO)3SiH
(0.75 mmol, 125.8 mg), according to the General Procedure in
1
47% yield (70.6 mg, l/b > 99:1): H NMR (400 MHz, CDCl3) δ
7.29-7.24 (m, 2 H), 7.23-7.19 (m, 2 H), 7.18-7.13 (m, 1 H), 3.82 (q,
J = 6.8 Hz, 6 H), 2.77-2.73 (m, 2 H), 1.23 (t, J = 6.8 Hz, 9 H),
1.02-0.97 (m, 2 H); 13C {1H} NMR (100 MHz, CDCl3) δ 144.6,
128.2, 127.7, 125.6, 58.3, 28.8, 18.3, 12.5; MS (ESI) m/z (relative
intensity) 300.1 (5), 163.1 (100) [M]+.
Trimethoxy(3-(phenylthio)propyl)silane (3r) was prepared
as pale yellow oil from 1a (0.50 mmol, 75.1 mg) and (MeO)3SiH
(0.75 mmol, 91.6 mg), according to the General Procedure in
68% yield (92.6 mg, l/b > 99:1): 1H NMR (400 MHz, CDCl3) δ
7.37-7.34 (m, 2 H), 7.31-7.25 (m, 2 H), 7.21-7.14 (m, 1 H), 3.57 (s,
9 H), 2.97 (t, J = 7.2 Hz, 2 H), 1.83-1.74 (m, 2 H), 0.85-0.81 (m,
2 H); 13C {1H} NMR (100 MHz, CDCl3) δ 136.6, 129.0, 128.8, 125.7,
50.4, 36.3, 22.5, 8.4; MS (ESI) m/z (relative intensity) 272.1 (12),
121.0 (100) [M]+.
1
66% yield (83.3 mg, l/b > 99:1): H NMR (400 MHz, CDCl3) δ
3.82 (q, J = 7.2 Hz, 6 H), 2.52 (t, J = 6.8 Hz, 2 H), 2.09 (s, 1 H),
1.78-1.69 (m, 2 H), 1.22 (t, J = 7.2 Hz, 9 H), 0.74 (t, J = 8.4 Hz, 2
H); 13C {1H} NMR (100 MHz, CDCl3) δ 58.4, 37.2, 22.6, 18.3, 18.3,
9.7; MS (ESI) m/z (relative intensity) 252.1 (7), 163.1 (100) [M]+.
(3-(Benzylthio)propyl)triethoxysilane (3l) was prepared as
pale yellow oil from 1l (0.50 mmol, 82.1 mg) and (EtO)3SiH
(0.75 mmol, 125.8 mg), according to the General Procedure in
1
73% yield (119.9 mg, l/b > 99:1): H NMR (400 MHz, CDCl3) δ
7.32-7.29 (m, 4 H), 7.25-7.20 (m, 1 H), 3.80 (q, J = 6.8 Hz, 6 H),
3.70 (s, 2 H), 2.44 (t, J = 7.2 Hz, 2 H), 1.72-1.64 (m, 2 H), 1.22 (t,
J = 6.8 Hz, 9 H), 0.72-0.68 (m, 2 H); 13C {1H} NMR (100 MHz,
CDCl3) δ 138.6, 128.8, 128.4, 126.8, 58.3, 36.1, 34.4, 22.7, 18.3, 9.9;
MS (ESI) m/z (relative intensity) 328.1 (5), 91.0 (100) [M]+.
Triethoxy(3-(tritylthio)propyl)silane (3m) was prepared as
white powder from 1m (0.50 mmol, 158.2 mg) and (EtO)3SiH
(0.75 mmol, 125.8 mg), according to the General Procedure in
Diethoxy(methyl)(3-(phenylthio)propyl)silane (3s) was pre-
pared as pale yellow oil from 1a (0.50 mmol, 75.1 mg) and ,
(EtO)2MeSiH (0.75 mmol, 100.8 mg)according to the General
1
Procedure in 79% yield (112.4 mg, l/b > 99:1): H NMR (400
MHz, CDCl3) δ 7.25-7.21 (m, 2 H), 7.19-7.14 (m, 2 H), 7.08-7.03
(m, 1 H), 3.64 (q, J = 7.2 Hz, 6 H), 2.85 (t, J = 7.2 Hz, 2 H), 1.67-
1.58 (m, 2 H), 1.10 (t, J = 7.2 Hz, 9 H), 0.69-0.64 (m, 2 H), 0.00
(s, 3 H); 13C {1H} NMR (100 MHz, CDCl3) δ 136.7, 129.0, 128.8,
125.7, 58.1, 36.7, 22.8, 18.3, 13.4, -4.9; MS (ESI) m/z (relative in-
tensity) 284.09 (9), 133.1 (100) [M]+.
1
72% yield (173.1 mg, l/b > 99:1): H NMR (400 MHz, CDCl3)
δ7.52-7.48 (m, 6 H), 7.36-7.32 (m, 6 H), 7.29-7.24 (m, 3 H), 3.83
(q, J = 7.2 Hz, 6 H), 2.28 (t, J = 7.2 Hz, 2H), 1.66-1.58 (m, 2H),
1.27 (t, J = 7.2 Hz, 9 H), 0.68 (t, J = 8.0 Hz, 2 H); 13C {1H} NMR
(100 MHz, CDCl3) δ 145.1, 129.6, 127.8, 126.5, 66.3, 58.3, 35.1, 22.3,
18.2, 10.3; HRMS m/z (CI) calcd. for C28H36O3SSiNa (M+Na)+
503.2052, found 503.2048.
Dimethyl(phenyl)(3-(phenylthio)propyl)silane (3t) was pre-
pared as pale yellow oil from 1a (0.50 mmol, 75.1 mg) and
PhMe2SiH (0.75 mmol, 102.3 mg), according to the General
1
Procedure in 85% yield (121.8 mg, l/b > 99:1): H NMR (400
MHz, CDCl3) δ 7.56-7.52 (m, 2 H), 7.42-7.39 (m, 2 H), 7.39-7.38
(m, 1 H), 7.34-7.27 (m, 4 H), 7.22-7.18 (m, 1 H), 2.96 (t, J = 7.2
Hz, 2 H), 1.76-1.68 (m, 2 H), 0.99-0.93 (m, 2 H), 0.31 (s, 6 H);
13C {1H} NMR (100 MHz, CDCl3) δ 138.9, 136.8, 133.5, 129.0, 128.9,
128.8, 127.8, 125.6, 37.1, 23.7, 15.2, -3.1; HRMS m/z (CI) calcd. for
C17H22SSiNa (M+Na)+ 309.1109, found 309.1132.
Triethoxy(3-((furan-2-ylmethyl)thio)propyl)silane (3n) was
prepared as pale yellow oil from 1n (0.50 mmol, 77.1 mg) and
(EtO)3SiH (0.75 mmol, 125.8 mg), according to the General
1
Procedure in 63% yield (100.3 mg, l/b > 99:1): H NMR (400
MHz, CDCl3) δ 7.36-7.34 (m, 1 H), 6.31-6.29 (m, 1 H), 6.18-6.16
(m, 1 H), 3.81 (q, J = 7.2 Hz, 6 H), 3.71 (s, 2 H), 2.53 (t, J = 7.6 Hz,
2 H), 1.73-1.64 (m, 2 H), 1.22 (t, J = 7.2 Hz, 9 H), 0.74-0.69 (m,
2 H); 13C {1H} NMR (100 MHz, CDCl3) δ 151.9, 142.0, 110.3, 107.2,
58.4, 34.8, 28.1, 22.8, 18.3, 9.9; HRMS m/z (CI) calcd. for
C14H26O4SSiNa (M+Na)+ 341.1219, found 341.1228.
Benzyldimethyl(3-(phenylthio)propyl)silane (3u) was pre-
pared as pale yellow oil from 1a (0.50 mmol, 75.1 mg) and
BnMe2SiH (0.75 mmol, 112.8 mg), according to the General
1
Procedure in 96% yield (144.3 mg, l/b > 99:1): H NMR (400
MHz, CDCl3) δ 7.37-7.31 (m, 4 H), 7.26-7.22 (m, 2 H), 7.21-7.18
(m, 1 H), 7.13-7.07 (m, 1 H), 7.02-6.98 (m, 2 H), 2.94 (t, J = 7.2
Hz, 2 H), 2.11 (s, 2 H), 1.70-1.62 (m, 2 H), 0.74-0.65 (m, 2 H),
(3-(Cyclohexylthio)propyl)triethoxysilane (3o) was prepared
as pale yellow oil from 1o (0.50 mmol, 78.1 mg) and (EtO)3SiH
ACS Paragon Plus Environment

The Journal of Organic Chemistry
Page 6 of 10
0.00 (s, 6 H); 13C {1H} NMR (100 MHz, CDCl3) δ 140.0, 136.8,
128.9, 128.8, 128.2, 128.0, 125.7, 123.9, 37.1, 25.4, 23.8, 14.4, -3.7;
HRMS m/z (CI) calcd. for C18H24SSiNa (M+Na)+ 323.1266,
found 323.1260.
2, 2'-Bis(3-(triethoxysilyl)propoxy)-1, 1'-binaphthalene (5e)
was prepared as pale yellow oil from 4e (0.50 mmol, 183.2 mg)
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2
3
4
5
6
7
8
and (EtO)3SiH (1.50 mmol, 251.6 mg), according to the General
1
Procedure in 88% yield (305.8 mg, l/b > 99:1): H NMR (400
1,4-Bis(dimethyl(3-(phenylthio)propyl)silyl)benzene
(3w)
MHz, CDCl3) δ 7.95-7.93 (m, 2 H), 7.88-7.84 (m, 2 H), 7.45-7.41
(m, 2 H), 7.34-7.29 (m, 2 H), 7.25-7.18 (m, 4 H), 4.01-3.91 (m, 4
H), 3.63 (q, J = 7.2 Hz, 12 H), 1.60-1.52 (m, 4 H), 1.15 (t, J = 7.2
Hz, 18 H), 0.38-0.24 (m, 4 H); 13C {1H} NMR (100 MHz, CDCl3)
δ 154.4, 134.2, 129.2, 128.9, 127.7, 126.0, 125.4, 123.3, 120.3, 115.4,
71.4, 58.1, 22.8, 18.2, 5.7; MS (ESI) m/z (relative intensity) 694.8
(12), 205.3 (100) [M]+.
was prepared as pale yellow oil from 1a (1.00 mmol, 150.2 mg)
and 1,4-bis (dimethylsilyl)benzene (0.50 mmol, 97.2 mg)ac-
cording to the General Procedure in 67% yield (165.8 mg, l/b >
1
99:1): H NMR (400 MHz, CDCl3) δ 7.50-7.48 (m, 4 H), 7.35-
7.22 (m, 8 H), 7.21-7.18 (m, 2 H), 2.96 (t, J = 7.2 Hz, 4 H), 1.79-
1.57 (m, 4 H), 0.95 (t, J = 8.0 Hz, 4 H), 0.29 (s, 12H); 13C {1H}
NMR (100 MHz, CDCl3) δ 139.6, 136.8, 132.9, 129.1, 128.8, 125.7,
37.2, 23.7, 15.2, -3.2; HRMS m/z (CI) calcd. for C28H38S2Si2Na
(M+Na)+ 517.1850, found 517.1829.
Dimethyl(2-methyl-3-(p-tolylthio)propyl)(phenyl)silane (3x)
was prepared as pale yellow oil from 8c (0.50 mmol, 89.1 mg)
and PhMe2SiH (0.75 mmol, 102.3 mg), according to the Gen-
eral Procedure in 74% yield (116.3 mg, l/b > 99:1): 1H NMR (400
MHz, CDCl3) δ 7.61-7.58 (m, 2 H), 7.46-7.41 (m, 3 H), 7.30-7.24
(m, 2 H), 7.18-7.12 (m, 2 H), 2.94-2.79 (m, 2 H), 2.41 (s, 3 H),
2.05-1.90 (m, 1 H), 1.30-1.20 (m, 1 H), 1.10 (d, J = 6.8 Hz, 3 H),
0.90-0.80 (m, 1 H), 0.39 (s, 6 H); 13C {1H} NMR (100 MHz, CDCl3)
δ 139.4, 135.6, 133.5, 129.8, 129.5, 128.8, 127.7, 45.2, 29.7, 23.5, 22.3,
20.9, -2.0, -2.3; HRMS m/z (CI) calcd. for C19H30NSSi
(M+NH4+)+ 332.1863, found 332.1882.
Triethoxy(3-phenoxypropyl)silane (5a) was prepared as pale
yellow oil from 4a (0.50 mmol, 67.1 mg) and (EtO)3SiH (0.75
mmol, 125.8 mg), according to the General Procedure in 83%
yield (123.9 mg, l/b > 99:1): 1H NMR (400 MHz, CDCl3) δ 7.34-
7.27 (m, 2 H), 7.00-6.91 (m, 3 H), 3.98 (t, J = 6.8 Hz, 2 H), 3.87
(q, J = 7.2 Hz, 6 H), 2.00-1.90 (m, 2 H), 1.27 (t, J = 7.2 Hz, 9 H),
0.81 (t, J = 8.0 Hz, 2 H); 13C {1H} NMR (100 MHz, CDCl3) δ 159.0,
129.3, 120.4, 114.5, 69.7, 58.4, 22.8, 18.2, 6.5; MS (ESI) m/z (rela-
tive intensity) 298.1 (5), 163.1 (100) [M]+.
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Benzyl(3-methoxypropyl)dimethylsilane (5f) was prepared
as pale yellow oil from 4f (0.50 mmol, 36.1 mg) and BnMe2SiH
(0.75 mmol, 112.8 mg), according to the General Procedure in
96% yield (106.8 mg, l/b > 99:1): 1H NMR (400 MHz, CDCl3) δ
7.29-7.23 (m, 2 H), 7.15-7.09 (m, 1 H), 7.07-7.03 (m, 2 H), 3.38
(s, 3 H), 3.37 (t, J = 6.8 Hz, 2 H), 2.15 (s, 2 H), 1.66-1.59 (m, 2 H),
0.60-0.50 (m, 2 H), 0.04 (s, 6 H); 13C {1H} NMR (100 MHz,
CDCl3) δ 140.2, 128.1, 128.0, 123.8, 75.5, 58.4, 25.4, 23.8, 10.7, -3.8;
MS (ESI) m/z (relative intensity) 222.1 (5), 149.1 (100) [M]+.
(2-Butoxyethyl)triethoxysilane (5g) was prepared as pale
yellow oil from 4g (0.50 mmol, 50.1 mg) and (EtO)3SiH (0.75
mmol, 125.8 mg), according to the General Procedure in 92%
1
yield (121.6 mg, l/b > 99:1): H NMR (400 MHz, CDCl3) δ 3.75
(q, J = 7.2 Hz, 6 H), 3.50-3.47 (m, 2 H), 3.33 (t, J = 6.8 Hz, 2 H),
1.52-1.43 (m, 2 H), 1.35-1.25 (m, 2 H), 1.16 (t, J = 7.2 Hz, 9 H), 1.01
(t, J = 8.0 Hz, 2 H), 0.85 (t, J = 7.2 Hz, 3 H); 13C {1H} NMR (100
MHz, CDCl3) δ 70.2, 66.3, 58.4, 31.9, 19.4, 18.2, 13.9, 12.9; MS
(ESI) m/z (relative intensity) 264.1 (5), 163.1 (100) [M]+.
(R)-tert-Butyl 2-((3-(triethoxysilyl)propoxy)methyl)pyrroli-
dine-1-carboxylate (5h) was prepared as pale yellow oil from
4h (0.50 mmol, 120.7 mg) and (EtO)3SiH (0.75 mmol, 125.8 mg),
according to the General Procedure in 80% yield (162.2 mg,
l/b > 99:1): 1H NMR (400 MHz, CDCl3) δ 4.00-3.80 (m, 2 H),
3.79 (q, J = 6.8 Hz, 6 H), 3.52-3.49 (m, 1 H), 3.44-3.32 (m, 2 H),
3.33-3.22 (m, 2 H), 1.92-1.85 (m, 2 H), 1.82-1.72 (m, 2 H)，1.70-
1.51 (m, 2 H), 1.44 (s, 9 H), 1.20 (t, J = 6.8 Hz, 9 H), 0.63-0.58
(m, 2 H); 13C {1H} NMR (100 MHz, CDCl3) δ 154.4, 79.0, 73.4,
71.4, 70.8, 58.2, 56.4, 46.7, 46.3, 28.4, 23.0, 18.2, 6.4; HRMS m/z
(CI) calcd. for C19H39NO6SiNa (M+Na)+ 428.2445, found
428.2448.
(3-([1, 1'-Biphenyl]-2-yloxy)propyl)triethoxysilane (5b) was
prepared as pale yellow oil from 4b (0.50 mmol, 105.1 mg) and
(EtO)3SiH (0.75 mmol, 125.8 mg), according to the General
1
Procedure in 99% yield (185.4 mg, l/b > 99:1): H NMR (400
MHz, CDCl3) δ7.49-7.44 (m, 2 H), 7.32-7.27 (m, 2 H), 7.27-7.18
(m, 3 H), 6.96-6.86 (m, 2 H), 3.86 (t, J = 6.4 Hz, 2 H), 3.70 (q, J
= 7.2 Hz, 6 H), 1.79-1.71 (m, 2 H), 1.12 (t, J = 7.2 Hz, 9 H), 0.64-
0.59 (m, 2 H); 13C {1H} NMR (100 MHz, CDCl3) δ 155.9, 138.6,
130.9, 130.8, 129.6, 128.5, 127.7, 126.6, 120.7, 112.5, 70.3, 58.3, 22.8,
18.2, 6.5; HRMS m/z (CI) calcd. for C21H30O4SiNa (M+Na)+
397.1811, found 397.1810.
8, 8-diethoxy-2, 2, 3, 3-tetramethyl-4, 9-dioxa-3, 8-disilaun-
decane (5c) was prepared as pale yellow oil from 4c (0.50 mmol,
95.1 mg) and (EtO)3SiH (0.75 mmol, 125.8 mg), according to
the General Procedure in 92% yield (238.6 mg, l/b > 99:1): 1H
NMR (400 MHz, CDCl3) δ 3.81 (q, J = 7.2 Hz, 6 H), 3.56 (t, J =
6.8 Hz, 2 H), 1.68-1.58 (m, 2 H), 1.21 (t, J = 7.2 Hz, 9 H), 0.88 (s,
9 H), 0.65-0.59 (m, 2 H), 0.03 (s, 6 H); 13C {1H} NMR (100 MHz,
CDCl3) δ 65.4, 58.3, 26.1, 25.9, 18.3, 18.2, 6.1, -5.3; MS (ESI) m/z
(relative intensity) 336.2 (5), 237.3 (100) [M]+.
1, 4-Bis(3-(triethoxysilyl)propoxy)benzene (5d) was prepared
as pale yellow oil from 4d (0.50 mmol, 95.1 mg) and (EtO)3SiH
(1.50 mmol, 251.6 mg), according to the General Procedure in
92% yield (238.6 mg, l/b > 99:1): 1H NMR (400 MHz, CDCl3) δ
6.73 (s, 4 H), 3.81 (t, J = 6.8 Hz, 4 H), 3.75 (q, J = 6.8 Hz, 12 H),
1.83-1.76 (m, 4 H), 1.15 (t, J = 6.8 Hz, 18 H), 0.70-0.66 (m, 4 H);
13C {1H} NMR (100 MHz, CDCl3) δ 153.0, 115.3, 70.4, 58.3, 22.8,
18.2, 6.4. HRMS m/z (CI) calcd. for C24H46O8Si2Na (M+Na)+
541.2629, found 541.2624.
Triethoxy(3-(((1R,
2S,
5R)-2-isopropyl-5-methylcyclo-
hexyl)oxy)propyl)silane (5i) was prepared as pale yellow oil
from 4i (0.50 mmol, 98.2 mg) and (EtO)3SiH (0.75 mmol, 125.8
mg), according to the General Procedure in 89% yield (160.3
mg, l/b > 99:1): 1H NMR (400 MHz, CDCl3) δ 3.80 (q, J = 7.2 Hz,
6 H), 3.58-3.53 (m, 1 H), 3.25-3.20 (m. 1 H), 3.05-2.92 (m, 1 H),
2.26-2.16 (m, 1 H), 2.10-2.03 (m, 1 H), 1.69-1.63 (m, 2 H), 1.61-1.55
(m, 2 H), 1.38-1.26 (m, 1 H), 1.20 (t, J = 7.2 Hz, 9 H), 0.99-0.90
(m, 2 H), 0.89 (d, J = 6.8 Hz, 3 H), 0.86 (s, 3 H), 0.84-0.78 (m,
2 H), 0.75 (d, J = 7.2 Hz, 3 H), 0.67-0.60 (m, 2 H); 13C {1H} NMR
(100 MHz, CDCl3) δ 79.1, 70.9, 58.2, 48.3, 40.6, 34.6, 31.5, 25.5,
23.5, 23.3, 22.3, 20.9, 18.2, 16.2, 6.6; MS (ESI) m/z (relative in-
tensity) 360.2 (5), 95.1 (100) [M]+.
Triethoxy(3-(((2S,3R,4S,5R,6R)-3,4,5-tris(benzyloxy)-6-
((benzyloxy)methyl)tetrahydro-2H-pyran-2-yl)oxy)pro-
pyl)silane (5j) was prepared as pale yellow oil from 4j (0.50
mmol, 290.4 mg) and (EtO)3SiH (0.75 mmol, 125.8 mg), ac-
cording to the General Procedure in 70% yield (260.7 mg, l/b >
1
99:1): H NMR (400 MHz, CDCl3) δ 7.46-7.30 (m, 18 H), 7.26-
7.20 (m, 2 H), 5.10-5.03 (m, 1 H), 4.95-4.89 (m, 2 H), 4.89-4.82
(m, 2 H), 4.76-4.67 (m, 2 H), 4.58-4.49 (m, 2 H), 4.09 (t, J = 9.2
Hz, 1 H), 3.94-3.86 (m, 6 H), 3.84-3.80 (m, 1 H), 3.79-3.74 (m, 1
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The Journal of Organic Chemistry
H), 3.74-3.68 (m, 2 H), 3.67-3.63 (m, 1 H), 3.61-3.48 (m, 2 H),
13C {1H} NMR (100 MHz, CDCl3) δ 148.3, 147.6, 127.9, 125.8, 122.7,
1.90-1.81 (m, 2 H), 1.33-1.28 (m, 9 H), 0.83-0.71 (m, 2 H); 13C {1H}
NMR (100 MHz, CDCl3) δ 138.8, 138.5, 138.4, 138.3, 138.2, 138.1,
138.0, 137.9, 128.3, 128.2, 128.2, 128.0, 127.9, 127.8, 127.8, 127.8,
127.7, 127.6, 127.5, 127.4, 127.4, 103.5, 96.7, 84.6, 82.2, 82.0,
80.077.8, 77.6, 75.5, 74.9, 74.7, 73.3, 72.9, 72.1, 70.2, 70.0, 68.9,
68.4, 58.2, 23.1, 22.7, 18.2, 6.6, 6.5; HRMS m/z (CI) calcd. for
C43H56O9SiNa (M+Na)+ 767.3592, found 767.3584.
117.4, 75.2, 74.7, 58.4, 40.1, 39.4, 37.5, 37.5, 37.4, 37.3, 32.8, 32.7,
31.3, 28.0, 24.8, 24.4, 23.9, 23.6, 22.7, 22.6, 21.0, 20.6, 19.7, 19.6,
18.3, 12.8, 11.9, 11.8, 6.7; MS (ESI) m/z (relative intensity) 634.8
(10), 430.7 (100) [M]+.
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4
5
6
7
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Triethoxy(3-(phenylsulfonyl)propyl)silane (7a) was prepared
as pale yellow oil from 6a (0.50 mmol, 91.1 mg) and (EtO)3SiH
(0.75 mmol, 125.8 mg), according to the General Procedure in
1
(3-(((3aR,5R,6S,6aR)-5-((R)-2,2-Dimethyl-1,3-dioxolan-4-
yl)-2,2-dimethyltetrahydrofuro[2,3-d][1,3]dioxol-6-
99% yield (171.5 mg, l/b > 99:1): H NMR (400 MHz, CDCl3) δ
7.88-7.85 (m, 2 H), 7.64-7.59 (m, 1 H), 7.55-7.51 (m, 2 H), 3.73
(q, J = 6.8 Hz, 6 H), 3.15-3.10 (m, 2 H), 1.84-1.75 (m, 2 H), 1.14 (t,
J = 6.8 Hz, 9 H), 0.64 (t, J = 8.0 Hz, 2 H); 13C {1H} NMR (100
MHz, CDCl3) δ 139.0, 133.4, 129.0, 127.9, 58.3, 58.2, 18.0, 16.7, 9.1;
MS (ESI) m/z (relative intensity) 346.1 (5), 91.0 (100) [M]+.
Bis(3-(triethoxysilyl)propyl)phthalate (7b) was prepared as
pale yellow oil from 6b (0.50 mmol, 123.1 mg) and (EtO)3SiH
(1.50 mmol, 251.6 mg), according to the General Procedure in
80% yield (229.9 mg, l/b > 99:1): 1H NMR (400 MHz, CDCl3) δ
7.74-7.70 (m, 2 H), 7.55-7.51 (m, 2 H), 4.31-4.26 (m, 4 H), 3.87-
3.80 (m, 12 H), 1.88-1.81 (m, 4 H), 1.26-1.21 (m, 18 H), 0.74-0.68
(m, 4 H); 13C {1H} NMR (100 MHz, CDCl3) δ 167.5, 132.2, 130.8,
128.8, 67.6, 58.3, 22.1, 18.2, 6.5; MS (ESI) m/z (relative intensity)
574.4 (5), 207.3 (100) [M]+.
9
yl)oxy)propyl)triethoxysilane (5k) was prepared as pale yellow
oil from 4k (0.50 mmol, 150.2 mg) and (EtO)3SiH (0.75 mmol,
125.8 mg), according to the General Procedure in 67% yield
(155.7 mg, l/b > 99:1): 1H NMR (400 MHz, CDCl3) δ 5.87 (d, J =
3.6 Hz, 1 H), 4.54 (d, J = 3.6 Hz, 1 H), 4.32 (q, J = 6.4 Hz, 1 H),
4.14 (q, J = 3.2 Hz, 1 H), 4.10-4.06 (m, 2 H), 4.01-3.97 (m, 1 H),
3.82 (q, J = 7.2 Hz, 6 H), 3.62-3.46 (m, 2 H), 1.72-1.64 (m, 2 H),
1.50 (s, 3H), 1.43 (s, 3H), 1.35 (s, 3H), 1.32 (s, 3H), 1.23 (t, J = 7.2
Hz, 9 H), 0.68-0.63 (m, 2 H); 13C {1H} NMR (100 MHz, CDCl3)
δ 111.7, 108.8, 105.2, 82.5, 82.0, 81.1, 72.7, 72.5, 67.1, 58.3, 26.8,
26.7, 26.2, 25.3, 23.1, 18.3, 6.5; HRMS m/z (CI) calcd. for
C21H40O9SiNa (M+Na)+ 487.2340, found 487.2337.
(8R, 9S, 13S, 14S)-13-Methyl-3-(3-(triethoxysilyl)propoxy)-7,
8, 9, 11, 12, 13, 15, 16-octahydro-6H-cyclopenta[a]phenanthren-
17(14H)-one (5l) was prepared as pale yellow oil from 4l (0.50
mmol, 155.2 mg) and (EtO)3SiH (0.75 mmol, 125.8 mg), accord-
ing to the General Procedure in 81% yield (192.3 mg, l/b > 99:1):
1H NMR (400 MHz, CDCl3) δ 7.18 (d, J = 8.6 Hz, 1 H), 6.73-6.68
(m, 1 H), 6.65-6.62 (m, 1 H), 3.91 (t, J = 6.8 Hz, 2 H), 3.83 (q, J =
7.2 Hz, 6 H), 2.91-2.85 (m, 2 H), 2.54-2.46 (m, 1 H), 2.43-2.36
(m, 1 H), 2.29-2.20 (m, 1 H), 2.19-2.04 (m, 2 H), 2.03-1.93 (m, 2
H), 1.92-1.84 (m, 2 H), 1.66-1.57 (m, 2 H), 1.55-1.52 (m, 2 H), 1.49-
1.35 (m, 2 H), 1.23 (t, J = 7.2 Hz, 9 H), 0.91 (s, 3 H), 0.78-0.73 (m,
2 H); 13C {1H} NMR (100 MHz, CDCl3) δ 157.1, 137.6, 131.8, 126.2,
114.5, 112.1, 69.9, 58.4, 50.4, 48.0, 44.0, 38.4, 35.8, 31.6, 29.6, 56.5,
25.9, 22.8, 21.6, 18.3, 13.8, 6.5; HRMS m/z (CI) calcd. for
C27H42O5SiNa (M+Na)+ 497.2700, found 497.2701.
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58
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60
1-(3-(Triethoxysilyl)propyl)-1H-indole (7c) was prepared as
pale yellow oil from 6c (0.50 mmol, 78.6 mg) and (EtO)3SiH
(0.75 mmol, 125.8 mg), according to the General Procedure in
1
70% yield (112.5 mg, l/b > 99:1): H NMR (400 MHz, CDCl3) δ
7.63-7.59 (m, 1 H), 7.36-7.32 (m, 1 H), 7.21-7.14 (m, 1 H), 7.10-
7.05 (m, 2 H), 6.48-6.45 (m, 1 H), 4.10 (t, J = 7.2 Hz, 2 H), 3.78
(q, J = 6.8 Hz, 6 H), 2.00-1.89 (m, 2 H), 1.20 (t, J = 6.8 Hz, 9 H),
0.60 (t, J = 8.0 Hz, 2 H); 13C {1H} NMR (100 MHz, CDCl3) δ 135.9,
128.5, 127.8, 121.2, 120.8, 119.1, 109.4, 100.7, 58.4, 48.6, 23.8, 18.2,
7.6; HRMS m/z (CI) calcd. for C17H28NO3Si (M+H)+ 322.1839,
found 322.1842.
N-(3-(Triethoxysilyl)propyl)aniline (7d) was prepared as col-
orless oil from 6d (0.50 mmol, 66.6 mg) and (EtO)3SiH (1.50
mmol, 251.6 mg), according to the General Procedure in 92%
yield (136.8 mg, l/b > 99:1): 1H NMR (400 MHz, CDCl3) δ 7.21-
7.18 (m, 2 H), 6.72-6.68 (m, 1 H), 6.66-6.63 (m, 2 H), 3.86 (q, J
= 7.2 Hz, 6 H), 3.16 (t, J = 7.2 Hz, 2 H), 1.82-1.73 (m, 2 H), 1.26
(t, J = 7.2 Hz, 9 H), 0.77-0.72 (m, 2 H); 13C {1H} NMR (100 MHz,
CDCl3) δ 148.2, 129.2, 117.1, 112.8, 58.4, 46.5, 22.7, 18.3, 7.8; MS
(ESI) m/z (relative intensity) 297.2 (6), 84.3 (100) [M]+.
Diethyl(3-(triethoxysilyl)propyl)phosphine oxide (7e) was
prepared as pale yellow oil from 6e (0.50 mmol, 73.1 mg) and
(EtO)3SiH (0.75 mmol, 125.8 mg), according to the General
(8R, 9S, 10R, 13S, 14S)-10, 13-Dimethyl-17-(3-(triethoxysi-
lyl)propoxy)-6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17-dodecahydro-
1H-cyclopenta[a]phenanthren-3 (2H)-one (5m) was prepared
as pale yellow oil from 4m (0.50 mmol, 164.2 mg) and
(EtO)3SiH (0.75 mmol, 125.8 mg), according to the General
1
Procedure in 57% yield (140.4 mg, l/b > 99:1): H NMR (400
MHz, CDCl3) δ 5.66 (s, 1 H), 3.75 (q, J = 7.2 Hz, 6 H), 3.39-3.27
(m, 2 H), 3.22 (t, J = 8.4 Hz, 1 H), 2.37-2.26 (m, 2 H), 2.26-2.16
(m, 1 H), 2.00-1.90 (m, 2 H), 1.90-1.84 (m, 1 H), 1.80-1.74 (m, 1
H), 1.67-1.61 (m, 2 H), 1.55-1.43 (m, 4 H), 1.43-1.34 (m, 2 H), 1.26-
1.18 (m, 2 H), 1.16 (t, J = 7.2 Hz, 9 H), 1.12 (s, 3 H), 0.96-0.86 (m,
1
Procedure in 98% yield (152.1 mg, l/b > 99:1): H NMR (400
MHz, CDCl3) δ 4.12-3.98 (m, 4 H), 3.77 (q, J = 6.8 Hz, 6 H), 1.81-
1.64 (m, 4 H), 1.27 (t, J = 7.2 Hz, 6 H), 1.18 (t, J = 6.8 Hz, 9 H),
0.69 (t, J = 8.0 Hz, 2 H); 13C {1H} NMR (100 MHz, CDCl3) δ 61.1,
58.2, 29.3, 27.9, 18.1, 16.3, 11.6; HRMS m/z (CI) calcd. for
C13H32O6PSi (M+H)+ 343.1707, found 343.1696.
Triethoxy(3-(4, 4, 5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-
yl)propyl)silane (7f) was prepared as pale yellow oil from 6f
(0.50 mmol, 67.5 mg) and BnMe2SiH (0.75 mmol, 112.8 mg),
according to the General Procedure in 93% yield (132.7 mg, l/b >
99:1): 1H NMR (400 MHz, CDCl3) δ 7.25-7.20 (m, 2 H), 7.11-7.06
(m, 1 H), 7.03-6.99 (m, 2 H), 3.41 (t, J = 6.8 Hz, 2 H), 2.1 (s, 2 H),
1.92-1.82 (m, 2 H), 1.49-1.41 (m, 2 H), 0.54-0.50 (m, 2 H), 0.0 (s,
6 H); 13C {1H} NMR (100 MHz, CDCl3) δ 140.2, 128.2, 128.0, 123.9,
36.2, 33.5, 25.5, 22.3, 13.8, -3.7; MS (ESI) m/z (relative intensity)
284.0 (6), 149.3 (100) [M]+.
2 H), 0.86-0.78 (m, 2 H), 0.73 (s, 3 H), 0.60-0.54 (m, 2 H): 13
C
{1H} NMR (100 MHz, CDCl3) δ 199.6, 171.4, 123.8, 88.7, 72.3, 58.3,
53.9, 50.7, 42.8, 38.6, 37.7, 35.7, 35.5, 33.9, 32.8, 31.6, 28.1, 23.5,
23.3, 20.7, 18.3, 17.4, 11.6, 6.5; HRMS m/z (CI) calcd. for
C28H49O5Si (M+H)+ 493.3350, found 493.3348.
Triethoxy(3-(((R)-2,5,7,8-tetramethyl-2-((4R,8R)-4,8,12-tri-
methyltridecyl)chroman-6-yl)oxy)propyl)silane (5n) was pre-
pared as pale yellow oil from 4n (0.50 mmol, 235.4 mg) and
(EtO)3SiH (0.75 mmol, 125.8 mg), according to the General
1
Procedure in 87% yield (276.3 mg, l/b > 99:1): H NMR (400
MHz, CDCl3) δ 3.85 (q, J = 7.2 Hz, 6 H), 3.61 (t, J = 6.8 Hz, 2 H),
2.56 (t, J = 6.8 Hz, 2 H), 2.16 (s, 3 H), 2.12 (s, 3 H), 2.07 (s, 3 H),
1.95-1.86 (m, 2 H), 1.84-1.70 (m, 2 H), 1.56 (s, 3 H), 1.54-1.50 (m,
2 H), 1.49-1.31 (m, 6 H), 1.26-1.22 (m, 15 H), 1.14 (t, J = 7.6 Hz, 2
H), 1.11-1.04 (m, 4 H), 0.88-0.82 (m, 13 H), 0.81-0.76 (m, 2 H);
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Triethoxy(3-(4, 4, 5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-
14.9, 6.6; HRMS m/z (CI) calcd. for C22H48O6Si2Na (M+Na)+
487.2887, found 487.2885.
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2
3
4
5
6
7
8
yl)propyl)silane (7g) was prepared as pale yellow oil from 6g
(0.50 mmol, 84.0 mg) and (EtO)3SiH (0.75 mmol, 125.8 mg),
according to the General Procedure in 96% yield (159.5 mg,
l/b > 99:1): 1H NMR (400 MHz, CDCl3) δ 3.82 (q, J = 7.2 Hz, 6
H), 1.61-1.52 (m, 2 H), 1.25 (s, 12 H), 1.23 (t, J = 7.2 Hz, 9 H), 0.86
(t, J = 7.6 Hz, 2 H), 0.71-0.66 (m, 2 H); 13C {1H} NMR (100 MHz,
CDCl3) δ 82.8, 58.2, 24.8, 18.2, 17.4, 13.3; MS (ESI) m/z (relative
intensity) 332.2 (5), 163.1 (100) [M]+.
2,4-Bis(allylthio)pyrimidine (2g): NaOt-Bu (13.0 mmol) was
added to ethanol (20.0 mL) in a reflux apparatus, and stirred
until NaOtBu was totally dissolved. Then pyrimidine-2, 4-di-
thiol (5.0 mmol) was added slowly. The reaction mixture was
refluxed for 1 h. Allyl bromide (13.0 mmol) was added and re-
fluxed for another 12 h. The solution was allowed to cool to
room temperature, and then water (10.0 mL) was added to
quench the reaction. The mixture was extracted with EtOAc
(10.0 mL x 3), and the combined organic layer was washed with
brine and dried over anhydrous sodium sulfate, filtered and
concentrated in vacuum. The crude was purified by flash col-
umn chromatography on silica gel to afford pure product 2g:
1H NMR (400 MHz, CDCl3) δ 8.12 (d, J = 5.6 Hz, 1 H), 6.81 (d, J
= 5.2 Hz, 1 H), 6.05-5.80 (m, 2 H), 5.35-5.32 (m, 1 H), 5.30-5.28
(m, 1 H), 5.20-5.11 (m, 2 H), 3.86-3.80 (m, 4 H); 13C {1H} NMR
(100 MHz, CDCl3) δ 171.1, 169.5, 154.4, 133.4, 132.7, 118.3, 117.7,
114.3, 33.6, 31.9; HRMS m/z (CI) calcd. for C10H12N2S2Na
(M+Na)+ 247.0340, found 247.0337.
Triethoxy(2-(trimethylsilyl)ethyl)silane (7h) was prepared as
pale yellow oil from 6h (0.50 mmol, 50.1 mg) and (EtO)3SiH
(0.75 mmol, 125.8 mg), according to the General Procedure in
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18
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37
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41
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56
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58
59
60
1
70% yield (92.6 mg, l/b > 99:1): H NMR (400 MHz, CDCl3) δ
3.84 (q, J = 7.2 Hz, 6 H), 1.52-1.44 (m, 2 H), 1.25 (t, J = 7.2 Hz, 9
H), 0.76-0.70 (m, 2 H), 0.64-0.59 (m, 2 H), 0.0 (s, 9 H); 13C {1H}
NMR (100 MHz, CDCl3) δ 58.2, 20.9, 18.2, 17.4, 14.8, -1.7; MS
(ESI) m/z (relative intensity) 278.1 (5), 163.0 (100) [M]+.
6, 6-Diethoxy-3-methoxy-3-methyl-2, 7-dioxa-3, 6-disilanon-
ane (7i) was prepared as pale yellow oil from 6i (0.50 mmol,
66.1 mg) and (EtO)3SiH (0.75 mmol, 125.8 mg), according to
1
the General Procedure in 76% yield (112.7 mg, l/b > 99:1): H
ASSOCIATED CONTENT
NMR (400 MHz, CDCl3) δ 3.71 (q, J = 7.2 Hz, 6 H), 3.40 (s, 6 H),
1.11 (t, J = 7.2 Hz, 9 H), 0.58-0.45 (m, 4 H), 0.0 (s, 3 H); 13C {1H}
NMR (100 MHz, CDCl3) δ 58.4, 50.2, 18.3, 4.0, 1.4, -6.6; HRMS
m/z (CI) calcd. for C11H28O5Si2Na (M+H)+ 319.1373, found
319.1381.
Triethoxy(4-phenylbutyl)silane (7j) was prepared as pale yel-
low oil from 6j (0.50 mmol, 59.1 mg) and (EtO)3SiH (0.75
mmol, 125.8 mg), according to the General Procedure in 71%
yield (100.3 mg, l/b > 99:1): 1H NMR (400 MHz, CDCl3) δ 7.28-
7.23 (m, 2 H), 7.19-7.13 (m, 3 H), 3.80 (q, J = 6.8 Hz, 6 H), 2.64
(t, J = 7.6 Hz, 2 H), 1.79-1.71 (m, 2 H), 1.21 (t, J = 6.8 Hz, 9 H),
0.69-0.65 (m, 2 H); 13C {1H} NMR (100 MHz, CDCl3) δ 142.3,
128.5, 128.1, 125.6, 58.3, 39.2, 24.8, 18.2, 10.1; MS (ESI) m/z (rela-
tive intensity) 282.2 (5), 163.1 (100) [M]+.
Triethoxy(4-phenylbutyl)silane (7k) was prepared as pale
yellow oil from 6k (0.50 mmol, 66.1 mg) and (EtO)3SiH (0.75
mmol, 125.8 mg), according to the General Procedure in 83%
yield (123.0 mg, l/b > 99:1): 1H NMR (400 MHz, CDCl3) δ 7.27-
7.23 (m, 2 H), 7.17-7.13 (m, 3 H), 3.82 (q, J = 7.2 Hz, 6 H), 2.60
(t, J = 7.6 Hz, 2 H), 1.71-1.61 (m, 2 H), 1.51-1.43 (m, 2 H), 1.21 (t, J
= 7.2 Hz, 9 H), 0.70-0.63 (m, 2 H); 13C {1H} NMR (100 MHz,
CDCl3) δ 142.6, 128.3, 128.1, 125.5, 58.2, 35.5, 34.8, 22.4, 18.2, 10.2;
MS (ESI) m/z (relative intensity) 296.1 (5), 250.1 (100) [M]+.
Triethoxy(phenethyl)silane (7l) was prepared as pale yellow
oil from 6l (0.50 mmol, 52.1 mg) and (EtO)3SiH (0.75 mmol,
125.8 mg), according to the General Procedure in 88% yield
(118.1 mg, l/b > 99:1): 1H NMR (400 MHz, CDCl3) δ 7.29-7.24 (m,
2 H), 7.24-7.18 (m, 2 H), 7.18-7.13 (m, 1 H), 3.82 (q, J = 6.8 Hz, 6
H), 2.77-2.71 (m, 2 H), 1.23 (t, J = 6.8 Hz, 9 H), 1.02-0.97 (m, 2
H); 13C {1H} NMR (100 MHz, CDCl3) δ 144.6, 128.2, 127.7, 125.6,
58.3, 28.8, 18.3, 12.5; MS (ESI) m/z (relative intensity) 268.1 (20),
163.1 (100) [M]+.
4,4,9,9-Tetraethoxy-6-(4-methylpent-3-en-1-yl)-3,10-dioxa-
4,9-disiladodecane (7m) was prepared as pale yellow oil from
6m (0.50 mmol, 68.1 mg) and (EtO)3SiH (1.50 mmol, 251.6 mg),
according to the General Procedure in 44% yield (102.3 mg, l/b >
99:1): 1H NMR (400 MHz, CDCl3) δ5.14-5.10 (m, 1 H), 3.86-3.80
(m, 12 H), 1.97 (q, J = 7.6 Hz, 2 H), 1.69 (s, 3 H), 1.62 (s, 3 H),
1.50-1.43 (m, 2 H), 1.40-1.33 (m, 2 H), 1.28-1.26 (m, 1 H), 1.28-1.22
(m, 18 H), 0.66-0.59 (m, 4 H); 13C {1H} NMR (100 MHz, CDCl3)
δ 130.9, 125.0, 58.3, 58.2, 35.3, 35.0, 28.4, 25.7, 25.1, 18.3, 18.2, 17.6,
Supporting Information.
The Supporting Information is available free of charge on
the ACS Publications website at http://pubs.acs.org.
1H and 13C NMR spectra of products (PDF).
AUTHOR INFORMATION
Corresponding Author
*stding@mail.buct.edu.cn.
ORCID
Shengtao Ding: 0000-0003-1515-2931
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
This work was financially supported by the National Natural
Science Foundation of China (No.21702015), State Key Labora-
tory of Organic−Inorganic Composites, Beijing University of
Chemical Technology (oic-201801011), the Fundamental Re-
search Funds for the Central Universities (buctrc201719).
REFERENCES
(1) For recent reviews, see: (a) Komiyama, T.; Minami Y.; Hiyama,
T. Recent Advances in Transition-Metal-Catalyzed Synthetic
Transformations of Organosilicon Reagents. ACS Catal. 2017, 7,
631-651. For recent examples, see: (b) Shin, K.; Park, Y.; Baik, M.-
H.; Chang, S. Iridium-Catalysed Arylation of C-H Bonds Enabled
by Oxidatively Induced Reductive Elimination. Nat. Chem. 2018,
10, 218-224. (c) Shibata, M.; Ito H.; Itami, K. C–H Arylation of Phe-
nanthrene with Trimethylphenylsilane by Pd/o-Chloranil Cataly-
sis: Computational Studies on the Mechanism, Regioselectivity,
and Role of o-Chloranil. J. Am. Chem. Soc. 2018, 140, 2196-2205. (d)
Komiyama, T.; Minami, Y.; Furuya Y.; Hiyama, T. Palladium/Cop-
per Dual Catalysis for the Cross-Coupling of Aryl(trialkyl)silanes
with Aryl Bromides. Angew. Chem., Int. Ed. 2018, 57, 1987-1990. (e)
Xu, P.; Wang, F.; Fan, G.; Xu X.; Tang, P. Hypervalent Iodine(III)-
Mediated Oxidative Fluorination of Alkylsilanes by Fluoride Ions.
Angew. Chem., Int. Ed. 2017, 56, 1101-1104. (f) Wang, F.; Xu, P.; Cong
F.; Tang, P. Silver-Mediated Oxidative Functionalization of Al-
kylsilanes. Chem. Sci. 2018, 9, DOI: 10.1039/c8sc03730b.
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