Cu(I)-Catalyzed Coupling of Bis(trimethylsilyl)diazomethane with Terminal Alkynes: A Synthesis of 1,1-Disilyl Allenes

Article abstract of DOI:10.1021/acs.joc.8b00651

A Cu(I)-catalyzed cross-coupling reaction of terminal alkynes and bis(trimethylsilyl)diazomethane is reported. Mechanistically, the reaction is based on the recently developed cross-coupling reactions through metal-carbene migratory insertion. This reaction provides an efficient synthetic method for 1,1-disilyl allenes. Subsequent transformations of 1,1-disilyl allenes are investigated, which show diverse reactivities of these allenes.

Full text of DOI:10.1021/acs.joc.8b00651

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Note
Cu(I)-Catalyzed Coupling of Bis(trimethylsilyl)diazomethane
with Terminal Alkynes: A Synthesis of 1,1-Disilyl Allenes
Shuai Xu, Ri Chen, Zihao Fu, Yunpeng Gao, and Jianbo Wang
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.8b00651 • Publication Date (Web): 03 May 2018
Downloaded from http://pubs.acs.org on May 3, 2018
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The Journal of Organic Chemistry
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Cu(I)-Catalyzed Coupling of Bis(trimethylsilyl)diazomethane with
Terminal Alkynes: A Synthesis of 1,1-Disilyl Allenes
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Shuai Xu,† Ri Chen,† Zihao Fu,† Yunpeng Gao† and Jianbo Wang*,†,‡
†Beijing National Laboratory of Molecular Sciences (BNLMS), Key Laboratory of Bioorganic
Chemistry and Molecular Engineering of Ministry of Education, College of Chemistry, Peking
University, Beijing 100871, China; ‡The State Key Laboratory of Organometallic Chemistry, Chinese
Academy of Sciences, Shanghai 200032, China
RECEIVED DATE (to be automatically inserted after your manuscript is accepted if required
according to the journal that you are submitting your paper to)
ABSTRACT.
A
Cu(I)-catalyzed cross-coupling reaction of terminal alkynes and
bis(trimethylsilyl)diazomethane is reported. Mechanistically, the reaction is based on the recently
developed cross-coupling reactions through metal-carbene migratory insertion. This reaction provides an
efficient synthetic method for 1,1-disilyl allenes. Subsequent transformations of 1,1-disilyl allenes are
investigated, which shows diverse reactivities of these allenes.
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Geminal disilyl compounds are a special kind of organosilicon compounds, which can take part in many
synthetically useful transformations.1 For example, they have great potential for bifunctional
transformations and the construction of C=C bonds in modified Peterson reaction. Traditional methods
to construct this type of bimetallic compounds include substitution reactions under strong basic
conditions, Kumada cross-coupling reactions,2 carbene insertion reaction of Si-H or Si-Si bonds,3,4
hydrosilylation of internal alkynes,5 and rearrangement reactions.6 However, most of these methods can
only construct sp3-geminal disilyl compounds. The methods that are applicable for the synthesis of sp2-
geminal disilyl compounds are rare.5 To the best of our knowledge, the methods for the synthesis of 1,1-
disilyl allenes have few documents in the literature.7 Moreover, the synthetic application of this type of
allene compounds has not been explored.
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On the other hand, transition-metal catalyzed cross-coupling of diazo compounds have emerged as
efficient methods for the construction of carbon-carbon bonds.8 In particular, we have previously
developed an efficient method for the synthesis of allenes through Cu(I)-catalyzed cross-coupling of
terminal alkynes with N-tosylhydrazones or diazo compounds (Scheme 1A).9-11 Allenes have diverse
reactivities and have attracted considerable attention in recent years.12 While many synthetic methods
towards allenes have been developed,13 the direct coupling with terminal alkynes and diazo compounds
represents a useful alternative approach. The allene formation through Cu(I)-catalyzed coupling is
proposed to involve a Cu(I) carbene migratory insertion process. To further expand the scope of this
coupling reaction, we have conceived to use bis(trimethylsilyl)diazomethane 1 to access gem-disilyl
allene compounds (Scheme 1B). Bis(trimethylsilyl)diazomethane 1 has been previously synthesized,14
however, their application in organic synthesis has not been explored. Due to the significant steric and
electron-withdrawing effect of the two trimethylsilyl groups, compound 1 shows higher stability and
different reactivity as compared with the corresponding (trimethylsilyl)diazomethane (TMSCHN2). For
example, compound 1 usually undergoes isomerization process rather than metal carbene
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formation.14b,15 Herein we demonstrate that bis(trimethylsilyl)diazomethane 1 undergoes efficient
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coupling in the presence of Cu(I) catalyst, affording 1,1-disilyl allenes in moderate to excellent yields.
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Scheme 1. Allene Synthesis through Cu(I)-Catalyzed Cross-Coupling Reaction
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First, we have examined the reactivity of bis(trimethylsilyl)diazomethane 1 in the presence of
various transition metal catalysts. Upon testing the reaction with transition-metal catalysts such as Cu(I),
Pd(II), Rh(II), we found Cu(I) catalyst could decompose compound 1 at high temperature, while 1
remained inert with other transition metals. Subsequently, we began to optimize the reaction conditions
for the Cu(I)-catalyzed coupling of 1 with terminal alkyne 2a (Table 1). Copper iodide was evaluated as
the Cu(I) catalyst. The diazo compound 1 was found stable below 60 oC and trace amount of the allene 1
could be observed (entry 1). When elevating the reaction temperature, the yield of the desired allene
o
product increased (entries 2 and 3). At 110 C, the ligand 1,10-phenanthroline (1,10-phen) was added,
but the reaction failed to give allene product (entry 4). When Cu(MeCN)4PF6 was used as the catalyst,
no allene product could be observed (entry 5). With CuCl as the catalyst, the allene product was formed
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in moderate yields at the reaction temperature ranging from 100 to 120 C (entries 6-9). When CuCl2
was the catalyst, the allene product was formed in slightly lower yield (entry 10). Finally, it was found
that with 10 mol% CuBr the reaction gave allene product in 80% isolated yield (entry 11).
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Table 1. Optimization of the Reaction Conditionsa
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entry
1
[Cu] (mol%)
CuI (20)
T (oC)
60
yieldb
trace
11%
32%
0%
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CuI (20)
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CuI (20)
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110
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CuI/1,10-Phen (20)
Cu(MeCN)4PF6 (20)
CuCl (20)
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0%
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60%
62%
58%
65%
46%
80%c
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CuCl (20)
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CuCl (20)
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CuCl (10)
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CuCl2 (10)
CuBr (10)
aReaction conditions: bis(trimethylsilyl)diazomethane 1 (0.10 mmol), 2a (1.0 equiv), Pr2NH (0.10
i
b
mmol, 1.0 equiv), dioxane (1.0 mL) for 6 h. If not otherwise noted, the yields were determined by the
1H NMR using CH3NO2 as the internal standard. cIsolated yield.
With the optimized reaction conditions in hand (Scheme 2), we explored the substrate scope of this
reaction. As for aryl acetylenes, both electron-donating (3b-d) and electron-withdrawing groups (3e-k)
are tolerated. Ester group that is sensitive to basic condition is also tolerated in this reaction, affording
the desired product 3i in good yield. Substituents on meta (3l) or ortho (3m, 3n) positions are found not
to affect the reaction, indicating that this reaction is not sensitive to steric effect. Besides, naphthyl (3o)
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and thienyl (3p) acetylenes also take part in this transformation effectively. Apart from aryl acetylenes,
alkenyl acetylene (3q) is also a good substrate for the reaction.
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Scheme 2. Scope of Aryl Acetylenes and Alkenyl Acetylenea
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aReaction conditions: bis(trimethylsilyl)diazomethane 1 (0.10 mmol), 2a-q (0.10 mmol, 1.0 equiv),
CuBr (10 mol%), iPr2NH (0.10 mmol, 1.0 equiv), dioxane (1.0 mL), 110 oC, 6 h.
Next, we explored the scope of alkyl acetylenes (Scheme 3). Gratifyingly, the reaction also works
with a broad scope of alkyl terminal alkynes. Not only simple alkyl groups with different substituted
type (3r-w) are suitable substrates, the alkynes with some sensitive functional group such as hydroxyl
group (3x) can also take part in this reaction, affording the corresponding allene products in good yields.
Notably, when using trimethylsilylethyne (2y) as the substrate, we can also obtain the allene product
with good chemoselectivity. This result is different from the Cu(I)-catalyzed cross-coupling reaction of
N-tosylhydrazones and trimethylsilylethyne, in which case C(sp)-C(sp3) bond formation occurs to afford
alkyne products.16 We have reasoned that this chemoselectivity derives from the steric effect of the
trimethylsilyl groups of the diazo substrate 1.
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Scheme 3. Scope of Alkyl Acetylenesa
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aReaction conditions: Bis(trimethylsilyl)diazomethane 1 (0.10 mmol), 2r-y (0.10 mmol, 1.0 equiv),
CuBr (10 mol%), iPr2NH (0.10 mmol, 1.0 equiv), dioxane (1.0 mL), 110 oC, 6 h.
Since the allene moiety is reactive under Cu(I) catalysis, it is possible to develop tandem reactions
following the generation of allene moiety through the cross-coupling reactions. Thus, with o-amino or o-
hydroxyl aromatic acetylenes as the substrates, it was possible to obtain the annulation products in good
yields. Mechanistically, these reactions are proposed to proceed through intramolecular nucleophilic
attack of the NH2, NHAc, or OH groups to the Cu(I)-activated allene moiety (Scheme 4).
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The Journal of Organic Chemistry
Scheme 4. CuBr-Catalyzed Tandem Reaction
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aReaction conditions: Bis(trimethylsilyl)diazomethane 1 (0.10 mmol), 4a-e (0.10 mmol, 1.0 equiv),
CuBr (10 mol%), iPr2NH (0.10 mmol, 1.0 equiv), dioxane (1.0 mL), 110 oC, 6 h.
The 1,1-disilyl allenes obtained from simple Cu(I)-catalyzed cross-coupling between terminal
alkynes and diazo compound 1 open up the possibility to explore their synthetic applications. However,
to the best of our knowledge the reactivity of 1,1-disilyl allenes has few report in the literature. Thus, we
proceeded to investigate the reaction of 1,1-disilyl allenes (Scheme 5). Preliminary studies indicated that
aryl allenes (3a, 3f) and alkyl allene (3t) can react with NBS, yielding propargyl bromide derivatives
(Scheme 5a). The propargyl bromides can further react with nucleophiles such as aniline or alcohol to
give the corresponding products 6b and 6c (Scheme 5b).17 Interestingly, when the aryl allene 3f was
treated with NIS, the expected propargyl iodide was not obtained. Instead, allenic iodide 6d was formed
in good yield and excellent chemoselectivity.
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Scheme 5. Reaction of 1,1-Disilyl Allenes
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In summary, we have developed
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Cu(I)-catalyzed cross-coupling reaction of
bis(trimethylsilyl)diazomethane 1 with terminal alkynes via metal carbene migratory insertion process.
With this coupling reaction, a series of 1,1-disilyl allenes can be obtained from easily available starting
materials. Preliminary investigation on the reactivity of 1,1-disilyl allenes shows that this type of allene
compounds may find useful applications in organic synthesis.
EXPERIMENTAL SECTION
General Methods. All the reactions were performed under a nitrogen atmosphere in oven-dried
reaction flasks. All solvents were freshly distilled and degassed according to the handbook Purification
of Laboratory Chemicals (4th Edition, Butterworth Heinemann, W. L. F. Armarego and Douglas Dalzell
o
Perrin). The boiling point of petroleum ether (PE) was between 60 and 90 C. Commercially available
reagents were used as received. For chromatography, 200-300 mesh silica gel (Qingdao, China) was
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used. H NMR spectra were recorded on Bruker ARX 400 (400 MHz); 13C {1H} NMR spectra were
recorded on Bruker ARX 400 (101 MHz); The data for NMR spectra were reported as follows: chemical
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shifts (δ) were reported in ppm; coupling constants (J) were in Hertz (Hz). IR spectra were recorded on a
Nicolet Avatar 330 Fourier transform spectrometer (FT-IR) and were reported in wave numbers (cm-1).
HRMS data were obtained on VG ZAB-HS mass spectrometer, Brucker Apex IV FTMS spectrometer
and ThermoFisher Q Exactive hybrid quadrupole-orbitrap GC-MS/MS system. PE: petroleum ether; EA:
ethyl acetate.
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Preparation of bis(trimethylsilyl)diazomethane 1.14b A solution of trimethylsilyldiazomethane (9.6
mmol, 2.0 M solution in hexane, 4.8 mL) in n-hexane (15 mL) was cooled to -100 °C, then n-BuLi (9.6
mmol, 1.6 M solution in hexane, 6.0 mL) was added dropwise over a period of one hour. The resulting
reddish solution was stirred for 15 min at -100 °C. Trimethylsilyl chloride TMSCl (9.6 mmol, 0.82 mL)
was added dropwise by syringe at -80 °C, which was slowly warmed to ambient temperature over 2
hours. After further three hours at room temperature, the suspension was filtered and the solvent was
removed in vacuo. The resulting red colored liquid was purified by column chromatography saturated
with Et3N, which yielded 0.864 g of bis(trimethylsilyl)diazomethane 1 as a yellow liquid (50%). 1H
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NMR (400 MHz, CDCl3) δ 0.17 (s, 18H); C {1H} NMR (101 MHz, CDCl3) δ 16.6, -0.29; Si NMR
(101 MHz, CDCl3) δ 1.27; GC-MS (EI, m/z, relative intensity) 186 (M+, 40), 171 (15), 143 (80), 83 (40),
73 (100); IR (film): 2955, 2046, 1252, 840 cm-1.
General procedure for Cu(I)-catalyzed coupling of bis(trimethylsilyl)diazomethane 1 with
terminal alkynes. CuBr (10 mol%, 0.01 mmol, 1.4 mg), terminal alkyne (1.0 equiv, 0.10 mmol), and 1.0
mL dioxane were mixed in an oven-dried reaction flask. Then bis(trimethylsilyl)diazomethane 1 (1.0
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equiv, 0.10 mmol, 18.6 mg) and Pr2NH (1.0 equiv, 0.10 mmol, 10.1 mg, 14.0 μL) were added to the
mixture. The mixture was stirred at 110 oC under nitrogen atmosphere for about 6 hours. Then the crude
mixture was cooled to room temperature. Petroleum ether was added to the mixture. The mixture was
filtered through celite. Solvent was evaporated under reduced pressure and the residue was purified by
flash chromatography on silica gel.
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(3-Phenylpropa-1,2-diene-1,1-diyl)bis(trimethylsilane) 3a. Yield 80% (20.8 mg); colorless oil; TLC
Rf = 0.80 (PE); 1H NMR (400 MHz, CDCl3) δ 7.23 (t, J = 7.5 Hz, 2H), 7.13 (d, J = 7.1 Hz, 2H), 7.06 (t,
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J = 7.5 Hz, 1H), 5.51 (s, 1H), 0.18 (s, 18H); C {1H} NMR (101 MHz, CDCl3) δ 210.0, 136.6, 128.6,
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125.1, 124.8, 94.0, 81.2, 0.4. GC-MS (EI, m/z, relative intensity) 260 (M+, 40), 245 (10), 172 (100), 73
(80); HRMS (ESI-FTICR) calcd for: C15H24Si2 [M]+ 260.1416, found: 260.1412; IR (film): 1907, 1597,
1250, 841 cm-1.
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(3-(p-Tolyl)propa-1,2-diene-1,1-diyl)bis(trimethylsilane) 3b. Yield 70% (19.2 mg); colorless oil;
TLC Rf = 0.70 (PE); 1H NMR (400 MHz, CDCl3) δ 7.17-6.84 (m, 4H), 5.49 (s, 1H), 2.30 (s, 3H), 0.17 (s,
18H); 13C {1H} NMR (101 MHz, CDCl3) δ 209.9, 134.4 133.4, 129.4, 125.0, 94.0, 90.0, 21.1, 0.4. GC-
MS (EI, m/z, relative intensity) 274 (M+, 40), 259 (5), 186 (100), 73 (60); HRMS (ESI-FTICR) calcd for:
C16H26Si2 [M]+ 274.1573, found: 274.1568; IR (film): 1907, 1512, 1249, 840 cm-1.
(3-(4-Methoxyphenyl)propa-1,2-diene-1,1-diyl)bis(trimethylsilane) 3c. Yield 73% (21.2 mg);
colorless oil; TLC Rf = 0.80 (PE : EA = 20:1); 1H NMR (400 MHz, CDCl3) δ 7.06 (d, J = 8.7 Hz, 2H),
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6.81 (d, J = 8.7 Hz, 2H), 5.49 (s, 1H), 3.78 (s, 3H), 0.17 (s, 18H); C {1H} NMR (101 MHz, CDCl3) δ
210.2, 157.3, 128.6, 126.0, 114.3, 94.2, 80.6, 55.4, 0.4. GC-MS (EI, m/z, relative intensity) 290 (M+, 70),
275 (90), 218 (20), 202 (80), 73 (80); HRMS (ESI-FTICR) calcd for: C16H26OSi2 [M]+ 290.1522, found:
290.1516; IR (film): 1908, 1606, 1247, 839 cm-1.
4-(3,3-Bis(trimethylsilyl)propa-1,2-dien-1-yl)-N,N-dimethylaniline 3d. Yield 91% (27.6 mg);
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colorless oil; TLC Rf = 0.80 (PE:EA = 10:1); H NMR (400 MHz, CDCl3) δ 7.04 (d, J = 8.8 Hz, 2H),
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6.69 (d, J = 8.8 Hz, 2H), 5.48 (s, 1H), 2.91 (s, 6H), 0.16 (s, 18H); C {1H} NMR (101 MHz, CDCl3) δ
211.0, 148.6, 125.8, 124.3, 113.5, 94.1, 80.8, 41.0, 0.4. GC-MS (EI, m/z, relative intensity) 303 (M+, 90),
288 (10), 230 (100), 215 (40), 73 (10); HRMS (ESI-FTICR) calcd for: C17H29NSi2 [M]+ 303.1838,
found: 303.1831; IR (film): 1906, 1519, 1249, 892, 820 cm-1.
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(3-(4-Fluorophenyl)propa-1,2-diene-1,1-diyl)bis(trimethylsilane) 3e. Yield 81% (22.5 mg); colorless
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oil; TLC Rf = 0.75 (PE); H NMR (400 MHz, CDCl3) δ 7.11-7.03 (m, 2H), 6.99-6.83 (m, 2H), 5.48 (s,
1H), 0.17 (s, 18H); 13C {1H} NMR (101 MHz, CDCl3) δ 209.5, 160.7 (d, JF = 242.9 Hz), 132.4 (d, JF =
3.0 Hz), 126.1 (d, JF = 7.8 Hz), 115,5 (d, JF = 21.7 Hz), 94.4, 80.3, 0.3. GC-MS (EI, m/z, relative
intensity) 278 (M+, 60), 263 (5), 190 (100), 73 (90); HRMS (ESI-FTICR) calcd for: C15H23FSi2 [M]+
278.1322, found: 278.1314; IR (film): 1909, 1606, 1250, 887, 834 cm-1.
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(3-(4-Chlorophenyl)propa-1,2-diene-1,1-diyl)bis(trimethylsilane) 3f. Yield 81% (23.8 mg); colorless
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oil; TLC Rf = 0.80 (PE); H NMR (400 MHz, CDCl3) δ 7.19 (d, J = 8.4 Hz, 2H), 7.05 (d, J = 8.4 Hz,
2H), 5.47 (s, 1H), 0.18 (s, 18H); 13C {1H} NMR (101 MHz, CDCl3) δ 209.1, 135.3, 130.0, 128.7, 126.1,
94.5, 80.4, 0.3. GC-MS (EI, m/z, relative intensity) 294 (M+, 45), 279 (10), 206 (80), 73 (100); HRMS
(ESI-FTICR) calcd for: C15H23ClSi2 [M]+ 294.1026, found: 294.1020; IR (film): 1906, 1590, 1250, 841
cm-1.
(3-(4-Bromophenyl)propa-1,2-diene-1,1-diyl)bis(trimethylsilane) 3g. Yield 78% (26.4 mg); colorless
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oil; TLC Rf = 0.85 (PE); H NMR (400 MHz, CDCl3) δ 7.35-7.32 (m, 2H), 7.00-6.98(m, 2H), 5.45 (s,
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1H), 0.17 (s, 18H); C {1H} NMR (101 MHz, CDCl3) δ 209.0, 135.8, 131.6, 126.5, 117.9, 94.6, 80.5,
0.3. GC-MS (EI, m/z, relative intensity) 338 (M+, 20), 250 (60), 73 (100); HRMS (ESI-FTICR) calcd for:
C15H23BrSi2 [M]+ 338.0521, found: 338.0516; IR (film): 1907, 1251, 845, 759 cm-1.
(3-(4-(Trifluoromethyl)phenyl)propa-1,2-diene-1,1-diyl)bis(trimethylsilane) 3h. Yield 80% (26.2
mg); colorless oil; TLC Rf = 0.85 (PE); 1H NMR (400 MHz, CDCl3) δ 7.47 (d, J = 8.2 Hz, 2H), 7.20 (d,
J = 8.2 Hz, 2H), 5.52 (s, 1H), 0.19 (s, 18H); 13C {1H} NMR (101 MHz, CDCl3) δ 208.5, 141.2, 126.6 (q,
JF = 32.3 Hz), 125.6(q, JF = 3.8 Hz), 124.8, 124.6(q, JF = 271.2 Hz), 94.5, 80.6, 0.3. GC-MS (EI, m/z,
relative intensity) 328 (M+, 20), 313 (10), 221 (60), 73 (90); HRMS (ESI-FTICR) calcd for: C16H23F3Si2
[M]+ 328.1290, found: 328.1285; IR (film): 1905, 1618, 1251, 841 cm-1.
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Methyl 4-(3,3-bis(trimethylsilyl)propa-1,2-dien-1-yl)benzoate 3i. Yield 85% (27.0 mg); colorless oil;
TLC Rf = 0.80 (PE:EA = 10:1); 1H NMR (400 MHz, CDCl3) δ 7.90 (d, J = 8.3 Hz, 2H), 7.17 (d, J = 8.3
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Hz, 2H), 5.53 (s, 1H), 3.88 (s, 3H), 0.19 (s, 18H); C {1H} NMR (101 MHz, CDCl3) δ 208.6, 167.2,
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142.6, 130.1, 126.3, 124.6, 94.2, 80.5, 51.9, 0.4. GC-MS (EI, m/z, relative intensity) 318 (M+, 30), 303
(10), 214 (100), 73 (50); HRMS (ESI-FTICR) calcd for: C17H26O2Si2 [M]+ 318.1471, found: 318.1464;
IR (film): 1902, 1720, 1604, 1250, 843 cm-1.
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(3-(4-Nitrophenyl)propa-1,2-diene-1,1-diyl)bis(trimethylsilane) 3j. Yield 85% (26.0 mg); colorless
oil; TLC Rf = 0.85 (PE:EA = 10:1); 1H NMR (400 MHz, CDCl3) δ 8.10 (d, J = 8.8 Hz, 2H), 7.21 (d, J =
8.8 Hz, 2H), 5.56 (s, 1H), 0.21 (s, 18H); 13C {1H} NMR (101 MHz, CDCl3) δ 207.7, 145.5, 144.8, 124.8,
124.3, 94.6, 80.7, 0.3. HRMS (ESI-FTICR) calcd for: C15H24NO2Si2 [M+H]+ 306.1340, found: 306.1341;
IR (film): 1918, 1655, 1594, 1250, 845 cm-1.
1-(4-(3,3-Bis(trimethylsilyl)propa-1,2-dien-1-yl)phenyl)ethanone 3k. Yield 73% (22.0 mg); colorless
oil; TLC Rf = 0.30 (PE:EA = 20:1); 1H NMR (400 MHz, CDCl3) δ 7.84 (d, J = 8.4 Hz, 2H), 7.19 (d, J =
8.4 Hz, 2H), 5.54 (s, 1H), 2.55 (s, 3H), 0.20 (s, 18H); 13C {1H} NMR (101 MHz, CDCl3) δ 208.6, 197.4,
143.0, 133.8, 129.0, 124.7, 94.2, 81.0, 26.5, 0.4. GC-MS (EI, m/z, relative intensity) 302 (M+, 100), 287
(10), 214 (50), 73 (80); HRMS (ESI-FTICR) calcd for: C17H27OSi2 [M+H]+ 303.1595, found: 303.1598;
IR (film): 1902, 1680, 1597, 1269, 1250, 842 cm-1.
(3-(m-Tolyl)propa-1,2-diene-1,1-diyl)bis(trimethylsilane) 3l. Yield 86% (23.6 mg); colorless oil;
TLC Rf = 0.60 (PE); 1H NMR (400 MHz, CDCl3) δ 7.13 (t, J = 7.5 Hz, 1H), 7.00-6.92 (m, 2H), 6.88 (d,
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J = 7.5 Hz, 1H), 5.48 (s, 1H), 2.30 (s, 3H), 0.18 (s, 18H); C {1H} NMR (101 MHz, CDCl3) δ 209.7,
138.1, 136.5, 128.5, 125.7, 122.1, 93.9, 81.2, 21.5, 0.4. GC-MS (EI, m/z, relative intensity) 274 (M+, 30),
259 (5), 186 (100), 73 (50); HRMS (ESI-FTICR) calcd for: C16H26Si2 [M]+ 274.1573, found: 274.1568;
IR (film): 1907, 1600, 1250, 841 cm-1.
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(3-(2-Chlorophenyl)propa-1,2-diene-1,1-diyl)bis(trimethylsilane) 3m. Yield 71% (20.9 mg);
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colorless oil; TLC Rf = 0.70 (PE); 1H NMR (400 MHz, CDCl3) δ 7.30-7.26 (m, 2H), 7.13 (t, J = 7.5 Hz,
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1H), 7.01-6.93 (m, 1H), 5.95 (s, 1H), 0.19 (s, 18H); C {1H} NMR (101 MHz, CDCl3) δ 208.9, 134.5,
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130.1, 129.7, 126.8, 126.2, 125.6, 93.7, 77.5, 0.4. GC-MS (EI, m/z, relative intensity) 294 (M+, 45), 279
(10), 206 (50), 73 (100); HRMS (EI-hybrid quadrupole-orbitrap) calcd for: C15H23ClSi2 [M]+ 294.1022,
found: 274.1021; IR (film): 1906, 1588, 1250, 841 cm-1.
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(3-([1,1'-Biphenyl]-2-yl)propa-1,2-diene-1,1-diyl)bis(trimethylsilane) 3n. Yield 56% (18.8 mg);
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colorless oil; TLC Rf = 0.45 (PE); H NMR (400 MHz, CDCl3) δ 7.72-6.91 (m, 9H), 5.56 (s, 1H), 0.18
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(s, 18H); C {1H} NMR (101 MHz, CDCl3) δ 209.9, 141.5, 138.6, 134.0, 130.2, 129.8, 128.2, 127.5,
126.8, 125.6, 124.7, 93.3, 79.1, 0.4. GC-MS (EI, m/z, relative intensity) 336 (M+, 80), 321 (5), 248 (80),
233 (100), 73 (90); HRMS (ESI-FTICR) calcd for: C21H28Si2 [M]+ 336.1729, found: 336.1723; IR (film):
1905, 1594, 1247, 842 cm-1.
(3-(6-Methoxynaphthalen-2-yl)propa-1,2-diene-1,1-diyl)bis(trimethylsilane) 3o. Yield 85% (28.9
mg); colorless oil; TLC Rf = 0.30 (PE); 1H NMR (400 MHz, CDCl3) δ 7.61 (d, J = 8.5 Hz, 2H), 7.43 (s,
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1H), 7.30 (d, J = 8.5 Hz, 1H), 7.11-7.05 (m, 2H), 5.67 (s, 1H), 3.89 (s, 3H), 0.20 (s, 18H); C {1H}
NMR (101 MHz, CDCl3) δ 210.2, 156.9, 132.7, 131.7, 129.6, 128.7, 127.1, 124.5, 122.6, 118.7, 106.1,
94.3, 81.6, 55.4, 0.4. GC-MS (EI, m/z, relative intensity) 340 (M+, 80), 325 (100), 252 (90), 73 (80);
HRMS (ESI-FTICR) calcd for: C20H28OSi2 [M]+ 340.1678, found: 340.1673; IR (film): 1907, 1600,
1501, 1247, 840 cm-1.
(3-(Thiophen-3-yl)propa-1,2-diene-1,1-diyl)bis(trimethylsilane) 3p. Yield 73% (19.4 mg); colorless
oil; TLC Rf = 0.70 (PE); 1H NMR (400 MHz, CDCl3) δ 7.22 (dd, J = 5.0, 2.9 Hz, 1H), 6.91 (dd, J = 5.0,
0.9 Hz, 1H), 6.82 (dd, J = 2.8, 0.9 Hz, 1H), 5.61 (s, 1H), 0.17 (s, 18H); 13C {1H} NMR (101 MHz,
CDCl3) δ 210.8, 136.9, 125.8, 125.5, 116.2, 93.5, 76.3, 0.3. GC-MS (EI, m/z, relative intensity) 266 (M+,
50), 251 (5), 178 (100), 73 (80); HRMS (ESI-FTICR) calcd for: C13H22SSi2 [M]+ 266.0980, found:
266.0975; IR (film): 1909, 1251, 1121, 840 cm-1.
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(3-(Cyclohex-1-en-1-yl)propa-1,2-diene-1,1-diyl)bis(trimethylsilane) 3q. Yield 92% (24.3 mg);
colorless oil; TLC Rf = 0.80 (PE); 1H NMR (400 MHz, CDCl3) δ 5.42 (t, J = 3.8 Hz, 1H), 5.27 (s, 1H),
5.48 (s, 1H), 2.91 (s, 6H), 0.16 (s, 18H); 13C {1H} NMR (101 MHz, CDCl3) δ 210.8, 132.0, 119.8, 92.6,
84.6, 26.1, 25.9, 22.9, 22.8, 0.2. GC-MS (EI, m/z, relative intensity) 264 (M+, 40), 249 (10), 190 (10),
176 (100), 73 (90); HRMS (ESI-FTICR) calcd for: C15H28Si2 [M]+ 264.1729, found: 264.1723; IR (film):
2151, 1714, 1448, 1249, 843 cm-1.
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(4-Phenylbuta-1, 2-diene-1,1-diyl)bis(trimethylsilane) 3r. Yield 76% (20.8 mg); colorless oil; TLC
Rf = 0.70 (PE); 1H NMR (400 MHz, CDCl3) δ 7.57-7.02 (m, 5H), 4.67 (t, J = 6.8 Hz, 1H), 3.35 (d, J =
6.8 Hz, 2H), 0.15 (s, 18H); 13C {1H} NMR (101 MHz, CDCl3) δ 210.5, 141.7, 128.7, 128.2, 125.9, 89.4,
76.0, 34.1, 0.2. GC-MS (EI, m/z, relative intensity) 274 (M+, 60), 259 (5), 186 (100), 73 (90); HRMS
(ESI-FTICR) calcd for: C16H26Si2 [M]+ 274.1573, found: 274.1568; IR (film): 2176, 1604, 1492, 1250,
841, cm-1.
(5-Phenylpenta-1, 2-diene-1,1-diyl)bis(trimethylsilane) 3s. Yield 81% (23.3 mg); colorless oil; TLC
Rf = 0.70 (PE); 1H NMR (400 MHz, CDCl3) δ 7.34-7.30 (m, 2H), 7.27-7.18 (m, 3H), 4.48 (t, J = 6.7 Hz,
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1H), 2.82-2.61 (m, 2H), 2.44-2.22 (m, 2H), 0.15 (s, 18H); C {1H} NMR (101 MHz, CDCl3) δ 210.4,
142.3, 128.5, 128.4, 125.8, 89.1, 75.4, 36.9, 29.5, 0.2. GC-MS (EI, m/z, relative intensity) 288 (M+, 5),
273 (5), 73 (100); HRMS (ESI-FTICR) calcd for: C17H28Si2 [M]+ 288.1729, found: 288.1723; IR (film):
1921, 1248, 840, 759 cm-1.
Nona-1,2-diene-1,1-diylbis(trimethylsilane) 3t. Yield 84% (21.3 mg); colorless oil; TLC Rf = 0.95
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(PE); H NMR (400 MHz, CDCl3) δ 4.38 (t, J = 6.8 Hz, 1H), 1.91 (q, J = 6.8 Hz, 1H), 1.43-1.19 (m,
6H), 0.89 (t, J = 6.6 Hz, 3H), 0.10 (s, 18H); 13C {1H} NMR (101 MHz, CDCl3) δ 210.9, 88.5, 76.0, 31.6,
30.1, 27.4, 22.6, 14.2, 0.2. GC-MS (EI, m/z, relative intensity) 254 (M+, 20), 239 (15), 109 (20), 73
(100); HRMS (ESI-FTICR) calcd for: C14H30Si2 [M]+ 254.1886, found: 254.1881; IR (film): 1909, 1461,
1254, 1046, 851 cm-1.
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(3-Cyclohexylpropa-1,2-diene-1,1-diyl)bis(trimethylsilane) 3u. Yield 84% (22.3 mg); colorless oil;
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TLC Rf = 0.90 (PE); H NMR (400 MHz, CDCl3) δ 4.40 (d, J = 5.9 Hz, 1H), 2.01-1.81 (m, 1H), 1.72-
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1.69 (m, 4H), 1.44-0.86 (m, 6H), 0.11 (s, 18H); C {1H} NMR (101 MHz, CDCl3) δ 209.8, 89.5, 82.4,
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36.1, 34.2, 26.5, 26.4, 0.2. GC-MS (EI, m/z, relative intensity) 266 (M+, 50), 251 (15), 192 (10), 178
(70), 73 (100); HRMS (ESI-FTICR) calcd for: C15H30Si2 [M]+ 266.1886, found: 266.1881; IR (film):
2095, 2846, 2172, 1728, 1448, 1250, 1031, 892, 841, 759 cm-1.
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(3-Cyclopropylpropa-1,2-diene-1,1-diyl)bis(trimethylsilane) 3v. Yield 88% (19.7 mg); colorless oil;
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TLC Rf = 0.95 (PE); H NMR (400 MHz, CDCl3) δ 4.53 (d, J = 5.7 Hz, 2H), 1.13-1.01 (m, 1H), 0.65-
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0.52 (m, 2H), 0.30-0.18 (m, 2H), 0.10 (s, 18H); C {1H} NMR (101 MHz, CDCl3) δ 210.7, 91.2, 79.7,
29.8, 7.5, 6.5, 0.2. GC-MS (EI, m/z, relative intensity) 224 (M+, 20), 209 (30), 181 (20), 151 (20), 97
(60), 73 (100); HRMS (ESI-FTICR) calcd for: C12H24Si2 [M]+ 224.1416, found: 224.1410; IR (film):
3085, 2955, 2927, 2896, 2175, 1912, 1714, 1250, 1031, 842, 760 cm-1.
(4,4-Dimethylpenta-1,2-diene-1,1-diyl)bis(trimethylsilane) 3w. Yield 61% (14.6 mg); colorless oil;
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TLC Rf = 0.90 (PE); H NMR (400 MHz, CDCl3) δ 4.42 (s, 1H), 1.01 (s, 1H), 0.11 (s, 18H); C {1H}
NMR (101 MHz, CDCl3) δ 208.7, 90.8, 88.7, 31.1, 30.7, 0.2. GC-MS (EI, m/z, relative intensity) 240
(M+, 30), 225 (50), 152 (15), 137 (100); HRMS (ESI-FTICR) calcd for: C13H28Si2 [M]+ 240.1729, found:
240.1725; IR (film): 1919, 1665, 1457, 1248, 840 cm-1.
5,5-Bis(trimethylsilyl)penta-3,4-dien-1-ol 3x. Yield 91% (20.7 mg); colorless oil; TLC Rf = 0.30
(PE:EA = 10:1); 1H NMR (400 MHz, CDCl3) δ 4.35 (t, J = 7.0 Hz, 1H), 3.63 (t, J = 6.4 Hz, 2H), 2.20 (q,
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J = 6.6 Hz, 2H), 1.54 (brs, 1H), 0.13 (s, 18H); C {1H} NMR (101 MHz, CDCl3) δ 210.3, 88.9, 71.4,
63.1, 31.1, 0.2. GC-MS (EI, m/z, relative intensity) 228 (M+, 10), 213 (5), 147 (50), 123 (100), 73 (90);
HRMS (ESI-FTICR) calcd for: C11H25OSi2 [M+H]+ 229.1438, found: 229.1443; IR (film): 3357, 1920,
1248, 840 cm-1.
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Propa-1,2-diene-1,1,3-triyltris(trimethylsilane) 3y. Yield 65% (16.6 mg); colorless oil; TLC Rf =
0.95 (PE); 1H NMR (400 MHz, CDCl3) δ 3.86 (s, 1H), 0.11 (s, 18H), 0.06 (s, 9H); 13C {1H} NMR (101
MHz, CDCl3) δ 208.4, 75.5, 62.3, 0.3, -0.2. GC-MS (EI, m/z, relative intensity) 256 (M+, 50), 241 (60),
168 (100), 153 (60), 73 (80); HRMS (ESI-FTICR) calcd for: C12H28Si3 [M]+ 256.1498, found: 256.1492;
IR (film): 1895, 1405, 1248, 1090, 837 cm-1.
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2-(Bis(trimethylsilyl)methyl)-1H-indole 5a. Yield 66% (18.2 mg); colorless oil; TLC Rf = 0.30
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(PE:EA = 20:1); H NMR (400 MHz, CDCl3) δ 7.51 (s, 1H), 7.47-7.41 (m, 1H), 7.25-7.21 (m, 1H),
7.06-6.99 (m, 2H), 5.99 (d, J = 1.5 Hz, 1H), 1.54 (s, 1H), 0.08 (s, 18H); 13C {1H} NMR (101 MHz,
CDCl3) δ 140.2, 135.4, 130.1, 119.8, 119.4, 118.8, 109.7, 98.6, 22.2, 0.2. GC-MS (EI, m/z, relative
intensity) 275 (M+, 100), 260 (20), 202 (30), 172 (20), 73 (90); HRMS (ESI-FTICR) calcd for:
C15H26NSi2 [M]+ 276.1598, found: 276.1600; IR (film): 1711, 1526, 1458, 1414, 1369, 1250, 1220, 841
cm-1.
2-(Bis(trimethylsilyl)methyl)-5-chloro-1H-indole 5b. Yield 73% (22.6 mg); colorless oil; TLC Rf =
0.50 (PE:EA = 10:1); 1H NMR (400 MHz, CDCl3) δ 7.54 (s, 1H), 7.40 (d, J = 2.0 Hz, 1H), 7.12 ((d, J =
8.5 Hz, 1H), 6.98 (dd, J = 8.5, 2.0 Hz, 1H), 5.93 (d, J = 1.5 Hz, 1H), 1.53 (s, 1H), 0.07 (s, 18H); 13C {1H}
NMR (101 MHz, CDCl3) δ 142.1, 133.7, 131.2, 125.1, 119.9, 118.2, 110.6, 98.2, 22.5, 0.1. GC-MS (EI,
m/z, relative intensity) 309 (M+, 45), 294 (5), 73 (100); HRMS (ESI-FTICR) calcd for: C15H25ClNSi2
[M+H]+ 310.1209, found: 310.1211; IR (film): 2345, 1727, 1575, 1523, 1464, 1402, 1340, 1250, 1056,
1022 cm-1.
2-(Bis(trimethylsilyl)methyl)-5-bromo-1H-indole 5c. Yield 79% (27.9 mg); colorless oil; TLC Rf =
0.50 (PE:EA = 10:1); 1H NMR (400 MHz, CDCl3) δ 7.56 (s, 2H), 7.15-6.93 (m, 2H), 5.93 (d, J = 1.9 Hz,
1H), 1.53 (s, 1H), 0.07 (s, 18H); 13C {1H} NMR (101 MHz, CDCl3) δ 142.0, 133.9, 131.8, 122.5, 121.3,
112.8, 110.0, 98.1, 22.5, 0.1. GC-MS (EI, m/z, relative intensity) 353 (M+, 30), 274 (100), 73 (100);
HRMS (ESI-FTICR) calcd for: C15H25BrNSi2 [M+H]+ 354.0703, found: 354.0711; IR (film): 1727,
1566, 1523, 1460, 1303, 1250, 1023, 841, 769 cm-1.
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1-(2-(Bis(trimethylsilyl)methyl)-1H-indol-1-yl)ethanone 5d. Yield 52% (16.5 mg); colorless oil;
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TLC Rf = 0.75 (PE:EA = 10:1); H NMR (400 MHz, CDCl3) δ 7.59-7.49 (m, 1H), 7.47-7.37 (m, 1H),
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7.20-7.13 (m, 2H), 6.18 (d, J = 0.5 Hz, 1H), 3.16 (s, 1H), 2.76 (s, 3H), 0.06 (s, 18H); C {1H} NMR
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(101 MHz, CDCl3) δ 171.7, 144.2, 135.2, 130.7, 122.7, 121.9, 119.5, 113.7, 106.0, 28.2, 19.1, 0.2. GC-
MS (EI, m/z, relative intensity) 317 (M+, 60), 302 (50), 244 (50), 229 (10), 73 (100); HRMS (ESI-
FTICR) calcd for: C17H28NOSi2 [M+H]+ 318.1709, found: 318,1720; IR (film): 1705, 1547, 1458, 1295,
1249, 1105, 841 cm-1.
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(Benzofuran-2-ylmethylene)bis(trimethylsilane) 5e. Yield 50% (13.8 mg); colorless oil; TLC Rf =
0.70 (PE); 1H NMR (400 MHz, CDCl3) δ 7.44-7.37 (m, 1H), 7.34 (d, J = 7.5 Hz, 1H), 7.17-7.04 (m, 2H),
6.09 (s, 1H), 1.78 (s, 1H), 0.09 (s, 18H); 13C {1H} NMR (101 MHz, CDCl3) δ 161.2, 154.3, 130.2, 122.2,
121.7, 119.2, 110.3, 99.8, 22.6, 0.1. GC-MS (EI, m/z, relative intensity) 276 (M+, 50), 261 (10), 203 (10),
188 (50), 73 (100); HRMS (ESI-FTICR) calcd for: C15H25OSi2 [M+H]+ 277.1438, found: 277.1446; IR
(film): 1566, 1455, 1252, 1161, 1022, 849 cm-1.
Experimental procedure for the reaction of 1,1-disilyl allenes with NBS or NIS. 1,1-Disilyl allene
(1.0 equiv, 0.10 mmol), NBS (1.0 equiv, 0.10 mmol, 17.8 mg) or NIS (1.0 equiv, 0.10 mmol, 22.5 mg)
and 1.0 mL CH3CN were mixed in an oven-dried reaction flask. The mixture was stirred at room
temperature under nitrogen atmosphere for about 1 hour. Petroleum ether was added to the mixture. The
mixture was filtered through celite. The solvents were evaporated under reduced pressure and the crude
residue was purified by flash chromatography on silica gel.
Experimental procedure for three-component reaction of 1,1-disilyl allenes, NBS, aniline.17 1,1-
Disilyl allene (1.0 equiv, 0.10 mmol), NBS (1.0 equiv, 0.10 mmol, 17.8 mg) and 1.0 mL CH3CN were
mixed in an oven-dried reaction flask. The mixture was stirred at room temperature under nitrogen
atmosphere for about 1 hour. The solvents were evaporated under reduced pressure. Then the mixture,
aniline (1.5 equiv, 0.15 mmol), i-Pr2NEt (1.2 equiv, 0.12 mmol, 12.1 mg, 16.8 μL) and 1.0 mL toluene
were mixed in an oven-dried reaction flask. The mixture was stirred at 90 oC under nitrogen atmosphere
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for about 20 hours. Then the crude mixture was cooled to room temperature. Diethyl ether was added to
the mixture. The mixture was filtered through celite. The solvents were evaporated under reduced
pressure and the crude residue was purified by flash chromatography on silica gel.
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Experimental procedure for three-component reaction of 1,1-disilyl allenes, NBS, ethanol. 1,1-
Disilyl allene (1.0 equiv, 0.10 mmol), NBS (1.0 equiv, 0.10 mmol, 17.8 mg) and 1.0 mL CH3CN were
mixed in an oven-dried reaction flask. The mixture was stirred at room temperature under nitrogen
atmosphere for about 1 hour. The solvents were evaporated under reduced pressure. Then the mixture
and 1.0 mL ethanol were mixed in an oven-dried reaction flask. The solution was stirred at room
temperature for about 1 hour. Diethyl ether was added to the mixture. The mixture was filtered through
celite. The solvents were evaporated under reduced pressure and the crude residue was purified by flash
chromatography on silica gel.
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(3-Bromooct-1-yn-1-yl)trimethylsilane 6a. Yield 91% (23.7 mg); colorless oil; TLC Rf = 0.70 (PE);
1H NMR (400 MHz, CDCl3) δ 4.50 (t, J = 6.8 Hz, 1H), 2.01-1.96 (m, 2H), 1.59-1.46 (m, 2H), 1.37-1.26
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(m, 4H), 0.90 (t, J = 7.0 Hz, 3H), 0.18 (s, 9H); C {1H} NMR (101 MHz, CDCl3) δ 104.1, 92.0, 39.7,
37.5, 30.9, 27.1, 22.5, 14.0, -0.2. GC-MS (EI, m/z, relative intensity) 260 (M+, 2), 245 (2), 165 (5), 139
(10), 109 (10), 73 (100); HRMS (EI-hybrid quadrupole-orbitrap) calcd for: C11H21BrSi [M]+ 260.0590,
found: 260.0591.
N-(1-Phenyl-3-(trimethylsilyl)prop-2-yn-1-yl)aniline 6b. Yield 78% (21.8 mg); colorless oil; TLC Rf
= 0.50 (PE:EA = 20:1); 1H NMR (400 MHz, CDCl3) δ 7.59-7.56 (m, 2H), 7.42-7.28 (m, 3H), 7.22-7.15
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(m, 2H), 6.80-6.74 (m, 1H), 6.72-6.70 (m, 2H), 5.27 (s, 1H), 4.05 (s, 1H), 0.15 (s, 9H); C {1H} NMR
(101 MHz, CDCl3) δ 146.6, 139.7, 129.2, 128.8, 128.1, 127.3, 118.6, 114.2, 104.9, 89.8, 50.9, 0.0. GC-
MS (EI, m/z, relative intensity) 279 (M+, 50), 206 (30), 187 (80), 159 (100), 145 (10); HRMS (ESI-
FTICR) calcd for: C18H20NSi [M-H]+ 278.1360, found: 278.1352; IR (film): 2175, 1601, 1502, 1250,
844 cm-1.
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(3-(4-Chlorophenyl)-3-ethoxyprop-1-yn-1-yl)trimethylsilane 6c. Yield 65% (17.2 mg); colorless oil;
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TLC Rf = 0.80 (PE:EA = 20:1); H NMR (400 MHz, CDCl3) δ 7.45 (d, J = 8.4 Hz, 2H), 7.39-7.29 (m,
2H), 5.12 (s, 1H), 3.72 (dq, J = 9.0, 7.0 Hz, 1H), 3.54 (dq, J = 9.1, 7.0 Hz, 1H), 1.25 (t, J = 7.0 Hz, 3H),
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0.20 (s, 9H); C {1H} NMR (101 MHz, CDCl3) δ 137.4, 134.2, 128.9, 128.7, 102.9, 92.8, 71.1, 64.0,
15.2, - 0.1. GC-MS (EI, m/z, relative intensity) 266 (M+, 60), 237 (90), 231 (80), 193 (100), 73 (90);
HRMS (ESI-FTICR) calcd for: C14H18ClOSi [M-H]+ 265.0810, found: 265.0818; IR (film): 2169, 1488,
1408, 1250, 1089, 1015, 843 cm-1.
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(3-(4-Chlorophenyl)-1-iodopropa-1,2-dien-1-yl)trimethylsilane 6d. Yield 83% (28.9 mg); colorless
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oil; TLC Rf = 0.70 (PE); H NMR (400 MHz, CDCl3) δ 7.31-7.27 (m, 2H), 7.22-7.17 (m, 2H), 5.75 (s,
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1H), 0.24 (s, 9H); C {1H} NMR (101 MHz, CDCl3) δ 206.6, 133.2, 131.4, 129.2, 128.4, 92.3, 60.7, -
1.2; HRMS (EI-hybrid quadrupole-orbitrap) calcd for: C12H14ClSi [M-I]+ 221.0548, found: 221.0546.
ASSOCIATED CONTENT
AUTHOR INFORMATION
Corresponding Author
*Email: wangjb@pku.edu.cn.
ORCID
Jianbo Wang: 0000-0002-0092-0937
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
The project is supported by National Basic Research Program of China (973 Program, No.
2015CB856600) and NSFC (Grant 21472004 and 21332002).
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Supporting Information
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Copies of 1H and 13C spectra for all products. This material is available free of charge via the Internet at
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http://pubs.acs.org.
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REFERENCES
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