B(C6F5)3-Catalyzed C-Si/Si-H Cross-Metathesis of Hydrosilanes

Article abstract of DOI:10.1021/jacs.7b08053

The substituent redistribution of hydrosilanes on silicon through C-Si and Si-H bond cleavage and reformation is of great interest and importance, but this transformation is usually difficult to achieve in a selective fashion. By using electron-rich aromatic hydrosilanes, we have achieved for the first time the selective C-Si/Si-H bond homo- and cross-metathesis of a series of hydrosilanes in the presence of a boron catalyst B(C₆F₅)₃. This protocol features simple reaction conditions, high chemoselectivity, wide substrate scope, and high functionality tolerance, offering a new pathway for the synthesis of multisubstituted functional silanes.

Full text of DOI:10.1021/jacs.7b08053

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Communication
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B(CF)-Catalyzed C–Si/Si–H Cross-Metathesis of Hydrosilanes
Yuanhong Ma, Liang Zhang, Yong Luo, Masayoshi Nishiura, and Zhaomin Hou
J. Am. Chem. Soc., Just Accepted Manuscript • Publication Date (Web): 24 Aug 2017
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B(C6F5)3-Catalyzed C–Si/Si–H Cross-Metathesis of Hy-
drosilanes
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Yuanhong Ma,† Liang Zhang,*†,‡ Yong Luo,† Masayoshi Nishiura,†,‡ and Zhaomin Hou*†,‡
†Organometallic Chemistry Laboratory, RIKEN, 2ꢀ1 Hirosawa, Wako, Saitama 351ꢀ0198, Japan
‡Advanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2ꢀ1 Hirosawa, Wako, Saitama 351ꢀ
0198, Japan
Supporting Information Placeholder
offers an easy access to diverse silylated aromatic compounds
from hydrosilanes.
ABSTRACT: The substituent redistribution of hydrosilanes on
silicon through C–Si and Si–H bond cleavage and reformation is
of great interest and importance, but this transformation is usually
difficult to achieve in a selective fashion. By using electronꢀrich
aromatic hydrosilanes, we have achieved for the first time the
selective C–Si/Si–H bond homoꢀ and crossꢀmetathesis of a series
of hydrosilanes in the presence of a boron catalyst B(C6F5)3. This
protocol features simple reaction conditions, high chemoselectiviꢀ
ty, wide substrate scope, and high functionality tolerance, offering
a new pathway for the synthesis of multiꢀsubstituted functional
silanes.
Scheme 1. Substituent Redistribution of Hydrosilanes on
Silicon
(a) Previous work: Disproportionation of a hydrosilane to two or more
organosilicon compounds
(b) This work: Selective crossꢀmetathesis of two different hydrosilanes
Organosilicon compounds play a vital role in synthetic organic
chemistry and materials science.1 Therefore, the investigation of
C–Si bond formation and cleavage has constantly attracted interꢀ
est in the chemical community.2,3 One particularly interesting
reaction is the substituent redistribution or disproportionation of
hydrosilanes on silicon, which converts one hydrosilane to two or
more organosilicon compounds through C–Si and Si–H bond
cleavage and reformation (Scheme 1a).4ꢀ9 However, in spite of
being conceptually curious and potentially useful as a synthetic
route, this transformation has not been well examined to date. The
redistribution of hydrosilanes was often observed as a sideꢀ
reaction of transitionꢀmetalꢀcatalyzed dehydrocoupling of hyꢀ
drosilanes5a,d,f or in stoichiometric transformations mediated by
some organometallic complexes,5b,c,e while sporadic examples of
some catalytic versions were also reported.4,6ꢀ8 The stoichiometric
substituent exchange of tertiary hydrosilanes promoted by
[Ph3C][B(C6F5)4] was reported as a useful route for the generation
of triarylsilylium ions.9 The reactions (either stoichiometric or
catalytic) reported to date often suffered from poor selectivity or
limited substrate scope. In particular, the selective C–Si/Si–H
crossꢀmetathesis of two different hydrosilanes has remained unꢀ
known to date.
On the basis of our previous studies of the B(C6F5)3ꢀcatalyzed
C–H silylation of electronꢀrich arenes with hydrosilanes,11i we
envisioned that the introduction of an electronꢀdonating group to
the aromatic ring of an aryl substituent in hydrosilanes might
promote the aryl group transfer and thus enable selective substituꢀ
ent redistribution at the Si atom. By examining a set of aryl hyꢀ
drosilanes (See Table S1 in Supporting Information), we found
that tertiary hydrosilanes with an aryl group having the N,Nꢀ
dimethylamino substituent at the meta position selectively underꢀ
went aryl/hydride exchange in the presence of 5 mol % B(C6F5)3
at 100 °C in chlorobenzene.12 Besides the N,Nꢀdimethylamino
group, other amino groups such as ethylꢀ, benzylꢀ, and trifluoroalꢀ
kylꢀsubstituted amino groups as well as cyclic amino units all
worked effectively for the aryl (Ar) redistribution of a series of
hydrosilanes having a general formula of ArMe2SiH, which exꢀ
clusively afforded the corresponding diaryl dimethyl silane prodꢀ
ucts such as 2a–2j in high yields with release of Me2SiH2 (Table
1).13 The C–F and C–Br bonds (cf. 2c, 2h and 2i), which are useꢀ
ful in organic synthesis, were compatible with the catalytic reacꢀ
tion conditions. In addition to the aminoarylꢀsubstituted hyꢀ
drosilanes, ferrocenyl dimethyl hydrosilane also selectively unꢀ
derwent the redistribution reaction to give the di(ferrocenyl) diꢀ
methyl silane product 2k in 81% yield.
Boron Lewis acids, such as B(C6F5)3, have recently received
much attention as efficient catalysts for Si–H bond activation and
related transformations.10,11 In the course of our recent studies on
the B(C6F5)3ꢀcatalyzed aromatic C–H silylation with hyꢀ
drosilanes,11i we noticed that some hydrosilanes could undergo
redistribution in the presence of B(C6F5)3. Herein we report our
studies on the B(C6F5)3ꢀcatalyzed redistribution reactions of variꢀ
ous hydrosilanes. By appropriately tuning the electronic properꢀ
ties of the hydrosilane substrates, we have successfully achieved
for the first time both homoꢀ and crossꢀmetathesis of a wide range
of hydrosilanes in a selective fashion (Scheme 1b). This protocol
With the success of the selective redistribution (homoꢀ
metathesis) of the electronꢀrich aryl hydrosilanes, we then examꢀ
ined their crossꢀmetathesis with other hydrosilanes. At first, the
reaction of (mꢀMe2NC6H4)Me2SiH (1a) with
2 equiv. of
PhMe2SiH (3a) was carried out in the presence of 5 mol % of
B(C6F5)3, which afforded the crossꢀmetathesis product (mꢀ
Me2NC6H4)PhMe2Si (4a) in 79% isolated yield with release of
Me2SiH2 (Table 2).13 The solid structure of the HCl adduct of 4a
was confirmed by singleꢀcrystal Xꢀray analysis (Table 2). The
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homoꢀmetathesis product of 1a was formed in less than 5% yield
mixed aryl phenyl dimethyl silane products such as 4b−4g and
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(2a), while Ph2Me2Si (a homoꢀmetathesis product of 3a) was
negligible (see Table S2 in Supporting Information). In a similar
fashion, the crossꢀmetathesis reaction between 3a and a series of
acyclic and cyclic amino aryl dimethyl hydrosilanes also selecꢀ
tively took place, affording the corresponding
4j,k in 60−84% yields. The electronꢀwithdrawing fluorineꢀ and
bromineꢀsubstituted aryl silanes showed relatively lower activity
for the present crossꢀmetathesis reaction, which gave the expected
products (such as 4h and 4i) in 22−40% yields under the similar
conditions. Indolyl dimethyl hydrosilanes were suitable partners
for the crossꢀmetathesis with 3a, giving the corresponding mixed
indolyl phenyl dimethyl silane products such as 4l and 4m in
58−64% yields albeit with 10 mol % B(C6F5)3. Moreover, ferroꢀ
cenyl dimethyl silane also showed high reactivity with 3a, affordꢀ
ing the mixed ferrocenyl phenyl dimethyl silane product 4n in 72%
yield.
Table 1. B(C6F5)3ꢀCatalyzed Selective Substituent Redisꢀ
tribution of Hydrosilanesa
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Table 3. B(C6F5)3ꢀCatalyzed CrossꢀMetathesis of (mꢀ
Me2NC6H4)Me2SiH with Various Hydrosilanesa
N
N
B(C6F5)3 (5 mol%)
PhCl, 100 oC, 24 h
[Si]
H
+
H
[Si]
Si
H
Me2Si
5
1a
3
H
N
N
N
N
SMe
Si
Si
Si
Si
5c, 79%
N
5d, 82%
5a, 84%
5b, 73%
N
N
N
F
Cl
Br
CF3
Si
Si
Si
Si
aReaction conditions: hydrosilane 1 (0.25 mmol), B(C6F5)3 (5.0
mol %) and chlorobenzene (0.5 mL) under N2 at 100 °C for 24 h.
Isolated yield.
5e, 67%
5f, 70%
5g, 65%
5h, 72%
N
N
N
N
N
Ph
Table 2. B(C6F5)3ꢀCatalyzed CrossꢀMetathesis of
PhMe2SiH with Various Electronꢀrich Hydrosilanesa
Si
Si
Si
Br
Si
Cl
5k, 45%
5j, 57%
5l, 75%
5i, 73%
FG
B(C6F5)3 (5 mol%)
Ar
FG
+
H
Si
Si
H
Ar
PhCl, 100 oC, 24 h
N
Si
N
N
H
3a
S
O
O
1
Me2Si
4
H
Si
Si
5o, 57%
Si
Si
5n, 66%
Bn
N
N
5p, 66%
5m, 40%
N
N
N
N
Si
Si
4a, 79%
4b, 71%
Si
4a HCl
Si
Si
Si
S
Ph
H
H
Ph
5t, 56%
5q, 76%
5s, 61%
5r, 69%
Et
Et
Bn
Bn
N
N
N
CF3
N
N
N
N
Si
Si
Si
4c, 70%
Si
4f, 81%
Si
Si
Si
4e, 76%
4d, 73%
5w, 81%b
5u, 47%
5v, 82%
aReaction conditions: 1a (0.25 mmol), hydrosilane 3 (0.50 mmol),
N
N
N
N
B(C6F5)3 (5.0 mol %) and chlorobenzene (0.5 mL) under N2 at
b
100 °C for 24 h. Isolated yield. 1.25 mmol of EtMe2SiH was
Si
Br
Si
4i, 36%
F
Si
4h, 22% (40%)b
Si
used.
4j, 75%
4g, 84%
We then chose 1a as an electronꢀrich partner for the crossꢀ
metathesis with various hydrosilanes. Some representative results
are summarized in Table 3. A wide range of aryl dimethyl hyꢀ
drosilanes bearing alkyl, phenyl, trifluoromethyl, methylsulfide,
and halogen (F, Cl, Br) substituents at the aromatic ring smoothly
reacted with 1a, selectively affording the desired crossꢀmetathesis
products such as 5a−l in moderate to high yields. A substituent at
the ortho position of the aromatic ring (see 5j and 5k) slightly
lowered the reactivity, possibly because of the steric hindrance.
Many kinds of heteroaromatic groups such as thienyl, furyl, benꢀ
zofuryl and dibenzothienyl were compatible with this catalyst
system, giving the corresponding crossꢀmetathesis products such
as 5n−5q in 57−76% yields. Secondary hydrosilanes such as
PhMeSiH2 and Ph2SiH2 were also suitable for the crossꢀ
Fe
N
N
Si
Si
N
Si
Si
4k, 60%
4m, 64%c
4l, 58%c,d
4n, 72%
aReaction conditions: hydrosilane 1 (0.25 mmol), 3a (0.50 mmol),
B(C6F5)3 (5.0 mol %) and chlorobenzene (0.5 mL) under N2 at
b
100 °C for 24 h, unless otherwise noted. Isolated yield. 120 °C,
d
48 h, 0.75 mmol of PhMe2SiH. cB(C6F5)3 (10.0 mol %). 120 °C,
36 h, 0.75 mmol of PhMe2SiH.
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metathesis with 1a, affording the desired products 5r and 5s in
On the basis of the above experimental observations, a possiꢀ
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69% and 61% yields, respectively. The reaction of diphenyl meꢀ
thyl silane Ph2MeSiH with 1a gave the desired crossꢀmetathesis
product 5t in 56% yield, despite relatively high steric bulkiness.
Moreover, dimethyl hydrosilanes bearing an alkynyl, alkenyl, or
ethyl group were also suitable substrates for the reaction with 1a,
affording the desired crossꢀmetathesis reaction products 5u−5w in
moderate to good yields.
ble reaction mechanism for the B(C6F5)3ꢀcatalyzed crossꢀ
metathesis reaction between 1a and 3a is proposed in Scheme 4.
An interaction between B(C6F5)3 and the hydride in 3a could give
a weak adduct like A, in which the Si−H bond could be polarized
to generate a cationic Si center.9,10a,e,11aꢀd The approach of 1a to A
from the back side may promote the migration of the electronꢀrich
Me2NC6H4 group from the Si atom in 1a to that in 3a via B to
give C.11aꢀc,12 Release of the volatile Me2SiH2 from C would finalꢀ
ly give the crossꢀmetathesis product 4a and regenerate B(C6F5)3.
Amino groupꢀcontaining organosilicon compounds are known
to be important components in many functional materials and
pharmaceuticals.14 Furthermore, amino groups can also undergo
synthetically useful transformations.15 To demonstrate the usefulꢀ
ness of the reaction products obtained in this work, the N,Nꢀ
dimethylaminophenylꢀcontaining products 4a and 5i were examꢀ
ined. Treatment of 4a and 5i with methyl trifluoromethanesulꢀ
fonate (MeOTf) in CH2Cl2 easily generated the quaternary amꢀ
monium salts 6a (R = H) and 6b (R = Ph), respectively in almost
quantitative yields (Scheme 2). The reaction of 6a with the arylꢀ
boronic acid 7 in the presence of a nickel catalyst16 afforded the
corresponding crossꢀcoupling product 8 in 65% isolated yield
(Scheme 2a). Similarly, the reaction of 6a with the Grignard reaꢀ
gent 9 in the presence of a palladium catalyst17 gave the crossꢀ
coupling product 10 in 70% yield (Scheme 2b). Treatment of 6b
9
Scheme 3. Substituent Redistribution Involving Different
Tertiary and Quaternary Silanes
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i
with PrONa in the presence of a nickel catalyst18 easily yielded
the deamination product 11 (Scheme 2c).
Scheme 2. Examples of transformation of N,Nꢀ
dimethylaminophenyl silane products 4a and 5i
Scheme 4. A Possible Mechanism of C−Si/Si−H Bond
CrossꢀMetathesis of 1a and 3a.
To gain information on the reaction mechanism, we carried
out several control experiments as shown in Scheme 3. The reacꢀ
tion of (mꢀMe2NC6H4)Me2SiH (1a) with Ph(CD3)2SiH (3aꢀd)
exclusively yielded the CD3ꢀcontaining crossꢀmetathesis product
(mꢀMe2NC6H4)Ph(CD3)2Si (4aꢀd) with release of Me2SiH2
(Scheme 3, eq. 1), suggesting that the electronꢀrich Me2NC6H4
group in 1a was transferred to the silicon atom of Ph(CD3)2SiH.
In consistence, the reaction of the quaternary silane (mꢀ
Me2NC6H4)Me3Si (1aꢀMe) with PhMe2SiH (3a) selectively gave
(mꢀMe2NC6H4)PhMe2Si (4a), as a result of migration of the
Me2NC6H4 group and release of Me3SiH (Scheme 3, eq. 2). In
contrast, in the coexistence of (mꢀMe2NC6H4)Me2SiH (1a) and
PhMe3Si (3aꢀMe), the homoꢀmetathesis product of 1a, namely 2a,
was selectively formed with release of Me2SiH2, while PhMe3Si
remained unchanged (Scheme 3, eq. 3). No crossꢀmetathesis
product was observed. Under the same conditions, the redistribuꢀ
tion of PhMe2SiH (3a) was very slow, giving only a trace amount
of the redistribution product Ph2Me2Si (2ꢀPh) (Scheme 3, eq. 4;
see also Table S1 in Supporting Information). These results clearꢀ
ly demonstrate that transfer of the relatively electronꢀrich
Me2NC6H4 group is much easier than that of Ph and a Si–H unit is
essential to receive the transfer of the Me2NC6H4 group in the
present redistribution reactions.
In summary, we have achieved for the first time the selective
C–Si/Si–H bond crossꢀmetathesis of two different hydrosilanes as
well as the metalꢀfree catalytic redistribution of a series of elecꢀ
tronꢀrich aromatic hydrosilanes by using the commercially availaꢀ
ble B(C6F5)3 as a catalyst. The reaction takes place selectively
through migration of a relatively electronꢀrich aryl group such as
Me2NC6H4 to the Si atom of a hydrosilane unit which is activated
by the HꢀꢀꢀB(C6F5)3 interaction. A wide range of hydrosilanes are
applicable for this selective transformation. Aromatic and aliphatꢀ
ic C–X (X = F, Cl, Br) bonds as well as alkenyl, alkynyl, and
various heteroaromatic groups are compatible. This protocol ofꢀ
fers a concise access to diverse silylated aromatic compounds and
may open a new window to the chemistry of boron and silicon.
ASSOCIATED CONTENT
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Chang, S. J. Am. Chem. Soc. 2015, 137, 15176. (g) Kim, Y.; Chang, S.
Supporting Information
Angew. Chem., Int. Ed. 2016, 55, 218. (h) Ren, X.; Du, H. J. Am. Chem.
Soc. 2016, 138, 810. (i) Ma, Y.; Wang, B.; Zhang, L.; Hou, Z. J. Am.
Chem. Soc. 2016, 138, 3663. (j) Yin, Q.; Klare, H. F. T.; Oestreich, M.
Angew. Chem., Int. Ed. 2016, 55, 3204. (k) Süsse, L.; Hermeke, J.; Oesꢀ
treich, M. J. Am. Chem. Soc. 2016, 138, 6940. (l) Han, Y.; Zhang, S.; He,
J.; Zhang, Y. J. Am. Chem. Soc. 2017, 139, 7399. (m) Chulsky, K.; Doꢀ
brovetsky, R. Angew. Chem., Int. Ed. 2017, 56, 4744. (n) Liu, Z.ꢀY.; Wen,
Z.ꢀH.; Wang, X.ꢀC. Angew. Chem., Int. Ed. 2017, 56, 5817.
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4
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Experimental procedures, characterization data and copies of
NMR spectra. This material is available free of charge via the
Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
(12) In the case of orthoꢀ and paraꢀN,Nꢀdimethylaminophenyl silanes,
desilylation was observed. For examples of electrophilic desilylation, see:
Angew. Chem., Int. Ed. 2017, 56, 52 and references cited therein.
houz@riken.jp;lzhang@riken.jp
Notes
The authors declare no competing financial interests.
9
(13) The 1H NMR signals of Me2SiH2 (500 MHz, C6D5Cl) were observed
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at δ 0.04 (t, J = 4.0 Hz, 6 H) and 3.83−3.87 (m, 2 H). Caution: Me2SiH2 is
ACKNOWLEDGMENT
a flammable gas (bp = ‒20 °C), so safety precautions should be made
when opening the reaction vessel at the end of the reaction. Especially,
precautions are required to run these reactions in large scales. No accident
was encountered in our studies. Also see: Buslov, I.; Keller, S. C.; Hu, X.
Org. Lett. 2016, 18, 1928 and references cited therein.
This work was supported in part by a GrantꢀinꢀAid for Scientific
Research (S) (26220802) from JSPS. We gratefully appreciate
Mrs. Akiko Karube at Organometallic Chemistry Laboratory and
Dr. Takemichi Nakamura at Molecular Structure Characterization
Unit, RIKEN Center for Sustainable Resource Science for highꢀ
resolution mass spectrum measurements.
(14) (a) Lukinavičius, G.; Umezawa, K.; Olivier, N.; Honigmann, A.;
Yang, G.; Plass, T.; Mueller, V.; Reymond, L.; Jr, I. R. C.; Luo, Z.ꢀG.;
Schultz, C.; Lemke, E. A.; Heppenstall, P.; Eggeling, C.; Manley, S.;
Johnsson, K. Nature Chem. 2013, 5, 132. (b) Myochin, T.; Hanaoka, K.;
Iwaki, S.; Ueno, T.; Komatsu, T.; Terai, T.; Nagano, T.; Urano, Y. J. Am.
Chem. Soc. 2015, 137, 4759. (c) Lukinavičius, G.; Reymond, L.; Umezaꢀ
wa, K.; Sallin, O.; D’Este, E.; Göttfert, F.; Ta, H.; Hell, S. W.; Urano, Y.;
Johnsson, K. J. Am. Chem. Soc. 2016, 138, 9365. (d) Franz, A. K.; Wilson,
S. O. J. Med. Chem. 2013, 56, 388.
(15) Ouyang, K.; Hao, W.; Zhang, W.ꢀX.; Xi, Z. Chem. Rev., 2015, 115,
12045.
(16) Blakey, S. B.; MacMillan, D. W. C. J. Am. Chem. Soc. 2003, 125,
6046.
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