Rhodium-Catalyzed Intermolecular trans-Disilylation of Alkynones with Unactivated Disilanes

Article abstract of DOI:10.1002/anie.201804223

Disilylation of alkynes could provide rapid entry to synthetically useful 1,2-bissilyl-alkenes, but is currently limited to activated disilanes reacting in an intramolecular fashion. Reported herein is an efficient rhodium(I)-catalyzed intermolecular disi

Full text of DOI:10.1002/anie.201804223

A Journal of the Gesellschaft Deutscher Chemiker
Angewandte
Chemie
International Edition
www.angewandte.org
Accepted Article
Title: Rhodium Catalyzed Intermolecular trans-Disilylation of Alkynones
with Unactivated Disilanes
Authors: Wei He, Tao He, Li-Chuan Liu, Le Guo, Bin Li, and Qing-Wei
Zhang
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201804223
Angew. Chem. 10.1002/ange.201804223
Link to VoR: http://dx.doi.org/10.1002/anie.201804223
http://dx.doi.org/10.1002/ange.201804223

10.1002/anie.201804223
Angewandte Chemie International Edition
COMMUNICATION
Rhodium Catalyzed Intermolecular trans-Disilylation of Alkynones
with Unactivated Disilanes
Tao He[a], Li-Chuan Liu[a], Le Guo[a], Bin Li[a], Qing-Wei Zhang*[b] and Wei He*[a]
Abstract: Disilylation of alkynes could provide rapid entry to
synthetically useful 1,2-bissilyl-alkenes, which is currently limited to
activated disilanes reacting in an intramolecular fashion. Herein, we
reported an efficient rhodium (I) catalyzed intermolecular disilylation
of a wide array of alkynones with unactivated disilanes. Importantly,
our reaction produced exclusively trans-disilylation products, a
selectivity that has been rarely reported. These disilylation products
were transformed to an interesting pentacyclic vinyl silane ethers,
among a number of further synthetic manipulations. Mechanistic
studies uncovered that the unactivated disilanes underwent facile Si-
Si activation and crossover under the reaction conditions.
appeared to be much more challenging, requiring harsher
conditions and resulting in lower yields. Importantly, the
intermolecular reactions with no exceptions produced cis-
products.
Our group has been working on the Rh catalyzed silicon
chemistry in the past years[9]. Along this line of research, we now
report a Rh(I) catalyzed disilylation of alkynones with unactivated
disilanes, leading exclusively to trans-disilylation
products
(Scheme 1c).
The incorporation of silicon atoms in organic compounds has
been shown to foster distinct physical, physiological and
optoelectronic properties, rendering numerous applications in
material[1] and pharmaceutical[2] sciences. In this context,
synthetic method that allows rapid entry into silicon building
blocks is not only a prerequisite but also a driven force to realize
the full potential of silicon containing compounds. Among them,
the synthesis of vinylsilanes[3] has remained a central topic due to
their versatile reactivities[4]. As a special subtype of vinylsilanes,
1,2-bissilyl-alkenes are perceived as useful building blocks
because manipulation of the two vicinal silicons may lead to
functionalized scaffolds such as densely substituted olefins.
Disilylation of alkynes, involving the 1,2-addition of Si-Si
compounds to alkynes in a stereo-controlled manner, is the most
straightforward and atom economic strategy to access 1,2-
bissilyl-alkenes[5].
Disilylation of alkynes has been achieved in both an
intramolecular[6] and intermolecular[7] fashion. Due to the
preorganization, the intramolecular reactions are usually efficient,
leading to five or six-membered ring bearing an exo vinylsilane
substitution (Scheme 1a). The reaction mechanism is believed to
involve Si-Si activation by oxidative addition, migratory insertion,
reduction elimination sequence, which inevitably result in cis-
products[7q]. In one exception, Matsuda and co-workers reported
unusual trans-products, which was proposed to originate from a
ring expansion pathway[8]. On the other hand, the intermolecular
reactions are best achieved with activated disilanes such as
strained cyclic disilanes and hetero-atom containing disilanes
(Scheme 1b). The reactions with non-activated disilanes
Scheme 1. Transition metal catalyzed disilylation of alkynones.
We commenced our study by using alkynone 1a and
diphenyltetramethyldisilane 2a (2.0 equiv) as model substrates,
with [Rh(cod)OH]2 (5 mol%) as the catalyst. Upon heating for 24
h at 80 oC, the reaction gave exclusively the trans-product[10] 3a,
albeit in a modest 24% yield (Figure 1). We noted that both in
literature and in our hands, the Pd-catalyzed reactions gave
mainly the cis-product. This striking contrast invoked us to explore
if such a reactivity is universal and if the reaction could be
optimized to a synthetically useful level.
[a]
[b]
T, He, L.-C. Liu, L. Guo, B. Li. Prof. Dr. W, He
School of Pharmaceutical Sciences and MOE Key Laboratory of
Bioorganic Phosphorus Chemistry & Chemical Biology
Tsinghua University, Beijing, P.R. China, 100084
E-mail: whe@tsinghua.edu.cn
Prof. Dr. Q.-W. Zhang
Department of Chemistry
University of Science and Technology of China, Hefei, China, 230026
E-mail: qingweiz@ustc.edu.cn
Figure 1. X-ray crystal structure of 3a.
We thus screened a large set of reaction parameters so as to
improve the reaction yield (Table 1). When the reaction was
conducted at lowered temperature (60 C), a lower conversion
and yield (8%) was obtained (entry 2). Increasing the reaction
temperature to 100 oC resulted in some improvement in
conversion and yield (28%) (entry 3). We then shifted our focus to
o
Supporting information for this article is given via a link at the end of
the document.
This article is protected by copyright. All rights reserved.

10.1002/anie.201804223
Angewandte Chemie International Edition
COMMUNICATION
other Rh catalysts: among [Rh(cod)Cl]2, [Rh(cod)OMe]2,
Rh(cod)2BF4 and Rh(nbd)2BF4, the cationic catalysts appeared to
superior (cf., entries 6, 7 vs entries 1-5) (also see supporting
information). Rh(nbd)2BF4 is the catalyst of choice, which gave
the best yield (82%) (entry 7). Solvents also played an important
role (entries 8-12). Another ethereal solvent DME gave a lower
yield of 51% (entry 8). Further lowering the polarity of the solvent,
as seen in the cases of dichloroethane (DCE) (entry 9) and
toluene (entry 10), resulted in further diminished yields of 49%
and 26%, respectively. Coordinative solvent acetonitrile
completely shut down the reaction (entry 11). Reducing the
rhodium catalyst loading to 2 mol% decreased the yield to 52%
(entry 12) and no product was observed in the absence of the
rhodium catalyst (entry 13). Reducing the amount of disilane to
1.1 equiv also compromised the yield (42%) (entry 14). Hence,
the optimal conditions are listed in entry 7, which was successfully
applied to gram scale reactions. For example, disilylated product
3a was obtained in a 64% yield on 2.5 mmol scale. Other types of
disilanes (hexamethlydisilane, 1, 2-diethoxy-tetramethyldisilane
and etc.) gave unsatisfactory yields (8-35%, supporting
information).
Trimethylsilyl (3o) substitution was also compatible with the
reaction conditions. Substrates containing heterocycles, such as
thiophene 3p and furan 3q, could furnish the desired products,
albeit in lower yields. Alkyl substitution were also examined. For
example, a n-propyl group on the ketone (3r) furnished a similar
yield (32%) to that of heterocyclic substrates (cf. 3p and 3q), while
a n-butyl group on the alkynone did not affect the reactivity as
compared to a phenyl group (3s vs 3a). This trend suggested that
the substitution on the alkynone (i.e., R group) is more forgiven
than that on the ketone (i.e., R’ group). Not surprisingly, when
both R and R’ were an alkyl groups, the reaction failed.
Table 2. Reaction scopes[a,b]
.
Table 1. Reaction conditions optimization[a]
.
Entry
Cat.
Solvent
Temp.(oC)
Yield (%)[b]
1
2
3
4
5
6
7
8
[Rh(cod)OH]2
[Rh(cod)OH]2
[Rh(cod)OH]2
[Rh(cod)Cl]2
[Rh(cod)OMe]2
Rh(cod)2BF4
Rh(nbd)2BF4
Rh(nbd)2BF4
Rh(nbd)2BF4
Rh(nbd)2BF4
Rh(nbd)2BF4
Rh(nbd)2BF4
none
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
dioxane
DME
DCE
Toluene
MeCN
dioxane
dioxane
dioxane
80
60
100
80
80
80
80
80
80
80
80
80
80
80
24
8
28
8
15
77
82
51
49
26
Trace
52
0
9
10
11
12[c]
13
14[d]
Rh(nbd)2BF4
42
[a] Conditions: alkynone 1a (0.05 mmol) and disilane 2a (0.10 mmol) under Ar
with rhodium catalyst (5 mol%) in solvent (0.25 mL) for 24 h. [b] NMR yields
using 2-nitrobenzaldehyde as internal standard. [c] 2 mol% of catalyst loading.
[d] 1.1 equiv of disilane.
[a] Conditions: alkynone 1 (0.10 mmol) and disilane 2a (0.20 mmol) under Ar in
dioxane (0.50 mL) for 24 h. [b] Isolated yields. [c] On 2.5 mmol scale. [d] At 100
oC. [e] On 1.05 mmol scale. [f] Catalyzed by [Rh(cod)OH]2.
With the optimized conditions in hand, we demonstrated the
reaction scope as shown in Table 2. The aryl substituents (R or
R’) with different electronic properties were tested first. Electron-
donating groups such as methyl,methoxyl and thiomethyl gave a
72%, 86% and 64% of yield, respectively (3b-3d). Electron-
withdrawing groups such as fluorine on either side of the alkynone
(3e, 3h) did not influence the yields. However, ester (3f) or
trifluoromethyl (3g) groups resulted in lower yields. Importantly,
halogen atoms were tolerated in this reaction, as shown in the
cases by the para-chlorine (3i), para-bromine (3j), meta-chlorine
(3k), meta-bromine (3l) and ortho-chlorine[10] (3m). Although the
yields were only moderate, the compatibility is important since
these aryl-halogen bond suffered undesired silylation as reported
by Naoto Chatani[11]. These remaining halogen atoms would allow
for further synthetic manipulations. The more bulky naphthyl (3n)
We further explored if such a trans-disilylation is also
practicable on other alkynes. The corresponding alkyne ester 1t
did not generate the disilylated product 3t using Rh(nbd)2BF4 as
the catalyst. However, changing the catalyst into [Rh(cod)OH]2
successfully afforded the trans-disilylated product 3t with 40%
yield (Table 2, 3t). In comparison, the disilylation of
diphenylacetylene 1u with Rh(nbd)2BF4 was also unsuccessful.
But with [Rh(cod)OH]2, the cis-disilylated product[10] 3u was
obtained in 20% yield (Scheme 2), similar to the results obtained
by Navarro and Spencer using a Pd catalyst[7r]. These results
suggested that the trans-product is substrate dependent, rather
than catalyst dependent.
A number of synthetic manipulations were investigated to
explore the synthetic utility of the trans-disilylated products. When
the disilylated product 3a was treated with excess TBAF, similar
substrate reacted smoothly to give
a good yield (80%).
This article is protected by copyright. All rights reserved.

10.1002/anie.201804223
Angewandte Chemie International Edition
COMMUNICATION
to the report of Fleming and co-workers[12], phenyl-migrated
d5 was produced in 29% yield (eq. 1). The reaction of 2a with
hexamethyldisilane 2b also produced the mixed disilane 2e albeit
in a low yield. These experiments suggested that the crossover
could take place regardless of ensuing disilylation of the
alkynones. This result could explain why crossover products were
obtained in disilylation reaction. As far as we know, this is the first
example of rhodium catalyzed cross metathesis of unactivated
product 4 was obtained in a moderate yield (Scheme 3).
disilanes[14]
.
Scheme 2. Cis-disilylation of diphenylacetylene. Conditions: 1u (0.10 mmol)
and 2a (0.20 mmol) under Ar with rhodium catalyst (5 mol%) in dioxane (0.50
mL) for 24 h.
Scheme 4. Cross over reaction of disilanes.
Scheme 3. Treatment by TBAF.
Table 3. Synthesis of pentacyclic vinyl silane ethers by reduction and Si-Ph
bond cleavege.
Figure 2. Proposed catalytic cycle.
Based on these observations, a plausible catalytic cycle was
proposed (Figure 2). Initially, the disassociation of one nbd ligand
from the precatalyst and subsequent oxidative insertion into the
disilane (e.g. 2a) would afford Si-Rh-Si species A. The σ bond
metathesis between coordinatively unsaturated A and another
disilane (e.g. 2a-d10), followed by reductive elimination could give
a combination of all possible disilanes (e.g., 2a, 2a-d5 and 2a-d10).
This process is independent from the remaining catalytic cycle.
As far as the disilylation is concerned, the catalytic cycle began
with the migratory insertion of the alkynone in to the Si-Rh bond,
forming mono-silicon intermediate B. The fate of B could diverge:
(1) reductive elimination to afford the cis-disilylated product. This
process may be disfavored as the stereo hindrance in B
prevented effective reductive elimination; (2) a competing but
sterically more favorable isomerization to intermediate D, which is
very likely to involve rhodium allenolate intermediate C[4l, 15]. The
observed side product 3r’ (in Z configuration but not in E
configuration) is another evidence that this isomerization did
occur (Supporting Information). Finally, reductive elimination
would lead to the trans-disilylated product and regenerate the
rhodium catalyst.
Notably, LiAlH4 as the reductant triggered an efficient ring
closure reaction to form pentacyclic vinyl silane ethers 5 in
generally good yields (Table 3). The skeleton of products 5 could
be regarded as a silicon embedded dihydrofuran. Such a novel
scaffold might be interesting in the search of silicon containing
bioactive small molecules. Further conversion of product 5a to
other synthetically useful building blocks via known
transformations such as the anion relay chemistry[13] was also
successfully achieved (see supporting information).
To elucidate the mechanism, we performed the deuterated
experiments. When deuterated disilane 2a-d5 (one phenyl group
was fully deuterated) was used, except for the expected product
3a-d5, two other products corresponding to 3a (no deuterium
incorporation) and 3a-d10 (10 deuterium atoms were incorporated)
were also detected in significant yields by GC-MS analysis (see
supporting information). When the reaction was carried out with
both 2a (1.0 equiv) and 2a-d10 (1.0 equiv, phenyl group on each
side were deuterated), very similar result was obtained. To
investigate at what stage the crossover occurred, we performed
the reaction of 2a and 2a-d10 in the absence of an alkynone under
otherwise identical conditions (Scheme 4). The mixed disilane 2a-
In conclusion, this Rh catalysed reaction overcomes both the
reactivity issue of unactivated dislanes and stereoselectivity issue
in obtaining trans-disilylation products. This method shows a good
substrate scope and functional group tolerance. The disilylated
products can be elaborated into interesting scaffold that are not
This article is protected by copyright. All rights reserved.

10.1002/anie.201804223
Angewandte Chemie International Edition
COMMUNICATION
M. Durandetti, J. Maddaluno, Angew. Chem. Int. Ed. 2017, 56, 2464-
2468; Angew. Chem. 2017, 129, 2504-2508.
easily accessed by other means. The interesting crossover
between disilanes partially explains why Rh is successful in this
difficult task, and suggests that Rh catalysis should be looked in
more detail in Si-Si activation, for the limited efforts (Matsuda[8]
and this work) as well as intriguing activity.
[7]
a) H. Sakurai, Y. Kamiyama, Y. Nakadaira, J. Am. Chem. Soc. 1975, 97,
931-932; b) H. Okinoshima, K. Yamamoto, M. Kumada, J. Organomet.
Chem. 1975, 86, C27-C30; c) K. Tamao, T. Hayashi, M. Kumada, J.
Organomet. Chem. 1976, 114, C19-C22; d) H. Watanabe, M. Kobayashi,
K. Higuchi, Y. Nagai, J. Organomet. Chem. 1980, 186, 51-62; e) H.
Matsumoto, I. Matsubara, T. Kato, K. Shono, H. Watanabe, Y. Nagai, J.
Organomet. Chem. 1980, 199, 43-47; f) H. Watanabe, M. Kobayashi, M.
Saito, Y. Nagai, J. Organomet. Chem. 1981, 216, 149-157; g) D. Seyferth,
E. W. Goldman, J. Escudie, J. Organomet. Chem. 1984, 271, 337-352;
h) H. Yamashita, M. Catellani, M. Tanaka, Chem. Lett. 1991, 241-244; i)
W. Finckh, B. Z. Tang, A. Lough, I. Manners, Organometallics 1992, 11,
2904-2911; j) Y. Pan, J. T. Mague, M. J. Fink, Organometallics 1992, 11,
3495-3497; k) T. Kusukawa, Y. Kabe, W. Ando, Chem. Lett. 1993, 985-
988; l) A. Naka, M. Hayashi, S. Okazaki, M. Ishikawa, Organometallics
1994, 13, 4994-5001; m) F. Ozawa, M. Sugawara, T. Hayashi,
Organometallics 1994, 13, 3237-3243; n) Y. Ito, M. Suginome, Pure Appl.
Chem. 1996, 68, 505-508; o) D. A. Loy, K. Rahimian, M. Samara, Angew.
Chem. Int. Ed. 1999, 38, 555-557; Angew. Chem. 1999, 111, 515-516;
p) K. H. Song, I. Jung, S. S. Lee, K. M. Park, M. Ishikawa, S. O. Kang, J.
J. Ko, Organometallics 2001, 20, 5537-5541; q) C. Gryparis, M.
Kidonakis, M. Stratakis, Org. Lett. 2013, 15, 6038-6041; r) M. B. Ansell,
D. E. Roberts, F. G. N. Cloke, O. Navarro, J. Spencer, Angew. Chem. Int.
Ed. 2015, 54, 5577-5582; Angew. Chem. 2015, 127, 5670-5674; s) P. H.
Xiao, Y. J. Cao, Y. Y. Gui, L. Gao, Z. L. Song. Angew. Chem. Int. Ed.
2018, 57, 4769-4773; Angew. Chem. 2018, 130, 4859-4863.
Acknowledgements
We gratefully acknowldege financial support form the National
Key R&D Program of China (No. 2017YFA0505200) and NSFC
(21625104, 21521091) .
Keywords: disilylation • rhodium • trans-addition • Si-Si
activation
[1]
[2]
a) M. Shimizu, T. Hiyama, Synlett 2012, 973-989; b) M. Driess, M.
Oestreich, Chemistry 2014, 20, 9144-9145.
a) G. A. Showell, J. S. Mills, Drug Discovery Today 2003, 8, 551-556; b)
J. S. Mills, G. A. Showell, Expert Opin. Invest. Drugs 2004, 13, 1149-
1157; c) M. W. Buttner, C. Burschka, J. O. Daiss, D. Ivanova, N. Rochel,
S. Kammerer, C. Peluso-Iltis, A. Bindler, C. Gaudon, P. Germain, D.
Moras, H. Gronemeyer, R. Tacke, Chembiochem 2007, 8, 1688-1699; d)
N. A. Meanwell, J. Med. Chem. 2011, 54, 2529-2591; e) J. B. G. Gluyas,
C. Burschka, S. Dorrich, J. Vallet, H. Gronemeyer, R. Tacke, Org. Biomol.
Chem. 2012, 10, 6914-6929; f) S. Fujii, Y. Miyajima, H. Masuno, H.
Kagechika, J. Med. Chem. 2013, 56, 160-166; g) A. K. Franz, S. O.
Wilson, J. Med. Chem. 2013, 56, 388-405.
[8]
[9]
T. Matsuda, Y. Ichioka, Org. Biomol. Chem. 2012, 10, 3175-3177.
a) Q. W. Zhang, K. An, W. He, Angew. Chem. Int. Ed. 2014, 53, 5667-
5671; Angew. Chem. 2014, 126, 5773-5777; b) Q. W. Zhang, K. An, L.
C. Liu, Y. Yue, W. He, Angew. Chem. Int. Ed. 2015, 54, 6918-6921;
Angew. Chem. 2015, 127, 7022-7025; c) Q. W. Zhang, K. An, L. C. Liu,
S. X. Guo, C. R. Jiang, H. F. Guo, W. He, Angew. Chem. Int. Ed. 2016,
55, 6319-6323; Angew. Chem. 2016, 128, 6427-6431; d) Q. W. Zhang,
K. An, C. Liu, Q. Zhang, H. F. Guo, W. He, Angew. Chem. Int. Ed. 2017,
56, 1125-1129; Angew. Chem. 2017, 129, 1145-1149.
[3]
[4]
a) I. Fleming, A. Barbero, D. Walter, Chem. Rev. 1997, 97, 2063-2192;
b) M. J. Curtis-Long, Y. Aye, Chem. Eur. J. 2009, 15, 5402-5416; c) D.
S. W. Lim, E. A. Anderson, Synthesis. 2012, 44, 983-1010.
a) R. J. Fessenden, M. D. Coon, J. Org. Chem. 1964, 29, 1607-1610; b)
B. L. Chenard, C. M. Vanzyl, J. Org. Chem. 1986, 51, 3561-3566; c) T.
N. Mitchell, R. Wickenkamp, A. Amamria, R. Dicke, U. Schneider, J. Org.
Chem. 1987, 52, 4868-4874; d) M. G. Voronkov, S. V. Kirpichenko, V. V.
Keiko, A. I. Albanov, J. Organomet. Chem. 1992, 427, 289-292; e) M.
Murakami, H. Amii, N. Takizawa, Y. Ito, Organometallics 1993, 12, 4223-
4227; f) G. Auer, M. Oestreich, Chem. Commun. 2006, 311-313; g) S.
Nakamura, M. Uchiyama, T. Ohwada, J. Am. Chem. Soc. 2004, 126,
11146-11147; h) A. Kuznetsov, V. Gevorgyan, Org. Lett. 2012, 14, 914-
917; i) K. B. Ouyang, Y. Liang, Z. F. Xi, Org. Lett. 2012, 14, 4572-4575;
j) S. T. Ding, L. J. Song, L. W. Chung, X. H. Zhang, J. W. Sun, Y. D. Wu,
J. Am. Chem. Soc. 2013, 135, 13835-13842; k) A. Kuznetsov, Y. Onishi,
Y. Inamoto, V. Gevorgyan, Org. Lett. 2013, 15, 2498-2501; l) J. A.
Calderone, W. L. Santos, Angew. Chem. Int. Ed. 2014, 53, 4154-4158;
m) R. T. H. Linstadt, C. A. Peterson, D. J. Lippincott, C. I. Jette, B. H.
Lipshutz, Angew. Chem. Int. Ed. 2014, 53, 4159-4163; Angew. Chem.
2014, 126, 4238-4242; n) E. Romain, C. Fopp, F. Chemla, F. Ferreira, O.
Jackowski, M. Oestreich, A. Perez-Luna, Angew. Chem. Int. Ed. 2014,
53, 11333-11337; Angew. Chem. 2014, 126, 11515-11519; o) Y. H. Xu,
L. H. Wu, J. Wang, T. P. Loh, Chem. Commun. 2014, 50, 7195-7197; p)
R. Shintani, H. Kurata, K. Nozaki, J. Org. Chem. 2016, 81, 3065-3069;
q) C. Fopp, E. Romain, K. Isaac, F. Chemla, F. Ferreira, O. Jackowski,
M. Oestreich, A. Perez-Luna, Org. Lett. 2016, 18, 2054-2057.
[10] CCDC 1816194 3a, CCDC 1816193 3m, CCDC 1816195 3u contain the
crystallographic data for this paper. These data can be obtained free of
charge from the Cambridge Crystallographic Data Centre.
[11] M. Tobisu, Y. Kita, Y. Ano, N. Chatani, J. Am. Chem. Soc. 2008, 130,
15982-15989.
[12] I. Fleming, T. W. Newton, V. Sabin, F. Zammattio, Tetrahedron 1992, 48,
7793-7802.
[13] A. B. Smith, R. B. Tong, W. S. Kim, W. A. Maio, Angew. Chem. Int. Ed.
2011, 50, 8904-8907; Angew. Chem. 2011, 123, 9066-9069.
[14] T. Kusukawa, Y. Kabe, B. Nestler, W. Ando, Organometallics, 1995, 14,
2556
[15] a) J. Klein, R. Levene, J. Chem. Soc., Perk. Trans. 2 1973, 1971-1978;
b) Y. Yamamoto, H. Yatagai, K. Maruyama, J. Org. Chem. 1979, 44,
1744-1746; c) J. P. Marino, R. J. Linderman, J. Org. Chem. 1983, 48,
4621-4628; d) M. C. P. Yeh, P. Knochel, Tetrahedron Lett. 1989, 30,
4799-4802; e) K. Nilsson, T. Andersson, C. Ullenius, A. Gerold, N.
Krause, Chem. Eur. J. 1998, 4, 2051-2058; f) G. G. Li, H. X. Wei, B. R.
Whittlesey, N. N. Batrice, J. Org. Chem. 1999, 64, 1061-1064; g) M. P.
Jennings, K. B. Sawant, Eur. J. Org. Chem. 2004, 3201-3204; h) M.
Ahlquist, T. E. Nielsen, S. Le Quement, D. Tanner, P. O. Norrby, Chem.
Eur. J. 2006, 12, 2866-2873; i) A. J. Mueller, M. P. Jennings, Org. Lett.
2007, 9, 5327-5329; j) S. Vercruysse, L. Cornelissen, F. Nahra, L. Collard,
O. Riant, Chem. Eur. J. 2014, 20, 1834-1838; k) E. Piers, R. M. Lemieux,
Organometallics 1998, 17, 4213-4217..
[5]
[6]
For reviews see: a) M. Suginome, Y. Ito, J.Chem. Soc., Dalton Trans.,
1998, 1925-1934; b) I. Beletskaya, C. Moberg, Chem. Rev. 1999, 99,
3435-3461; c) M. Suginome, Y. Ito, Chem. Rev. 2000, 100, 3221-3256;
d) I. Beletskaya, C. Moberg, Chem. Rev. 2006, 106, 2320-2354; e) M. B.
Ansell, O. Navarro, J. Spencer, Coord. Chem. Rev. 2017, 336, 54-77.
a) Y. Ito, M. Suginome, M. Murakami, J. Org. Chem. 1991, 56, 1948-
1951; b) M. Murakami, M. Suginome, K. Fujimoto, Y. Ito, Angew. Chem.
Int. Ed. Engl. 1993, 32, 1473-1475; Angew. Chem. 1993, 105, 1542; c)
M. Murakami, H. Oike, M. Sugawara, M. Suginome, Y. Ito, Tetrahedron
1993, 49, 3933-3946; d) M. Suginome, H. Oike, S. S. Park, Y. Ito, B.
Chem. Soc. Jpn. 1996, 69, 289-299; e) M. Suginome, A. Takama, Y. Ito,
J. Am. Chem. Soc. 1998, 120, 1930-1931; f) M. Ahmad, A. C. Gaumont,
This article is protected by copyright. All rights reserved.

10.1002/anie.201804223
Angewandte Chemie International Edition
COMMUNICATION
COMMUNICATION
Tao He, Li-Chuan Liu, Le Guo, Bin Li,
Qing-Wei Zhang* and Wei He*
Page No. – Page No.
Rhodium Catalyzed Intermolecular
trans-Disilylation of Alkynones with
Unactivated Disilanes
An unprecedented intermolecular trans-disilylation of alkynones with inert disilanes
has been realized. Under mild reaction conditions, various functional groups
including heterocyles and halides were tolerated. The disilylated products were
efficiently transformed to pentacyclic vinyl silane ethers which are interesting building
blocks. Cross-over experiment with deuterated disilanes has disclosed a Si-Si -
metathesis mechanism that is independent from the silylation reaction.
This article is protected by copyright. All rights reserved.