ChemComm
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COMMUNICATION
DOI: 10.1039/C5CC01569C
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1-methoxy-4-((4-
triethoxysilane,
(trifluoromethyl)phenyl)ethynyl)benzene
and
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) Y. Kawasaki, Y. Ishikawa, K. Igawa and
) D. A. Rooke
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followed by the treatment of the reaction mixture with methyllithium,
produced the corresponding silylindene in 48% yield as a mixture of
inseparable regioisomers. Other alkynes, such as bis(2-tolyl)acetylene,
b
c
bis(1-naphthyl)acetylene,
bis(4-pyridyl)acetylene,
bis(2-
d
thienyl)acetylene, 1-phenyl-1-propyne, and ethynylbenzene, did not
give the desired silylindenes.
e
reaction
between
diphenylacetylene
(1a
)
and
f
dimethyl(phenyl)silane (2a) in the presence of 5 equivalents of D2O
under the similar reaction conditions in Table 1, entry 9 gave
silylinedene 3a in 43% yield without incorporation of a deuterium
atom.
(g
6
7
For synthesis of dibenzophosphole oxides, see: Y. Kuninobu, T.
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Ogasawara, J. Am. Chem. Soc., 2001, 123, 9918.
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10 For examples of transition metal-catalysed reactions using a substrate
and 2 equivalents of alkyne moieties. See: ( ) Y. Kawanami and K. 24 (
Yamamoto, Synlett, 1995, 1232; ( ) M. Suginome, T. Matsuda and 46, 2578; (
Y. Ito, Organometallics, 1998, 17, 5233; ( ) H. Yoshida, E. Phys., 2014, 16, 24250.
Shirakawa, Y. Nakao, Y. Honda and T. Hiyama, Bull. Chem. Soc. 25 Because of an induction period in [RhCl(cod)]2/PPh3 catalysis, we
Jpn., 2001, 74, 637; ( ) K. Ueura, T. Satoh and M. Miura, J. Org. chose the Wilkinson’s catalyst for KIE experiments.
Chem., 2007, 72, 5362; ( ) S. Saito, S. Komagawa, I. Azumaya and 26 The desilylation was carried out according to the following literature:
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b
b
c
d
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) T. Fukutani, K.
W. M. Seganish and P. DeShong, J. Org. Chem., 2004, 69, 6790.
) Z. 27 The desilylation and iodination was performed according to the
following literature: S. R. Wilson and L. A. Jacob, J. Org. Chem.
1986, 51, 4833.
) R. V. Lerum, C. M. Russo, J. E. Marquez and J. 28 The desilylation and bromination was conducted according to the
g
,
(h
,
i
j) J. Hara, M.
following literature: G. Bruno, F. Babudri, A. Operamolla, G. V.
Bianco, M. Losurdo, M. M. Giangregorio, O. H. Omar, F. Mavelli, G.
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11 The structure of silylindene 3a was determined by single crystal X-
ray structure analysis (see the Supplementary Information). CCDC
1049645 contains the supplementary crystallographic data for this
paper. The data can be obtained free of charge from The Cambridge
Crystallographic
12 Investigation of several solvents: hexane, 49%; benzene, 44%;
xylene, 48%; chlorobenzene, 47%; 1,4-dioxane, 44%; THF, 44%;
1,2-dichloroethane, 32%; ethyl acetate, 46%;
dimethylformamide, 25%; DMSO, 22%.
Data
Centre
via
p
-
N,N-
13 Investigation of reaction temperatures: 90 °C, 40%; 120 °C, 44%;
170 °C, 42%.
14 Silylindene 3a showed
a strong blue fluorescence both in a
dichloromethane solution and solid state when 254 nm UV light was
irradiated.
15 (a) Eur. Pat., 0 653 433 A1, 1994; (b) A. A. Tsarev, M. V. Nikulin,
D. V. Uborsky, P. S. Kulyabin, I. S. Borisov, V. V. Izmer, Y. S.
Andreev, J. A. M. Canich and A. Z. Voskoboynikov, Russ. Chem.
Bull., Int. Ed., 2014, 63, 684.
4 | J. Name., 2012, 00, 1-3
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