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Journal Name
Dalton Transactions
ARTICLE
reaction will provide useful insights into the future possibilities
Amine
a
Entry
R
Time [h]
Yield [%]
DOI: 10.1039/C4DT03084B
Ph
1
2
3
24
24
24
90
90
92
(n-Bu)2NH
Acknowledgements
Financial support from the National Science Centre UMO-
2011/02/A/ST5/00472 (Maestro) is gratefully acknowledged
n-C4H9
Ph
Et2NH
Notes and references
a
n-C4H9
Department of Organometallic Chemistry, Faculty of Chemistry, Adam
Mickiewicz University in Poznan, Umultowska 89b, 61-614 Poznan
(Poland)
4
5
56
36
88
95
Ph
i-PrNH2
b
Center for Advanced Technologies, Adam Mickiewicz University
in Poznan, Umultowska 89c, 61-614 Poznan (Poland
)
Reaction conditions: [amine]:[RCH=CHSi(OEt)3]:[1] = 1:1:0.05,
a
o
toluene, 120 C, calculated by GC-MS
†
See Supporting Information for experimental procedures
and the 1H, 13C and 31P NMR spectra.
Electronic Supplementary Information (ESI) available: [details
of any supplementary information available should be included here]. See
DOI: 10.1039/b000000x/
The transfer of deuterium from an amine to the olefin molecule
was confirmed by the 1H and 2H NMR monitoring
of the reaction of (E)-styryl(triethoxy)silane with Et2ND (molar
ratio 1:1) in the presence of 10 mol%
1 in which deuterated
1
2
3
B. Marciniec, Acc. Chem. Res. 2007, 40, 943.
styrene was observed (peaks at 5.10 ppm and 5.6 ppm
at 2H NMR spectra) after heating the reaction mixture at 120°C
for 48h. All the above catalytic and stoichiometric studies allow
B. Marciniec, Coord. Chem. Rev. 2005, 249, 2374.
F. Kakiuchi, M. Matsumoto, M. Sonoda, T. Fukuyama, N. Chatani,
S. Murai, N. Furukawa and Y. Seki, Chem. Lett. 2000, 750.
(a) B. Marciniec, B. Dudziec and I. Kownacki, Angew. Chem. Int. Ed.
2006, 45, 8180; (b) B. Marciniec, H. Ławicka and B. Dudziec,
Organometallics 2007, 26, 5188; (c) B. Marciniec, H. Ławicka
and B. Dudziec, J. Organomet. Chem. 2008, 693, 235; (d) B. Dudziec
and B. Marciniec, Organometallics 2008, 27, 5598.
a
generalization of the N-silylation reaction mechanism
4
5
6
from terminal vinylsilanes to substituted vinylsilanes
and permit proposing a general catalytic cycle of this novel
reaction (Scheme 6).
(a) B. Marciniec, P. Pawluć, G. Hreczycho, A. Macina
and M. Madalska, Tetrahedron Lett. 2008, 49, 1310; (b) B. Marciniec
and J. Walkowiak, Chem. Commun. 2008, 2695; (c) G. Hreczycho,
D. Frąckowiak, P. Pawluć and B. Marciniec, Tetrahedron Lett. 2011,
52, 74.
(a) J.-W. Park, H.-J. Chang and Ch.-H. Jun, Synlett 2006, 771;
(b) J.-W. Park and Ch.-H. Jun, Org. Lett
. 2007, 9, 4073;
(c) B. Marciniec and J. Walkowiak, Synlett 2009, 2433.
7
8
J. Walkowiak and B. Marciniec, Tetrahedron Lett. 2010, 51, 6177.
(a) P. Neugebauer, B. Jaschke and U. Klingebiel, In The Chemistry
of Organic Silicon Compounds, Wiley: Chichester, England, 1989;
Vol. 3, p 429; (b) D. A. Armitage, In The Silicon-Heteroatom Bond,
Wiley: Chichester, England, 1991, p 365; (c) Y. Tanabe, T. Misaki,
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2677; (e) A. A. Andreev, V. V. Konshin, N. V. Komarov, M. Rubin,
C. Brouwer and V. Gevorgyan, Org. Lett. 2004, , 421.
,
6
9
P. G. M. Wuts and T. W. Greene, In Protecting Groups in Organic
Synthesis, 4th ed.; Wiley: New York, 2006.
Scheme
6 Proposed mechanism of N-silylation of amines
with (E)-alkenyl(triethoxy)silanes
10 (a) Y. Blum and R. M. Laine, Organometallics 1986,
5, 2081;
(b) W. D. Wang and R. Eisenberg, Organometallics 1991, 10, 2222;
(c) Y. D. Blum, K. B. Schwartz and R. M. Laine, J. Mater. Sci. 1989,
24, 1707.
Conclusions
We have developed
a catalytic route for the efficient
11 (a) J. X. Wang, A. K. Dash, J. C. Berthet, M. Ephritikhine
and M. S. Eisen, J. Organomet. Chem. 2000, 610, 49; (b) K. Takaki,
N
-silylation of aliphatic and aromatic primary and secondary
amines with substituted vinylsilanes, in which vinylsilane acts
as a silylating agent and hydrogen acceptor to form Si-N bond
with evolution of olefin. It is our hope that this novel silylation
T. Kamata, Y. Miura, T. Shishido and K. Takehira, J. Org. Chem
.
1999, 64, 3891; (c) F. Lunzer, C. Marschner and S. Landgraf,
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