Please d oC hn eo mt Ca do mj u ms t margins
Page 4 of 4
COMMUNICATION
ChemComm
2
As mentioned above, we assume that HMPA interacts with the
electro-positive Si atom to facilitate Si–O cleavage via the
nucleophilic substitution reaction. Indeed, both alkoxy silanes
with bulky substituents and/or electron-withdrawing aryl
groups on the Si atom required higher catalyst loading to furnish
the corresponding hydrosilanes (see Tables 3, 4, and Scheme 1).
It should also be noted that the bulky tBuO and less electron-
donating PhO groups suppressed the reactivity of alkoxy silanes.
Thus, the reactions are likely to be facilitated by the
K. Panda, ChemCatChem, 2016, 8, 1373.
DOI: 10.1039/C9CC01961H
5
(a) R. J. P. Corriu and J. J. E. Moreau, J. Organomet. Chem.,
976, 120, 337; (b) S. N. Blackburn, R. N. Haszeldine, R. V.
1
Parish and J. H. Setchfield, J. Organomet. Chem., 1980, 192,
329; (c) E. Lukevics, M. Dzintara, J. Organomet. Chem., 1985,
2
95, 265; (d) T. C. Bedard and J. Y. Corey, J. Organomet.
Chem., 1992, 428, 315; (e) B. T. Gregg and A. R. Cutler,
Organometallics, 1994, 13, 1039; (f) U. Schubert and C.
Lorenz, Inorg. Chem., 1997, 36, 1258; (g) J. M. Blackwell, K. L.
Foster, V. H. Beck, W. E. Piers, J. Org. Chem., 1999, 64, 4887;
(h) J. Ohshita, R. Taketsugu, Y. Nakahara and A. Kunai; J.
Organomet. Chem., 2004, 689, 3258; (i) S. Rubinsztajn, J. A.
Cella, Macromolecules, 2005, 38, 1061; (j) M. Jeon, J. Han
and J. Park, ACS Catal., 2012, 2, 1539.
coordination of the leaving alkoxy group to the incoming BH
3
and proceed via four-centered species (Scheme 3). It is assumed
that HMPA plays another role to enhance the nucleophilicity of
BH
mechanism, involving the close cooperation of alkoxy silane,
BH and HMPA, is somewhat complicated and not yet fully
3 3
via adduct formation with BH . Thus, the overall reaction
6
(a) T. D. Tilley, Acc. Chem. Res., 1993, 26, 22; (b) H.
Yamashita and M. Tanaka, Bull. Chem. Soc. Jpn., 1995, 68,
403; (c) F. Gauvin, J. F. Harrod and H. G. Woo, Adv.
Organomet. Chem., 1998, 42, 363; (d) J. Y. Corey, Adv.
Organomet. Chem., 2004, 51, 1.
(a) Y. Nagai, Org. Prep. Proced. Int., 1980, 12, 13; (b) G. L.
Larson and J. L. Fry, Ionic and Organometallics-Catalyzed
Organosilane Reductions, Wiley, Hoboken, 2008.
(a) A. E. Finholt, A. C. Bond Jr, K. E. Wilzbach and H. I.
Schlesinger, J. Am. Chem. Soc., 1947, 69, 2692; (b) H.
Westermark, Acta. Chem. Scand., 1954, 8, 1830.
L. H. Sommer, J. McLick and C. M. Golino, J. Am. Chem. Soc.,
1
0 M. A. Brook, Silicon in Organic, Organometallics, and
Polymer Chemistry, Wiley, NewYork, 2000.
1 (a) H. Jenkner, Chemiker Ztg.-Chem. Apparatus 1961, 85,
2
Sheludyakov, J. Gen. Chem. USSR, 1988, 58, 1649; (c) M. Ito,
M. Itazaki, T. Abe and H. Nakazawa, Chem. Lett., 2016, 45,
1
3
elucidated.
R
Si
O
R
R
Si
R
2
7
8
R
H
R
cat. HMPA
R
Si OR’
+
BH3
R
H
– (R'O)BH2
R
R’
BH2
1
Scheme 3
Possible reaction pathway.
9
1
1
972, 94, 669.
In conclusion, we demonstrated the effective synthesis of
hydrosilanes via reduction of alkoxy silanes with borane. By
using EtBr as a sacrificial reagent, the reactions can also be
achieved with easily handled NaBH as a hydride source.
4
Mechanistic studies including theoretical studies, are now
underway in our group and will be reported in due course.
64; (b) N. P. Sluchevkaya, V. M. Soldatov and V. D.
434.
This work was supported by the “Development of Innovative 12 (a) J. J. D’Errico and K. G. Sharp, Inorg. Chem., 1989, 28,
2
177; (b) J. J. D’Errico and K. G. Sharp, Inorg. Chem., 1989,
8, 2886; (c) U. Herzog, G. Roewer and U. Pätzold, J.
Catalytic Processes for Organosilicon Functional Materials”
project (PL: K.S.) from the New Energy and Industrial
Technology Development Organization (NEDO).
2
Organomet. Chem., 1995, 494, 143; (d) U. Pätzold, G. Roewer
and U. Herzog, J. Organomet. Chem., 1996, 508, 147; (e) U.
Herzog and G. Roewer, J. Organomet. Chem., 1997, 527, 117;
(
f) U. Herzog and G. Roewer, J. Organomet. Chem., 1997,
Conflicts of interest
There are no conflicts to declare.
544, 217.
1
1
3 (a) D. Tsushima, M. Igarashi, K. Sato and S. Shimada, S. Chem.
Lett., 2017, 46, 1532; (b) T. Beppu, K. Sakamoto, Y. Nakajima,
K. Matsumoto, K. Sato and S. Shimada, J. Organomet. Chem.,
2
018, 869, 75; (c) A. Glüer, J. I. Schweizer, U. S. Karaca, C.
Notes and references
Würtele, M. Diefenbach, M. C. Holthausen and S. Schneider,
Inorg. Chem., 2018, 57, 13822.
1
(a) B. Marciniec, J. Gulinski, W. Urbaniac and Z. Z. Kornetka,
Comprehensive Handbook on Hydrosilylation, Pergamon,
Oxford, UK, 1992; (b) B. Marciniec, Hydrosilation: A
4 (a) R. M. Laine, J. C. Furgal, P. Doan, D. Pan, V. Popova and X.
Xhang, Angew. Chem. Int. Ed., 2016, 55, 1065; (b) N. Fukaya,
S. J. Choi, T. Horikoshi, H. Kumai, M. Hasegawa, H. Yasuda, K.
Sato and J.-C. Choi, Chem. Lett., 2016, 45, 828; (c) N. Fukaya,
S. J. Choi, T. Horikoshi, S. Kataoka, A. Endo, H. Kumai, M.
Hasegawa, K. Sato and J.-C. Choi, New. J. Chem., 2017, 41,
Comprehensive Review on Recent Advances, Springer, Berlin,
2
2
2
009; (c) D. Troegel and J. Stohrer, Coord. Chem. Rev., 2011,
55, 1440; (d) Y. Nakajima and S. Shimada, RSC Adv., 2015, 5,
0603.
2
224.
2
3
(a) C. Cheng and J. F. Hartwig, Chem. Rev., 2015, 115, 8946;
b) X. Shang and Z.-Q. Liu, Org. Biomol. Chem., 2016, 14,
829.
(a) O. Riant, N. Mostefaï and J. Courmarcel, Synthesis, 2004,
1
1
5 K. Aoyagi, K. Matsumoto, S. Shimada, K. Sato and Y.
Nakajima, Organometallics, 2019, 38, 210.
(
7
6 (a) A. Brändström, U. Junggren and B. Lamm, Tetrahedron
Lett., 1972, 13, 3173; (b) R. O. Hutshins, D. Kandasamy, F.
Dux III, C. A. Maryanoff, D. Rotstein, G. Goldsmith, W.
Burgoyne, F. Cistone, J. Dalessandro and J. Puglis, J. Org.
Chem., 1978, 43, 2259; (c) F. Rolla, J. Org. Chem., 1981, 46,
2
2
943; (b) S.Díez-González and S. P. Nolan, Acc. Chem. Res.,
008, 41, 349; (c) K. Kuciński and G. Hreczycho,
ChemCatChem., 2017, 9, 1868.
4
(a) L. H. Sommer and J. D. Citron, J. Org. Chem., 1967, 32,
3
909.
2
470; (b) J. F. Dunne, S. R. Neal, J. Engelkemier, A. Ellern and
A. D. Sadow, J. Am. Chem. Soc., 2011, 133, 16782; (c) T.
Tsuchimoto, Y. Iketani and M. Sekine, Chem. Eur. J., 2012, 18,
9
500; (d) L. Greb, S. Tamke and J. Paradies, Chem. Commun.,
4
| Chem. Commun., 2019, 100, 1-3
This journal is © The Royal Society of Chemistry 2019
Please do not adjust margins