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to the corresponding products in 71% (1.74 g) and 90% (3.85 g,
Funken, P. Winterscheid and A. Gansäuer, Angew. Chem., Int.
DOI: 10.1039/C8CC03741H
9
,000 TON) yields, respectively (see details in ESI†). When a
Ed., 2015, 54, 6931; (h) Y.-Q. Zhang, C. Poppel, A. Panfilova, F.
Bohle, S. Grimme and A. Gansäuer, Angew. Chem., Int. Ed.,
chiral epoxide (98% ee) was subjected to the present conditions,
an enantioenriched alcohol product was obtained (>98% ee).
In summary, for the first time, we have developed the Piers’
borane-catalysed hydrosilylation of epoxides and cyclic ethers.
Mechanistic studies indicated that an alkyloxy(diaryl)borane is
a competent catalytic species, while the reaction proceeds via
an outer-sphere ionic pathway. Significantly, a selectivity
2
017, 56, 9719.
7
8
(a) J. M. Blackwell, K. L. Foster, V. H. Beck, W. E. Piers, J. Org.
Chem., 1999, 64, 4887; (b) V. Gevorgyan, M. Rubin, S. Benson,
J.-X. Liu and Y. Yamamoto, J. Org. Chem., 2000, 65, 6179; (c) V.
Gevorgyan, M. Rubin, J.-X. Liu and Y. Yamamoto, J. Org. Chem.,
2
001, 66, 1672; (d) L. L. Adduci, M. P. McLaughlin, T. A. Bender,
J. J. Becker and M. R. Gagné, Angew. Chem., Int. Ed., 2014, 53
,
,
6 5 3
reversal between Piers’ borane and B(C F ) catalyst systems
1646; (e) M. Tan and Y. Zhang, Tetrahedron Lett., 2009, 50
4
912; (f) C. K. Hazra, J. Jeong, H. Kim, M.-H. Baik, S. Park and
S. Chang, Angew. Chem., Int. Ed., 2018, 57, 2692.
Recently, Morandi reported single example of
hydrosilylation of an epoxyalcohol catalysed by B(C : N.
was observed, which could be in turn rationalized by the
difference in hydride donor ability of the presupposed
borohydride species. The present catalyst system is convenient
to perform under mild conditions and compatible with
functional groups, thus enabling applications in synthetic
organic chemistry plausible.
a
6 5 3
F )
Drosos, G.-J. Cheng, E. Ozkal, B. Cacherat, W. Thiel and B.
Morandi, Angew. Chem., Int. Ed., 2017, 56, 13377.
J. Zhang, S. Park and S. Chang, Angew. Chem., Int. Ed., 2017,
9
1
56, 13757.
This research was supported by the Institute for Basic
Science (IBS-R010-D1) in South Korea.
0 The observed 19F NMR shifts of the cyclopentyloxyborane
3
were well matched with those of the independently
synthesized borane compound. For synthesis of
alkyloxy(diaryl)boranes: (a) D. Donghi, D. Maggioni, T.
Beringhelli, G. D’Alfonso, P. Mercandelli and A. Sironi, Eur. J.
Inorg. Chem., 2008, 10, 1645; (b) L. E. Longobardi, C. Tang and
D. W. Stephan, Dalton Trans., 2014, 43, 15723.
Conflicts of interest
There are no conflicts to declare.
1
1
1 Although the reaction led to a quantitative conversion of 1a
the reaction mixture contained intractable ring-opened side
products in addition to the alkyloxyborane . These side
products are presumed to be formed upon a nucleophilic
attack by SMe . See details in ESI†.
2 For selected literature for outer-sphere ionic hydrosilylation:
a) M. Iglesias, F. J. Fernández-Alvarez and L. A. Oro,
ChemCatChem, 2014, , 2486; (b) M. C. Lipke, A. L. Liberman-
Martic and T. D. Tilley, Angew. Chem., Int. Ed., 2017, 56, 2260;
,
Notes and references
3
1
(a) S. Winstein and R. B. Henderson, in Heterocyclic
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2
1
950, vol. 1, pp. 1–60; (b) P. Crotti and M. Pineschi, in
(
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(
(
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014, 114, 8037.
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1
1
4 The (C
be a competitive pathway as we previously proposed it with
regard to the hydrosilylative C
O bond cleavage of sugars.9
5 The hydrosilylation of 1b with TMDS in the presence of
6 5 2
F ) BH-mediated outer-sphere hydrosilylation could
Yu and W. Zhou, Org. Lett., 2003,
Bras and J. Muzart, Green Chem., 2007,
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Lemaire applied a catalyst system composed of Pd/C and
5
, 4665; (c) E. Thiery, J. Le
9
, 326; (d) M. S. Kwon,
9
,
3
6 5 3
B(C F ) catalyst gave rise to exhaustively reduced alkanes
4
5
6
simultaneously with disproportionation of TMDS.
1
,1,3,3-tetramethyldisiloxane (TMDS) for hydrosilylation of
1
1
6 Z. M. Heiden and A. P. Lathem, Organometallics, 2015, 34,
epoxides and cyclic ethers: L. Pehlivan, E. Métay, O. Boyron, P.
1
818.
Demonchaux, G. Mignani and M. Lemaire, Eur. J. Org. Chem.,
7 A phenyl migration is generally known to be much faster than
that of a methyl group in the acid-mediated pinacol
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product selectivity observed in the reactions of 2,2,3,3-
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2
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4
1
139; (c) H. Sajiki, K. Hattori and K. Hirota, Chem. Commun.,
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,
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Chem., Int. Ed., 2012, 51, 8891; (f) D. S. G. Henriques, K.
Zimmer, S. Klare, A. Meyer, E. Rojo-Wiechel, M. Bauer, R. Sure,
S. Grimme, O. Schiemann, R. A. Flowers and A. Gansäuer,
1
8 Initially formed products were a mixture of silylated
compounds having several siloxane moieties of [Si], which
were cleanly converted to the corresponding alcohol products
upon hydrolysis.
4
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