Seminar: Martin Oestreich, Wed, 30th March. 13:15

2019-09-09

Seminar by Prof. Martin Oestreich.

Silicon Plus
The seminar will be held at 15:15 in the seminar room, Floor 1, House 7 at Ångström.

This talk tells the story of how our work on tamed silicon cations [1-3] led us to introduce the new concept of transfer hydrosilylation [4], even with monosilane [5]! The electron-deficient boron Lewis acid tris(pentafluoro-phenyl)borane catalyzes the release of hydrosilanes from cyclohexa-2,5-dien-1-yl-substituted silanes. The same boron catalyst will then activate the Si-H bond for the reaction with representative - and -donating substrates. The net transformation is a transfer hydrosilylation. The same approach is also applicable to cyclohexa-1,4-dienes, thereby enabling the Lewis acid-catalyzed transfer hydrogenation of the aforementioned unsaturated substrates [6].
The catalytic generation of silicenium ions by cooperative Si-H bond activation will also be presented, including a detailed mechanistic analysis of the heterolytic Si-H bond cleavage [7]. The new catalytic entry into these main-group electrophiles is of broad synthetic utility as highlighted by electrophilic C-H bond silylation [8] and partial heterocycle reduction [9] as well as a combination of both.

References
[1] H. F. T. Klare, K. Bergander, M. Oestreich, Angew. Chem. Int. Ed. 2009, 48, 9077-9079; R. K. Schmidt, K. Müther, C. Mück-Lichtenfeld, S. Grimme, M. Oestreich, J. Am. Chem. Soc. 2012, 134, 4421-4428.
[2] K. Müther, R. Fröhlich, C. Mück-Lichtenfeld, S. Grimme, M. Oestreich, J. Am. Chem. Soc. 2011, 133, 12442-12444; K. Müther, P. Hrobárik, V. Hrobáriková, M. Kaupp, M. Oestreich, Chem. Eur. J. 2013, 19, 16579-16594.
[3] A. Simonneau, T. Biberger, M. Oestreich, Organometallics 2015, 34, 3927-3929.
[4] A. Simonneau, M. Oestreich, Angew. Chem. Int. Ed. 2013, 52, 11905-11907; S. Keess, A. Simonneau, M. Oestreich, Organometallics 2015, 34, 790-799.
[5] A. Simonneau, M. Oestreich, Nat. Chem. 2015, 7, 816-822.
[6] I. Chatterjee, M. Oestreich, Angew. Chem. Int. Ed. 2015, 54, 1965-1968; I. Chatterjee, Z.-W. Qu, S. Grimme, M. Oestreich, Angew. Chem. Int. Ed. 2015, 54, 12158-12162.
[7] T. Stahl, P. Hrobárik, C. D. F. Königs, Y. Ohki, K. Tatsumi, S. Kemper, M. Kaupp, H. F. T. Klare, M. Oestreich, Chem. Sci. 2015, 6, 4324-4334.
[8] H. F. T. Klare, M. Oestreich, J.-i. Ito, H. Nishiyama, Y. Ohki, K. Tatsumi, J. Am. Chem. Soc. 2011, 133, 3312-3315; L. Omann, M. Oestreich, Angew. Chem. Int. Ed. 2015, 54, 10276-10279.
[9] C. D. F. Königs, H. F. T. Klare, M. Oestreich, Angew. Chem. Int. Ed. 2013, 52, 10076-10079.
[10] S. Wübbolt, M. Oestreich, Angew. Chem. Int. Ed. 2015, 54, 15876-15879.

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