Harder S, Spielmann J (2008)
Publication Type: Journal article, Original article
Publication year: 2008
Original Authors: Spielmann J., Harder S.
Publisher: Wiley-VCH Verlag
Pages Range: 1480-1486
Journal Issue: 9
Reactions of the dimeric calcium hydride complex [(DIPP-nacnac) CaH·thf] {1; DIPP-nacnac = CH[(CMe)(2,6-iPrC HN)]} with the α-hydrogen containing ketones acetophenone, acetone, dibenzylketone and 2-adamantone are smooth. In most cases not only addition but also substantial enolization is observed as a side reaction and in some cases also aldol condensation was found. Despite this unselectivity, the addition products could be isolated crystalline pure. Crystal structures of [(DIPP-nacnac)CaOCH(Me)Ph] (3), [(DIPP-nacnac) CaOCH(CHPh)] (6) and [(DIPP-nacnac)-Ca(2- adamantoxide)] (7) have been determined. The calcium hydride complex 1 is an effective catalyst in the hydrosilylation of ketones. Independent from the silane/ketone ratio, a strong preference for formation of bis-alkoxy silanes [PhSiH(OR)] is observed. In most cases no enoxy groups have been found in the product. This indicates that the mechanism does not involve addition of the calcium hydride to the ketone functionality. A concerted addition of silane to ketone through a six-coordinate hypervalent silicon intermediate is proposed. © Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
APA:
Harder, S., & Spielmann, J. (2008). Reduction of ketones with hydrocarbon-soluble calcium hydride: Stoichiometric reactions and catalytic hydrosilylation. European Journal of Inorganic Chemistry, 9, 1480-1486. https://doi.org/10.1002/ejic.200701255
MLA:
Harder, Sjoerd, and Jan Spielmann. "Reduction of ketones with hydrocarbon-soluble calcium hydride: Stoichiometric reactions and catalytic hydrosilylation." European Journal of Inorganic Chemistry 9 (2008): 1480-1486.
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