Hypervalent Silicon as a Reactive Site in Selective Bond-Forming Processes

Sebastian Rendler; Martin Oestreich

doi:10.1055/s-2005-869949

REVIEW

Hypervalent Silicon as a Reactive Site in Selective Bond-Forming Processes

Sebastian Rendler, Martin Oestreich*
Institut für Organische Chemie und Biochemie, Albert-Ludwigs-Universität, Albertstrasse 21, 79104 Freiburg im Breisgau, Germany
Fax: +49(761)2036100; e-Mail: martin.oestreich@orgmail.chemie.uni-freiburg.de;

Abstract

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Abstract

Silicon is a truly exceptional element as it serves as a reactive site for an almost infinite number of transformations pertinent to synthetic organic chemistry. Importantly, the intertwined relationship of the valency at silicon and its chemical reactivity represents the key to a profound understanding and the design of novel reactions. Thus, these so-called hypervalent silanes are crucial intermediates in silicon-based carbon-carbon bond-forming reactions, whereby tetravalent silanes are conventionally employed in carbon-silicon bond-forming processes. This review aims at a detailed discussion of these mechanistic aspects illustrated with some synthetically significant developments in modern organosilicon chemistry. Recent advances in silicon-mediated, organocatalytic C(sp³)-C(sp³) bond formation directed towards the preparation of aldol and aldol-like products are covered. Silicon-based transition-metal-catalyzed C(spⁿ)-C(sp²) bond formations involving hypervalent silicon intermediates are also included. These seemingly dissimilar reactions will be comparatively juxtaposed.

1 Introduction: Hypervalent Silicon
2 C(sp³)-C(sp³) Bond Formation
2.1 Silicon-Based Chiral Lewis Acids
2.2 Synthesis of Aldol and Aldol-Like Products
2.2.1 Addition of Allylic Silanes to Carbonyl Compounds
2.2.2 Addition of Silicon Enolates to Carbonyl Compounds
3 C(spⁿ)-C(sp²) Bond Formation: Transition-Metal-Catalyzed Cross-Coupling Reactions
4 Outlook and Perspective

Key words

aldol reactions - allylations - organocatalysis - cross-coupling - silicon

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