Allylsilanes in Organic Synthesis − Recent Developments

Abstract

Allylsilanes have been used extensively over the last 30 years. A survey of the most recent advances in this field is described, including transformations of allylsilanes through electrophilic, radical and organometallic processes. Particular

Carboazidation of Chiral Allylsilanes: Experimental and Theoretical Investigations

“…[10] Allylsilanes are known to react efficiently with radical species and possess an enhanced reactivity, compared to other olefins, toward radical intermediates with electrophilic character. [11] Allylsilanes exhibit a unique reactivity towards electrophiles, and while a wealth of data is available on the 1,2-stereocontrol arising from the reaction of chiral allylsilanes with ionic electrophilic reagents, [12] little is known on the stereocontrol occurring during radical reactions of chiral allylsilanes. [13] Porter et al first demonstrated that an allylic silicon group could control the stereochemistry of a new stereogenic center created during the radical addition (atom transfer) of a-bromo and a-iodo amides onto a chiral allylsilane.…”

Boron‐ and Silicon‐Substituted [3]‐1‐Heterodendralenes as Versatile Building Blocks for the Rapid Construction of Polycyclic Architectures

“…Furthermore, the first cycloaddition step or the combination of two Diels-Alder reactions generates an allylsilane or an allylboronic ester that constitutes an additional asset for creating structural diversity. [14] Finally, most of the final products share a common motif characterized by a cyclic lactol ether system, a structural element that, as such or as precursor of the corresponding lactones or tetrahydropyrans, has been found in many bioactive compounds and drugs. [15] Herein, we report the first results to illustrate the multiple synthesis possibilities offered by the polyfunctional building blocks 6 and 7 in diene-transmissive Diels-Alder reactions (Scheme 1).…”

Sugar Allyltin Compounds: Preparation and Application in Organic Synthesis

“…[11,12] The dissociation energy of the C-Sn bond in an allyltin is similar to that of the Sn-H bond; this linkage can be easily split into alkyl(aryl)tin and allyl radicals, allowing the allylation of organic compounds to be performed under radical conditions. [13] Allylation with allylstannanes (these being much more reactive than allylsilanes [14] ) has found wide application in organic synthesis since the beginning of the 1970s, because of its compatibility with the presence of various functional groups. [15] No wonder, therefore, that allyltin derivatives are one of the most useful classes of synthetic intermediates among organic stannanes.…”