Reactive intermediates silyl anions

The wide diversity of the foregoing reactions with electron-poor acceptors (which include cationic and neutral electrophiles as well as strong and weak one-electron oxidants) points to enol silyl ethers as electron donors in general. Indeed, we will show how the electron-transfer paradigm can be applied to the various reactions of enol silyl ethers listed above in which the donor/acceptor pair leads to a variety of reactive intermediates including cation radicals, anion radicals, radicals, etc. that govern the product distribution. Moreover, the modulation of ion-pair (cation radical and anion radical) dynamics by solvent and added salt allows control of the competing pathways to achieve the desired selectivity (see below). 

The aldol reactions introduced thus far have been performed under basic conditions where enolate species are involved as the reactive intermediate. In contrast to the commonly accepted carbon-anion chemistry, Mukaiyama developed another practical method in which enol species can be used as the key intermediates. He is the first chemist to successfully demonstrate that acid-catalyzed aldol reactions using Lewis acid (such as TiCU) and silyl enol ether as a stable enol equivalent can work as well.17 Furthermore, he developed the boron tri-fluoromethane sulfonate (triflate)-mediated aldol reactions via the formation of formyl enol ethers. 

The mechanism of the polycondensation reaction remains unclear. A variety of possible reactive intermediates have been suggested, including silyl radicals and silyl anions. An anionic propagation mechanism (100,101,103) has been strongly suggested, although the case is by no means settled (104). Other Synthetic Methods. 

In this section we will discuss various reactive intermediates that contain silicon. In particular, the silicon analogues of the classic organic reactive intermediates such as carbenes (silylenes), carbenium (silicenium) ions and carbanions (silyl anions) have attracted the interest of experimentalists and theoreticians. In light of the elusive nature of these species it is not surprising that much of what we know about their properties comes from theory, in particular ab initio molecular orbital calculations. 

A series of bis-silylated arenium ions 74 have been prepared as reactive intermediates by hydride abstraction from silanes (Scheme 25) <2002CEJ1163>. The success of the synthetic route can be attributed to the use of noncoordinating hydrocarbon solvents and a very weakly coordinating anion, [B(C6F5)4] addition of a stronger nucleophile such as MeCN results in desilylation of the arenium ion. 

Silacyclobutanes Head-to-Head Dimerization Versus Anionic Polymerization — a-Silyl Substituted Carbanions as Reactive Intermediates... 

Summary Reacting 2-neopentyl substituted silacyclobutanes la,b with MeLi/HMPA (hexamethylphosphoric triamide) anionic polymerization to give polymers 3a,b plays only a minor role for product formation. Instead, the head-to-head dimers 2a,b are isolated as main products. Their formation is explained by a complex reaction mechanism, in which various carbanionic, highly reactive intermediates are discussed. Obviously, the bis-a-silyl substituted carbanions 10a,b are remarkably stable, as can be concluded from Si NMR spectroscopic investigations at low temperature and from the products formed by trapping reactions with alcohols. 

Organosilicon chemistry has expanded its scope considerably in the last two decades. One of the most remarkable achievements is the progress which was made in the elucidation of the mechanisms in silicon chemistry, which now become comparable to those in carbon chemistry. The behavior of reactive intermediates such as silylenes, silyl radicals and silyl anions are well explored, although the chemistry of silyl cations is still controversial. Doubly-bonded silicon species are now well understood " but triply-bonded silicon is still elusive. 

In the cathodic reduction of activated olefins, chlorosilanes also act as trapping agents of anionic intermediates. Nishiguchi and coworkers described the electrochemical reduction of a,/ -unsaturated esters, nitriles, and ketones in the presence of Me3SiCl using a reactive metal anode (Mg, Zn, Al) in an undivided cell to afford the silylated compounds [78]. This reaction provides a valuable method for the introduction of a silyl group into activated olefins. 

A gold-catalyzed intramolecular alkenylsilylation reaction was reported and this unusual conversion was recently studied by DFT calculations. The electrophilic gold (I) catalyst is thought to generate carbocation and silyl cation intermediates in the conversion. The computational results suggest that the bistrifiimide anion modulates the reactivities of the cationic intermediates and controls rearrangement steps in the reaction. 

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