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Allylsilanes and vinylsilanes usually react with electrophiles to give substitution. These reactions are conveniently understood as the reactions of alkenes that have been significantly but only slightly modified by the presence of the silyl group. In both reactions, substitution is favored over addition, and both the site of attack and the site of the double bond in the product are usually determined by the site of the silyl group in the starting material. In this chapter only the electrophilic substitution reactions of allylsilanes, vinylsilanes, and allenylsilanes is discussed. It is further restricted to the reactions of tetraorganosilanes because they are synthetically the most interesting in the laboratory. However, although they are not included in the tables, allylsilanes and vinylsilanes that react by addition rather than substitution or that are not tetraorganosilanes are referred to occasionally in the text wherever their reactions illuminate the discussion. Many of the features of the reactions discussed here are shared by the reactions of arylsilanes, ethynylsilanes, propargylsilanes, cyclopropylsilanes, and cyclopropylmethylsilanes. The methods by which allylsilanes and vinylsilanes are synthesized have been summarized in several places. Stereochemsitry of reactions of allenylsilanes and vinylsilanes is discussed. Scope and limitations include discussions of protodesilylation and deuterodesilyation and the use of carbon, nitrogen, and oxygen as electrophiles. Other electrophiles include phosphorus, sulfur, metals, halogens, and selenium. All of these are covered in the extensive tabular material
Allylsilanes and vinylsilanes usually react with electrophiles to give substitution. These reactions are conveniently understood as the reactions of alkenes that have been significantly but only slightly modified by the presence of the silyl group. In both reactions, substitution is favored over addition, and both the site of attack and the site of the double bond in the product are usually determined by the site of the silyl group in the starting material. In this chapter only the electrophilic substitution reactions of allylsilanes, vinylsilanes, and allenylsilanes is discussed. It is further restricted to the reactions of tetraorganosilanes because they are synthetically the most interesting in the laboratory. However, although they are not included in the tables, allylsilanes and vinylsilanes that react by addition rather than substitution or that are not tetraorganosilanes are referred to occasionally in the text wherever their reactions illuminate the discussion. Many of the features of the reactions discussed here are shared by the reactions of arylsilanes, ethynylsilanes, propargylsilanes, cyclopropylsilanes, and cyclopropylmethylsilanes. The methods by which allylsilanes and vinylsilanes are synthesized have been summarized in several places. Stereochemsitry of reactions of allenylsilanes and vinylsilanes is discussed. Scope and limitations include discussions of protodesilylation and deuterodesilyation and the use of carbon, nitrogen, and oxygen as electrophiles. Other electrophiles include phosphorus, sulfur, metals, halogens, and selenium. All of these are covered in the extensive tabular material
The Markownikoff or Markovnikov rule assigns the orientation of the electrophilic addition of hydrogen halides to asymmetrical alkenes or alkynes in which hydrogen itself attaches to the least‐substituted carbon atom in a double bond (or triple bond). Moreover, during the hydroboration of alkene or alkyne, hydrogen also attaches to the carbon atom with more substituents. Such a reverse addition order to alkene or alkyne is known as the anti ‐Markownikoff rule. Similarly, the addition reaction that follows the Markownikoff rule is referred to as the Markownikoff addition. Several reactions have been discussed, which follow this rule. The study finds that acid‐promoted cleavage of the cyclopropane ring follows the Markownikoff rule. This rule has been applied to rationalize the addition products.
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