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5.2.1.B Applications of Product Subclass 1 in Organic Synthesis

DOI: 10.1055/sos-SD-005-00189

Clark, A. J.Science of Synthesis, (20035215.

In the last 35 years, tin hydrides have become very versatile reagents, mediating a range of important organic reactions, particularly reductions and additions.[‌33‌‌51‌] In the majority of these reactions, the mechanisms are thought to involve the generation of intermediate radical species in radical-chain processes. The most common reduction reactions are those in which alkyl, vinyl, or aryl halides are reduced to the corresponding hydrocarbons. For example, the reduction of alkyl halides using tributylstannane is thought to proceed via homolytic cleavage of the carbonhalogen bond to give carbon-centered radicals (Scheme 13).

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If the reaction product is moderately polar it is often easiest to remove the majority of the lipophilic tin residues by partitioning between a polar solvent (such as acetonitrile) and an immiscible nonpolar solvent (such as hexane).[‌138‌] In practice, washing an acetonitrile solution of the crude reaction mixture with hexane (two to three times) is often sufficient to remove a large amount of the toxic tin reagents. Of course, care must be taken to ensure that the desired product is not substantially soluble in the nonpolar layer. This approach is essentially similar to that developed by Curran involving perfluorous tin hydrides,[‌58‌] where the reaction mixture is partitioned between organic and perfluorous solvents. In other cases, treatment of the crude reaction mixture with either 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) and iodine,[‌139‌] or potassium fluoride[‌140‌] may be used to form an insoluble precipitate of a tin halide.

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References


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