2.12.17 The Role of Solvents and Additives in Reactions of Samarium(II) Iodide and Related Reductants

T. Chciuk; R. Flowers

Abstract

The use of additives with samarium(II) iodide (SmI₂) greatly impacts the rate, diastereoselectivity, and chemoselectivity of its reactions. Additives that are commonly utilized with samarium(II) iodide and other samarium(II)-based reductants can be classified into three major groups: (1) Lewis bases such as hexamethylphosphoric triamide (HMPA) and other electron-donor ligands and chelating ethers; (2) proton donors, such as water, alcohols, and glycols; and (3) inorganic additives such as nickel(II) iodide, iron(III) chloride, and lithium chloride. In addition, the solvent milieu can also play an important role in the reactivity of samarium(II) reductants, predominantly through changes in the coordination sphere of the metal. The main focus of this chapter is on the use of additives and solvent milieu to provide selective and efficient reactions, with at least one example being given for each subclass of samarium(II)-promoted reaction.

Key words

cross-coupling reactions - electron transfer - hexamethylphosphoric triamide - inorganic additives - intramolecular cyclization - Lewis bases - proton donors - reductive coupling - ring expansion - samarium(II) iodide - solvent effects

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