Nitronate structures facial selectivity

This chapter is divided into four major sections. The first (Section 2.1) will deal with the structure of both alkoxy and silyl nitronates. Specifically, this section will include physical, structural, and spectroscopic properties of nitronates. The next section (Section 2.2) describes the mechanistic aspects of the dipolar cycloaddition including both experimental and theoretical investigations. Also discussed in this section are the regio- and stereochemical features of the process. Finally, the remaining sections will cover the preparation, reaction, and subsequent functionalization of silyl nitronates (Section 2.3) and alkyl nitronates (Section 2.4), respectively. This will include discussion of facial selectivity in the case of chiral nitronates and the application of this process to combinatorial and natural product synthesis. 

It should be mentioned that the stereoselectivity of cycloaddition of chiral sugar-derived nitrone to an alkene is difficult to predict, and would appear to be dependent on minor structural changes in either component. Three structural features can influence the stereochemical outcome of nitrone/alkene cycloadditions /Z nitrone isomerization about the C = Nbond, alkene or/and nitrone facial selectivity, and endolexo preferences [6j. 

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