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In this chapter, we have subdivided the important topic of assigning molecular configuration into two broad categories: assigning relative configuration and assigning absolute configuration. The former is more extensively covered since it lends itself more readily to nuclear magnetic resonance (NMR) methods and is probably more familiar to many readers. The latter category is treated more briefly and reflects the narrower focus of NMR-based work in that area, as well as the relative difficulty of assigning absolute configuration. This chapter is not intended to be a rigorous treatise on methods for stereochemical analysis, but rather is intended to provide the interested reader with a pathway into the extensive literature associated with this area of NMR investigation that can be explored in more depth as necessary to solve a given problem.

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