Stereoelectronic Effects in Action The Many Doors Opened by Orbital Interactions

Stereoelectronic Effects in Action The Many Doors Opened by Orbital Interactions 

The scope and applications of stereoelecttonic concepts have increased so dramatically in the recent decades that providing a comprehensive coverage of this ever-expanding field is impossible within the confines of this book. This chapter will aim to illustrate the generality of stereoelectronic concepts, their interplay with other factors and their broad applicability to different areas of chemistry, biochemistry and materials science. We will provide examples of how recognizing the orbital interactions ability to play many different roles and serve many different purposes has led to the discovery of practically useful chenucal processes. 

We will organize our discussion according the three key patterns n o and n jt ) of orbital 

In the first of these sections, we will discuss a broad selection of examples related to organic reaction control, catalyst design, fatty acid mimics, conformations of biopolymers, structure of oligosaccharides that constitute part of the bacteria cell walls, and initiation of enzymaticprocesses associated with sensing hypoxia. Remarkably, each example from this diverse array originates from a common stereoelectronic source, the gauche effect 

Control of reactive conformations We have outlined the electronic origins and conformational consequences of the gauche effect in Chapter 6 and already illustrated its utility for the design of NMR probes of chirality (Chapter 10). However, the list of applications of the gauche effect in the control of chemical structure and reactivity is much more diverse. For example, the gauche effect has been ntilized to achieve efficient and strain-free conformational control in the first example of the elusive 5-endo-dig cyclization of 

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