Abstract
Metathesis is one of the most efficient methodologies for the synthesis of large heterocycles. The wide variety of densely functionalized natural structures containing macrocycles and the interest of other nonnatural macrocycles as potential drugs or useful structures for supramolecular chemistry has triggered the synthetic efforts en route to these structures. This chapter is an overview of successful metathesis reactions, both diene ring-closing metathesis (RCM) and ring-closing alkyne metathesis (RCAM) as the key steps in the construction of large heterocycles (12 or more members excluding peptides). The focus will be made on the different conditions that may favor the metathesis process including substrate design, catalyst nature, and reaction conditions.
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