5.10 Hetero-Diels–Alder Reactions

Abstract

Diels–Alder reactions that include a heteroatom in the dienes or dienophiles are called ‘hetero-Diels–Alder reactions.’ Hetero-Diels–Alder reactions are highly useful for the stereoselective construction of a variety of heterocycles, and have been extensively used in the syntheses of bioactive natural and synthetic compounds. Over the past 20 years, various diastereo- and enantioselective hetero-Diels–Alder reactions have been developed. This chapter describes recent significant advancements in this field since the publication of the first edition of Comprehensive of Organic Synthesis in 1991. First, we summarize enantioselective hetero-Diels–Alder reactions of carbonyl compounds, which are promoted by chiral Lewis acid catalysts or organocatalysts. Next, we describe representative examples of asymmetric aza-Diels–Alder reactions. We also summarize recent significant advances in the stereoselective hetero-Diels–Alder reactions of other dienes and dienophiles such as nitroso compounds. Finally, we present representative studies on the biomimetic synthesis of bioactive natural products using hetero-Diels–Alder reactions.