Many chiral ethers have important physiological activities. Although many asymmetric hydroalkoxylations of olefins with alcohols or phenols have been developed to make chiral ethers, challenges still remain in achieving high reactivity and selectivity over an ever-increasing diversity of alkenes and alcohols. In this review, recent developments on catalytic asymmetric alkene hydroalkoxylations are summarized based on the substitution patterns of alkenes. 1 Introduction 2 Asymmetric Hydroalkoxylation of Non-Activated Alkenes 2.1 Intramolecular Additions 2.2 Intermolecular Additions 3 Asymmetric Hydroalkoxylation of Enol Ethers 3.1 Intramolecular Additions 3.2 Intermolecular Additions 4 Asymmetric Hydroalkoxylation of α,β-Unsaturated Carbonyl Compounds 4.1 α,β-Unsaturated Ketones and Aldehydes as Substrates 4.2 α,β-Unsaturated Esters, Amides and Carboxylic Acids as Substrates 5 Asymmetric Hydroalkoxylation of Allenes 5.1 Intramolecular Additions 5.2 Intermolecular Additions 6 Conclusion
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