New Aspects of Stereoselective Synthesis of 1,3-Polyols

Abstract

Recent progress in the methodology for stereoselective synthesis of the 1,3-polyol functions is reviewed. Strategies for the synthesis of the extended 1,3-polyol chain are also described. 1 . Introduction 2. New Synthetic Methodologies for 1,3-Polyols 2.1. Stereoselective Functionalization of Homoallylic Alcohols 2.1.1. Route via a Cyclic Iodo Carbonate 2.1.2. A Reiterative Strategy Involving Homoallylic Alcohol Epoxidation Followed by Ring Opening with a Higher Order Mixed Organocuprate 2.1.3. Direct Functionalization of Homoallylic Alcohols 2.2. Synthesis Based on Functionalization of Allylic Alcohols and Related Compounds 2.2.1. A Reiterative Strategy Involving the Sharpless Asymmetric Epoxidation of Allylic Alcohols Followed by Regioselective Epoxide Reduction 2.2.2. Route via lodohydrins 2.2.3. Route via Hydroboration of Allylsilanes 2.3. Synthesis of syn-1,3-Polyols via Peroxides 2.4. Reduction of Acyclic ß-Hydroxy Ketones 2.4.1. Synthesis of syn-1,3-Diols 2.4.2. Synthesis of anti-1,3-Diols 2.5. Reduction of Cyclic Ketone Equivalents of Acyclic ß-Hydroxy Ketones 2.6. Synthesis of 1,3-Diols by Carbon-Carbon Bond Formation 2.6.1. Alkylation of ß-Alkoxy Aldehydes 2.6.2. Dialkylation of 1,3-Dioxins 2.6.3. Intramolecular Reformatsky-Type Reactions 2.6.4. The [1,2]-Wittig Rearrangement of ß-Alkoxyalkyl Allyl Ethers 2.6.5. Hydroxylation of 4-Butanolides with Bulky Substituents in Position 4 3. A Strategy for the Synthesis of Extended 1,3-Polyol Chains 3.1. Two-Directional 1,3-Polyol Chain Extension Strategy 3.2. Convergent Synthesis of the Extended Polyol Chain 3.2.1 Alkylation of Carbonyl Anion Equivalents Followed by Stereoselective Reduction of the Resulting Ketone 3.2.2. Coupling of Two Different Aldehydes Mediated by Carbonyl Dianion Equivalents Followed by Ancillary Stereocontrol 4. Conclusion