Oxidation of Alcohols by Activated Dimethyl Sulfoxide and Related Reactions: An Update

In 1981 Mancuso and Swern published an article1 in this journal entitled "Activated Dimethyl Sulfoxide: Useful Reagents for Synthesis" that has become a classic reference in chemistry. Particularly in the area of oxidation of alcohols to aldehydes and ketones the use of activated dimethyl sulfoxide (DMSO) has burgeoned, with more than 200 new literature citations of the use of these methods now appearing every year. These represent not only utilization of the procedures studied and reviewed by Swern and his co-workers, but also many new developments in the methodology that greatly enhance its utility. The current review is intended to emphasize the most important developments in the use of activated DMSO for the oxidation of alcohols since 1981 through 1989, but includes sufficient coverage of the earlier literature so as to be self-contained. Only enough of the vast number of recent references are cited to highlight advances in the methodology and to provide recent examples of the application of these reactions. Professor Swern died in 1982 but left a lasting legacy to synthetic organic chemistry, and it is hoped this article will provide an update worthy of the example he provided. 1 . Introduction 2. Oxidation Procedures 2.1. DMSO/Dicyclohexylcarbodiimide (Pfitzner-Moffatt Procedure) 2.2. DMSO/Oxalyl Chloride (Swern Procedure) 2.3. DMSO/Trifluoroacetic Anhydride (Swern Procedure) 2.4. DMSO/Acetic Anhydride (Albright-Goldman Procedure) 2.5. DMSO/Phosphorus Pentoxide (Onodera Procedure) 2.6. DMSO/Pyridine-Sulfur Trioxide (Parikh-Doering Procedure) 2.7. Dimethyl Sulfide/N-Chlorosuccinimide (Corey-Kim Procedure) 2.8. DMSO/Phenyl Dichlorophosphate (Liu Procedure) 2.9. Other Procedures 3. Scope of the Oxidation 3.1. Primary and Secondary Alcohols 3.2. Oxidation of Diols and Polyols 3.3. Selective Oxidation 3.4. Sequential Reactions 3.5. Oxidation of Silyl Ethers 4. Side Reactions 4.1. Methylthiomethyl Ether Formation 4.2. Displacement Reactions 4.3. Nucleophilic and Electrophilic Chlorination 4.4. Enolization 4.5. Oxidation with Elimination 4.6. Oxidation of Amine Functionalities 4.7. Reactions of Other Functional Groups 4.8. Hydration of Carbonyl Compounds 5. Conclusion