Nucleophilic Perfluoroalkylation Using Perfluoroalkyllithiums

The reaction of perfluoroalkyllithiums with polarized double bonds has been investigated. A variety of carbon-nitrogen double bonds undergo a smooth addition reaction with long chain perfluoroalkyllithiums, which are generated from perfluoroalkyl iodides and methyllithium-lithium bromide in the presence of boron trifluoride-diethyl ether complex at - 78°C. In marked contrast, the addition reactions do not take place with short chain or α-branched perfluoroalkyllithiums (e.g. CF3Li and i-C3F7Li), although these reagents can react with aldehydes and ketones. 1. Introduction 2. Stabilities of Perfluoroalkyllithiums 3. Perfluoroalkylation of Carbonyl Compounds 3.1. Reaction with Aldehydes and Ketones 3.2. Reaction with Esters, Imides, and Amides 3.3. Reaction with Quinones 4. Perfluoroalkylation of Carbon-Nitrogen Double Bonds 4.1. Reaction with Imines 4.2. Reaction with Oxime Ethers 4.3. Reaction with Azaarenes 4.4. Reactions with Other Carbon-Nitrogen Double Bonds 5. Summary