Electrophilic Perfluoroalkylating Agents.

3.2.1. Linear F-Alkyl/H-Alkyl Diblocks 1720 3.2.2. Unsaturated Diblocks 1721 3.2.3. Branched Diblocks 1722 3.2.4. Diblocks with Heteroatoms 1723 3.2.5. Diblocks with Heavy Halogens 1724 3.3. Triblocks and Multiblocks 1724 3.3.1. FnHmFn Triblocks 1724 3.3.2. HmFnHm Triblocks 1725 3.3.3. Star-Shaped Triblocks 1725 3.3.4. Multiblocks and Polyaffine Compounds 1726 4. Basic Properties of (F-Alkyl)alkyl Diblocks 1726 4.1. The “Polarity” Issues“Apolar”, yet Dipolar 1726 4.2. Surfactant Properties 1727 4.2.1. Surfactant Effects of FnHm Diblocks at Interfaces with Air, Fluorocarbons, and Hydrocarbons 1728

Chemistry, physical chemistry, and uses of molecular fluorocarbon--hydrocarbon diblocks, triblocks, and related compounds--unique "apolar" components for self-assembled colloid and interface engineering.

The sulfinatodehalogenation reaction represents one of the most important methodologies to incorporate fluorine into organic molecules. Using inexpensive sulfur-containing reactants such as Na2S2O4 under mild conditions, per- and polyfluoroalkyl halides (RFX, X = Br, I, CCl3) can be transformed smoothly into the corresponding sulfinate salts. This method is also used for the perfluoroalkylation of alkenes, dienes, alkynes and aromatics. Notably, after 1998, the sulfinatodehalogenation of perfluoroalkyl chlorides (RFCl) has been realized by using dimethylsulfoxide (DMSO) as a solvent instead of CH3CN/H2O in the Na2S2O4/NaHCO3 initiation system. Perfluoroalkyl chlorides, ethyl chlorofluoroacetates and chlorodifluoroacetates, and even nonfluorinated compounds, such as ethyl chloro- or dichloroacetates and chloroform, were either converted into the corresponding sulfinate salts or alkylated alkenes, alkynes and aromatics (including porphyrins). The sulfinatodehalogenation reaction has remarkable advantages. With the increasing demands to utilize the unique properties of fluorine and fluorinated functional groups in medicinal, agricultural and material sciences, we believe that there will continue to be useful developments in sulfinatodehalogenation chemistry and it will be applied more widely in the future.

Progress in fluoroalkylation of organic compounds via sulfinatodehalogenation initiation system

Phosphorus-based organocatalysis encompasses several subfields that have undergone rapid growth in recent years. This Outlook gives an overview of its various aspects. In particular, we highlight key advances in three topics: nucleophilic phosphine catalysis, organophosphorus catalysis to bypass phosphine oxide waste, and organophosphorus compound-mediated single electron transfer processes. We briefly summarize five additional topics: chiral phosphoric acid catalysis, phosphine oxide Lewis base catalysis, iminophosphorane super base catalysis, phosphonium salt phase transfer catalysis, and frustrated Lewis pair catalysis. Although it is not catalytic in nature, we also discuss novel discoveries that are emerging in phosphorus(V) ligand coupling. We conclude with some ideas about the future of organophosphorus catalysis.

Phosphorus-Based Catalysis.

Metal-Free Activation of C-I Bonds and Perfluoroalkylation of Alkenes with Visible Light Using Phosphine Catalysts.

Reaction of perfluoroalkyl iodides with alkenes initiated by organophosphine and related compounds

Perfluoroalkyl iodides reacted with alkenes in acetonitrile solution containing catalytic amounts of an organophosphine under mild conditions to give the corresponding adducts in moderate to high yields. Addition of hydroquinone to the reaction mixture suppressed the reaction. Diallyl ether reacted to afford tetrahydrofuran derivatives. These findings indicated that the reaction involved a free radical mechanism.

Han-Zhong Zhang

Papers

Reaction of perfluoroalkyl iodides with alkenes initiated by organophosphine and related compounds

Reaction of Perfluoroalkyl Iodides with Alkenes Initiated by Organophosphine and Related Compounds.