ABSTRACT
Styrenes with an electron-deficient double bond undergo cyanotrifluoromethylation with a trifluoromethylated hypervalent iodine reagent in the presence of CuCN. The reaction proceeds under mild conditions in the presence of bulky phosphines or B2pin2 additives. The process is highly regioselective and involves the consecutive formation of two C-C bonds in a single addition reaction. In the presence of a p-methoxy substituent in the styrene, oxytrifluoromethylation occurs instead of the cyanotrifluoromethylation.
Subject(s)
Copper/chemistry , Hydrocarbons, Fluorinated/chemistry , Hydrocarbons, Fluorinated/chemical synthesis , Styrenes/chemistry , Electrons , Methylation , Molecular Structure , StereoisomerismABSTRACT
Quinones undergo copper-mediated C-H trifluoromethylation reactions using a hypervalent iodine reagent. The reactions have a broad synthetic scope involving naphtho, alkyl, chloro and methoxy quinones.
Subject(s)
Copper/chemistry , Hydrocarbons, Fluorinated/chemical synthesis , Quinones/chemistry , Hydrocarbons, Fluorinated/chemistry , Molecular StructureABSTRACT
Regio- and stereoselective Cu-catalyzed addition of the above hypervalent iodine reagent to alkynes and alkenes was achieved. In the presence of CuI, the reaction is suitable to perform trifluoromethyl-benzoyloxylation and trifluoromethyl-halogenation of alkenes and alkynes. Electron-donating substituents accelerate the process, and alkenes react faster than alkynes emphasizing the electrophilic character of the addition reaction.
Subject(s)
Alkenes/chemistry , Alkynes/chemistry , Copper/chemistry , Iodine/chemistry , Catalysis , Combinatorial Chemistry Techniques , Hydrocarbons, Fluorinated/chemical synthesis , Hydrocarbons, Fluorinated/chemistry , Molecular Structure , StereoisomerismABSTRACT
Sodium perborate (SPB), a principal component of washing powders, was employed as an inexpensive and eco-friendly oxidant in the palladium-catalyzed C-H acyloxylation of alkenes in excellent regio- and stereochemistry. The reactions used anhydrides as acyloxy sources. The method applies to both terminal and internal alkenes, and even benzylic C-H oxidation.
Subject(s)
Borates/chemistry , Esters/chemical synthesis , Organometallic Compounds/chemistry , Oxidants/chemistry , Palladium/chemistry , Alkenes/chemistry , Catalysis , Esters/chemistry , Molecular Structure , StereoisomerismABSTRACT
Salicylidene acylhydrazides are inhibitors of type III secretion in several gram-negative pathogens. To further develop the salicylidene acylhydrazides, scaffold hopping was applied to replace the core fragment of the compounds. The novel 2-(2-amino-pyrimidine)-2,2-difluoroethanol scaffold was identified as a possible analog to the salicylidene acylhydrazide core structure. The synthesis of a library of 2-(2-amino-pyrimidine)-2,2-difluoro-ethanols is described in this paper.
