Trifluoromethyl Source Research Articles

Organometallic Aspects of Fluoroalkylation Reactions with Copper and Nickel

The development of perfluoroalkylation methods has become increasingly important in synthetic chemistry. However, many of the metal-mediated transformations that occur readily with alkyl substrates can proceed slowly, with limited scope, or not proceed at all with fluoroalkyl derivatives. To develop more sophisticated transformations with fluoroalkyl groups using base metals, a better understanding of their fundamental fluoro-organometallic chemistry is needed. This account describes our recent investigations into the organometallic chemistry of well-defined nickel– and copper–fluoroalkyl complexes, as well as our efforts towards trifluoromethoxylations and trifluoromethylthiolations using those metals. Synthetic routes to the new complexes are discussed, as are their structural and electrochemical properties and chemical reactivities. 1 Introduction 2 Bottling a Copper(I)–Trifluoromethyl Source 3 The Redox Chemistry of Copper– and Nickel–Fluoroalkyl Complexes 4 Nickel- and Copper-Mediated Trifluoromethylthiolations 5 The Organometallic Chemistry of Nickel–Perfluoroalkyl Complexes 6 Outlook

ChemInform Abstract: Nucleophilic Trifluoromethylation of Carbonyl Compounds: Trifluoroacetaldehyde Hydrate as a Trifluoromethyl Source.

AbstractSubstrate (I) is applied as CF3CH (OH)2·1/2H2O.

Nucleophilic Trifluoromethylation of Carbonyl Compounds: Trifluoroacetaldehyde Hydrate as a Trifluoromethyl Source

A feasible nucleophilic trifluoromethylating protocol has been developed using trifluoroacetaldehyde hydrate as an atom-economical trifluoromethyl source. The reaction was found to be applicable to the nucleophilic trifluoromethylation of a broad spectrum of carbonyl compounds with satisfactory yields in general. DFT calculations have been performed to provide mechanistic insight into the present and related reactions employing 2,2,2-trifluoro-1-methoxyethanol and hexafluoroacetone hydrate.

Efficient Trifluoromethylation of Activated and Non‐Activated Alkenyl Halides by Using (Trifluoromethyl)trimethylsilane

AbstractAn efficient method for the trifluoromethylation of halogenated double bonds by using in situ generated “trifluoromethyl copper” is described. Herein, the most common trifluoromethyl source, (trifluoromethyl)trimethylsilane, was converted selectively into “trifluoromethyl copper” by using copper iodide as copper source and potassium fluoride as promoter. In 1,3‐dimethyl‐3,4,5,6‐tetrahydro‐2(1H)‐pyrimidinone (DMPU) as chelating solvent the trifluoromethylation of activated and non‐activated alkenyl halides occurred mostly in good to excellent yields in up to a gram scale.

ChemInform Abstract: Trifluoropropene Oxide as a Trifluoromethyl Source Preparation of Optically Active Alcohols.

Abstract Optically active 3,3,3-trifluoropropene oxide(TFPO) was converted to 1,1,1-trifluoro-2-ols via Grignard type or Friedel-Crafts type reaction. The regio-selectivity of the latter reaction was discussed through an MO calculation.

The Productive Merger of Iodonium Salts and Organocatalysis: A Non-photolytic Approach to the Enantioselective α-Trifluoromethylation of Aldehydes

An enantioselective organocatalytic alpha-trifluoromethylation of aldehydes has been accomplished using a commercially available, electrophilic trifluoromethyl source. The merging of Lewis acid and organocatalysis provides a new strategy for the enantioselective construction of trifluoromethyl stereogenicity, an important chiral synthon for pharmaceutical, materials, and agrochemical applications. This mild and operationally simple protocol allows rapid access to enantioenriched alpha-trifluoromethylated aldehydes through a nonphotolytic pathway.

Trifluoropropene oxide as a trifluoromethyl source. Preparation of optically active alcohols

Optically active 3,3,3-trifluoropropene oxide(TFPO) was converted to 1,1,1-trifluoro-2-ols via Grignard type or Friedel-Crafts type reaction. The regio-selectivity of the latter reaction was discussed through an MO calculation.