1241960-07-5

Upstream product

• 3582-05-6 trifluoromethyl trifluoromethanesulfonate 
• 4392-24-9 Cinnamyl bromide 
• 655-07-2 2,4-dinitro-1-(trifluoromethoxy)benzene 
• 4392-24-9 3-bromo-1-phenyl-1-propenyl bromide 
• 81290-20-2 (trifluoromethyl)trimethylsilane 
• 4407-36-7 (2E)-3-phenyl-2-propen-1-ol 
• 300-57-2 allylbenzene 
• 2700-82-5 cesium trifluoromethoxide 
• 175676-42-3 trifluoromethyl 4-methylbenzenesulfonate 
• 1006904-72-8 silver(I) trifluoromethoxide 

Relevant academic research and scientific papers

Catalytic Oxidative Trifluoromethoxylation of Allylic C?H Bonds Using a Palladium Catalyst

A catalytic intermolecular allylic C?H trifluoromethoxylation reaction of alkenes has been developed based on the use of a palladium catalyst, CsOCF3 as the trifluoromethoxide source, and benzoquinone as the oxidant. This reaction provides an efficient route for directly accessing allylic trifluoromethoxy derivatives with excellent regioselectivities from terminal alkenes via an allylic C?H bond activation process.

Study of a Stable “Trifluoromethoxide Anion Solution” Arising from 2,4-Dinitro-Trifluoromethoxybenzene

Despite recent advances, trifluoromethoxylation remains a challenging reaction. Here we describe an efficient trifluoromethoxylative substitution, using an inexpensive and easy-to-handle reagent. By mixing DMAP with a slight excess of 1,4-dinitro-trifluoromethoxybenzene (DNTFB), a stable solution of trifluoromethoxide anion is obtained and can be used to perform a SN2 reaction without any silver additives. A precise study of the properties and behavior of this unusual stable solution of CF3O? species is also performed.

Direct Trifluoromethylation of Alcohols Using a Hypervalent Iodosulfoximine Reagent

The direct trifluoromethylation of a variety of aliphatic alcohols using a hypervalent iodosulfoximine reagent afforded the corresponding ethers in moderate to good yields (14–72 %). Primary, secondary, and even tertiary alcohols, including examples derived from natural products, underwent this transformation in the presence of catalytic amounts of zinc bis(triflimide). Typical reaction conditions involved a neat mixture of 6.0 equivalents of the alcohol with 1.0 equivalent of the reagent, with the majority of reactions complete within 2 h with 2.5 mol % of the Lewis acid catalyst. Furthermore, experimental evidence was provided that the C?O bond-forming process occurred via the coordination of the alcohol to the iodine atom and subsequent reductive elimination.

Facile Access to AgOCF3 and Its New Applications as a Reservoir for OCF2 for the Direct Synthesis of N?CF3, Aryl or Alkyl Carbamoyl Fluorides

The development of innovative fluorination strategies is greatly dependent also on the availability, safety and practicability of available fluorinating reagents. We herein show a straightforward and quantitative strategy for the preparation of valuable AgOCF3 at room temperature and showcase its performance in trifluoromethoxylations or as reservoir for O=CF2. This enabled the direct, practical and safe synthesis of valuable N-alkyl/aryl and N?CF3 carbamoyl fluorides from secondary amines and isothiocyanides, respectively. Our mechanistic data indicate that AgOCF3 does not liberate O=CF2 until it is activated by a nucleophilic co-reagent, reinforcing the stability of the salt under our new preparation strategy.

Direct Dehydroxytrifluoromethoxylation of Alcohols

The first example of a direct dehydroxytrifluoromethoxylation of alcohols has been developed. This method generated an alkyl fluoroformate in situ from alcohols, followed by nucleophilic trifluoromethoxylation with trifluoromethyl arylsulfonate (TFMS) as the trifluoromethoxylation reagent. The reaction is operationally simple and scalable, and it proceeds under mild reaction conditions to provide access to a wide range of trifluoromethyl ethers from alcohols. In addition, this method is suitable for the late-stage trifluoromethoxylation of complex small molecules.

Silver-Mediated Oxidative Trifluoromethylation of Alcohols to Alkyl Trifluoromethyl Ethers

The development of an efficient and practical method for the preparation of alkyl trifluoromethyl ethers is urgently demanding. The silver-mediated oxidative O-trifluoromethylation of primary, secondary, and tertiary alcohols with TMSCF3 under mild reaction conditions is established to provide a novel approach to a broad range of alkyl trifluoromethyl ethers. Further, this method is applied to the late-stage O-trifluoromethylation of complex natural products and prescribed pharmaceutical agents.

A new and direct trifluoromethoxylation of aliphatic substrates with 2,4-dinitro(trifluoromethoxy)benzene

The reaction of tetrabutylammonium triphenyldifluorosilicate with 2,4-dinitro(trifluoromethoxy)benzene, in acetonitrile and under microwave irradiation, generates a trifluoromethoxide anion which is able to substitute activated bromides (benzyl bromide, cinnamyl bromide), as well as, to some extent, alkyl iodides. Aliphatic trifluoromethyl ethers are thus formed. This is the first example of the nucleophilic displacement of the trifluoromethoxy group from an activated aromatic ring.

A deeper insight into direct trifluoromethoxylation with trifluoromethyl triflate

Commercially available fluorides (silver fluoride and n-tetrabutylammonium triphenyldifluorosilicate), combined with TFMT, allow a simple generation, in situ, of silver and n-tetrabutylammonium trifluoromethoxides which were able to react with electrophilic substrates. Silver trifluoromethoxide, which is usually more efficient than n-tetrabutylammonium trifluoromethoxide, converts, under mild conditions, primary aliphatic bromides and iodides, as well as primary and secondary benzylic or allylic bromides to the corresponding trifluoromethoxylated compounds. Several trifluoromethyl ethers, which could be valuable building-blocks, were prepared in such a way.