1174287-17-2

Upstream product

• 887144-94-7 Togni's reagent II 
• 619-73-8 4-nitrobenzyl chloride 
• 175676-42-3 trifluoromethyl 4-methylbenzenesulfonate 
• 3582-05-6 trifluoromethyl trifluoromethanesulfonate 
• 100-11-8 1-bromomethyl-4-nitro-benzene 
• 81290-20-2 (trifluoromethyl)trimethylsilane 

Relevant academic research and scientific papers

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.

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.

Enantioselective Construction of Trifluoromethoxylated Stereogenic Centers by a Nickel-Catalyzed Asymmetric Suzuki–Miyaura Coupling of Secondary Benzyl Bromides

Trifluoromethoxy-substituted stereogenic centers can be constructed with high enantioselectivity by a nickel-catalyzed Suzuki–Miyaura coupling of readily available α-bromobenzyl trifluoromethyl ethers with a variety of aryl pinacol boronates. The coupling proceeds under mild reaction conditions, and a variety of common functional groups, such as fluoride, chloride, bromide, ester, enolizable ketone, nitro, cyano, amino, and vinyl moieties, were well tolerated. Furthermore, the reaction can be easily scaled up to gram quantities without a decrease in enantioselectivity.

Aryl-BIAN-ligated silver(i) trifluoromethoxide complex

A reaction of acetonitrile-solvated AgOCF3 with 1 equiv. of Aryl-BIAN ligand in THF at room-temperature afforded the silver(i) complex (Aryl-BIAN)AgOCF3 (1) in 75% yield. The crystal structure of this silver(i) trifluoromethoxide was determined by single-crystal X-ray crystallography. The molecular structure of 1 shows the metal centre bound to one molecule of BIAN, one trifluoromethoxide and one THF solvate, resulting in a distorted tetrahedral silver. Density functional theory (DFT) calculations and the natural bond orbital (NBO) analysis were conducted to give insights into the electronic structure of 1 and the bonding characters of the OCF3 group. The reactivity of 1 towards trifluoromethoxylation of organic halides was also examined; a reaction with benzyl bromides gave the desired products of benzyl trifluoromethyl ethers in good to excellent yields.

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.