69843-11-4

Upstream product

• 76953-99-6 1-(3-chlorophenyl)-1-(trifluoromethyl)ethanol 
• 1514-82-5 2-bromo-3,3,3-trifluoropropene 
• 63503-60-6 3-chlorophenylboronic acid 
• 321-31-3 1-(3-chlorophenyl)-2,2,2-trifluoroethanone 
• 2065-66-9 methyl-triphenylphosphonium iodide 
• 108-37-2 1-bromo-3-chlorobenzene 
• 431-21-0 1,2-Dibromo-3,3,3-trifluoropropane 

Relevant academic research and scientific papers

A novel and convenient synthetic method for producing α-(trifluoromethyl)styrenes (3)

The Suzuki-type coupling reaction of arylboronic acids (1) with 2-bromo-3,3,3-trifluoropropene (2) in the presence of a catalytic amount of dichlorobis(triphenylphosphine)palladium {PdCl2(PPh3)2} and a base can easily give α-(trifluoromethyl)styrenes (3) in good yields. It was also found that 1,2-dibromo-3,3,3-trifluoropropane (4) underwent dehydrobromination in the presence of KOH, and subsequently, palladium-catalyzed cross-coupling with 1 to directly afford 3 in a one pot manner in excellent yields.

Photoredox/Hydrogen Atom Transfer Cocatalyzed C-H Difluoroallylation of Amides, Ethers, and Alkyl Aldehydes

Herein, we report a method that combines hydrogen atom transfer and photoredox catalysis to achieve the dehydrogenative difluoroallylation of amides, ethers, and alkyl aldehydes. This operationally convenient method transforms a broad scope of substrates into the corresponding gem-difluoroalkenes via the construction of C(sp3)-C(sp3) or C(sp3)-C(sp2) bonds. Excellent functional group compatibility and high selectivity make this method have a wide range of substrate types and render it suitable for late-stage modification of pharmaceutical intermediates.

Photoredox relay-catalyzedgem-difluoroallylation of alkyl iodides

Herein, a new example of relay catalysis, using a combination of Mn2(CO)10and an iridium-based photocatalyst, is reported. In our relay catalytic reaction, the Mn catalyst and iridium-based photocatalyst catalyze the reaction at different stages in the desired sequence under the same reaction conditions, and do not inhibit each other. This convenient method transforms a broad scope of alkyl iodides into the correspondinggem-difluoroalkenesviaC(sp3)-C(sp3) bond construction. The protocol has good functional group tolerance and is suitable for the late-stage modification of multifunctional complex molecules.

Visible-Light-Driven Sulfonation of α-Trifluoromethylstyrenes: Access to Densely Functionalized CF3-Substituted Tertiary Alcohol

Reported herein is a visible-light-induced sulfonation of α-trifluoromethylstyrenes with sodium sulfinates, which provides a series of α-trifluoromethyl-β-sulfonyl tertiary alcohols. This new synthetic protocol is enabled by a charge-transfer complex between oxygen and sulfinates, featuring broad substrate scope and scalability. Excellent functional group compatibility and chemoselectivity render this method suitable for sulfonation of pharmaceutically relevant molecules. In the presence of D2O, deuteriotrifluorinated products were also obtained, further demonstrating the flexibility and synthetic potentials of this strategy.

Electrochemical heterodifunctionalization of α-CF3alkenes to access α-trifluoromethyl-β-sulfonyl tertiary alcohols

An unprecedented electrochemical heterodifunctionalization of α-CF3alkenes with benzenesulfonyl hydrazides was accomplished in this work, wherein a β-sulfonyl and a α-hydroxyl group were simultaneously incorporated across the olefinic double bond in a single operation. Consequently, a series of potentially medicinally valuable and densely functionalized α-trifluoromethyl-β-sulfonyl tertiary alcohols were assembled under mild conditions. Electrochemically-driven oxidative 1,2-difunctionlization of electron-deficient alkenes well obviates the need for oxidizing reagents, thus rendering this protocol more eco-friendly.

Glycosyl-Radical-Based Synthesis of C-Alkyl Glycosides via Photomediated Defluorinative gem-Difluoroallylation

We have developed a stereoselective, glycosyl radical-based method for the synthesis of C-alkyl glycosides via a photomediated defluorinative gem-difluoroallylation reaction. We demonstrate for the first time that glycosyl radicals, generated from glycosyl bromides, can readily participate in a photomediated radical polar crossover process, affording a diverse array of gem-difluoroalkene containing C-glycosides. Notable features of this method include scalability, mild conditions, broad substrate scope, and suitability for the late-stage modification of complex molecules.

Visible-Light-Mediated C-I Difluoroallylation with an α-Aminoalkyl Radical as a Mediator

Herein, we report a protocol for direct visible-light-mediated C-I difluoroallylation reactions of α-trifluoromethyl arylalkenes with alkyl iodides at room temperature with an α-aminoalkyl radical as a mediator. The protocol permits efficient functionalization of various α-trifluoromethyl arylalkenes with cyclic and acyclic primary, secondary, and tertiary alkyl iodides and is scalable to the gram level. This mild protocol uses an inexpensive mediator and is suitable for late-stage functionalization of complex natural products and drugs.

Visible-Light-Induced Deoxygenation/Defluorination Protocol for Synthesis of γ,γ-Difluoroallylic Ketones

Herein, we describe an efficient, practical photocatalytic deoxygenation/defluorination protocol for the synthesis of γ,γ-difluoroallylic ketones from commercially available aromatic carboxylic acids, triphenylphosphine, and α-trifluoromethyl alkenes. The protocol has good functional group tolerance and a broad substrate scope. Using this method, we accomplished the late-stage functionalization of several bioactive molecules.

Visible-Light-Induced Radical Defluoroborylation of Trifluoromethyl Alkenes: An Access to gem-Difluoroallylboranes

A photoredox-catalyzed defluoroborylation of trifluoromethyl alkenes with N-heterocyclic carbene boranes is described for the synthesis of gem-difluoroallylboranes. This protocol exhibits a broad substrate scope and good functional group compatibility, which enables the late-stage functionalization of structurally complex compounds. Further transformations of the defluoroborylation products to valuable CF2-containing molecules are also demonstrated. (Figure presented.).

Flash generation and borylation of 1-(trifluoromethyl)vinyllithium toward synthesis of α-(trifluoromethyl)styrenes

Thermally unstable (3,3,3-trifluoroprop-1-en-2-yl)lithium was generated by lithiation of 2-bromo-3,3,3-trifluoroprop-1-ene and successively underwent borylation in a flow microreactor system. Direct use of the 1-(trifluoromethyl)vinylborate thus formed for the Suzuki–Miyaura coupling in a batch system afforded α-(trifluoromethyl)styrenes in high yields.