1540-63-2

Upstream product

• 567-56-6 1-chloro-2,2-bis-(4-chloro-phenyl)-1,1-difluoro-ethane 
• 420-32-6 thiocarbonyl fluoride 
• 1143-92-6 bis-(4-chlorophenyl)diazomethane 
• 108-90-7 chlorobenzene 
• 637-87-6 1-Chloro-4-iodobenzene 
• 1256278-61-1 2,2-difluoro-1-tributylstannylethenyl p-toluenesulfonate 
• 81290-20-2 (trifluoromethyl)trimethylsilane 
• 1679-18-1 4-Chlorophenylboronic acid 
• 1219454-89-3 2-((difluoromethyl)sulfonyl)pyridine 
• 90-98-2 4,4'-Dichlorobenzophenone 
• 5463-11-6 4,4'-dichlorobenzophenone hydrazone 

Downstream Products

• 72837-37-7 α,α-Bis-(4-chlorophenyl)-β-fluoro-β-(imidazolyl-1)-ethene 
• 63953-36-6 2,2-bis(4-chlorophenyl)-N,N-dimethylacetamide 
• 1642593-98-3 4,4'-(3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene-1,1-diyl)bis(chlorobenzene) 
• 1555-06-2 4,4'-(perfluoroprop-1-ene-1,1-diyl)bis(chlorobenzene) 

Relevant academic research and scientific papers

Dehalogenative Cross-Coupling of gem-Difluoroalkenes with Alkyl Halides via a Silyl Radical-Mediated Process

Herein, we describe a convenient general protocol for monofluoroalkenylation reactions of alkyl bromides involving cooperative visible-light photoredox catalysis and halogen abstraction. Mechanistic experiments showed that the products were generated by selective cross-coupling of aliphatic radicals with fluoroalkenyl radicals. Silyl radical-mediated halogen abstraction enabled the protocol to be used for the monofluoroalkenylation of a broad range of alkyl and heteroaryl halides. The protocol could be carried out on a gram scale and was applied to cholesterol, indicating its utility for late-stage monofluoroalkenylation reactions.

Direct α-Monofluoroalkenylation of Heteroatomic Alkanes via a Combination of Photoredox Catalysis and Hydrogen-Atom-Transfer Catalysis

In this study, a new C(sp3)-H monofluoroalkenylation reaction involving cooperative visible-light photoredox catalysis and hydrogen-atom-transfer catalysis to afford products generated by selective hydrogen abstraction and radical-radical cross-coupling was described. This mild, efficient reaction shows high regioselectivity for the α-carbon atoms of amines, ethers, and thioethers and thus allows the preparation of monofluoroalkenes bearing various substituents. The reaction was applied to two bioactive molecules, indicating its utility for late-stage monofluoroalkenylation of compounds with inert C(sp3)-H bonds.

Trifluoromethylation and Monofluoroalkenylation of Alkenes through Radical–Radical Cross-Coupling

The first visible-light-induced trifluoromethylation and monofluoroalkenylation of simple alkenes via a challenging radical–radical cross-coupling step was achieved. This method provided a mild, step-economical and redox-neutral route to privileged two different fluorinated difunctionalized allyl compounds. The utility of this method is illustrated by late-stage modification of medically important molecules.

Visible light photocatalytic decarboxylative monofluoroalkenylation of α-amino acids with: Gem -difluoroalkenes

α-Amino acids are among the most common biologically active molecules in nature, and their functionalization has attracted much attention. In this communication, a novel, efficient and general visible-light photocatalytic decarboxylative monofluoroalkenylation of N-protected α-amino acids with gem-difluoroalkenes is reported, affording the corresponding α-amino monofluoroalkenes which might find applications in medical chemistry and materials science. The reaction proceeded at room temperature with high efficiency and tolerance of various functional groups.

Reaction of Diazo Compounds with Difluorocarbene: An Efficient Approach towards 1,1-Difluoroolefins

A transition-metal-free difluoromethylenation of diazo compounds that proceeds under mild conditions has been developed and is based on the use of TMSCF2Br as the difluoromethylene source and tetrabutylammonium bromide (TBAB) as the promoter. T

gem-Difluoroolefination of Diazo Compounds with TMSCF3 or TMSCF2Br: Transition-Metal-Free Cross-Coupling of Two Carbene Precursors

A new olefination protocol for transition-metal-free cross-coupling of two carbene fragments arising from two different sources, namely, a nonfluorinated carbene fragment resulting from a diazo compound and a difluorocarbene fragment derived from Ruppert-Prakash reagent (TMSCF3) or TMSCF2Br, has been developed. This gem-difluoroolefination proceeds through the direct nucleophilic addition of diazo compounds to difluorocarbene followed by elimination of N2. Compared to previously reported Cu-catalyzed gem-difluoroolefination of diazo compounds with TMSCF3, which possesses a narrow substrate scope due to a demanding requirement on the reactivity of diazo compounds and in-situ-generated CuCF3, this transition-metal-free protocol affords a general and efficient approach to various disubstituted 1,1-difluoroalkenes, including difluoroacrylates, diaryldifluoroolefins, as well as arylalkyldifluoroolefins. In view of the ready availability of diazo compounds and difluorocarbene reagents and versatile transformations of 1,1-difluoroalkenes, this new gem-difluoroolefination method is expected to find wide applications in organic synthesis.

Gem-difluoroolefination of diaryl ketones and enolizable aldehydes with difluoromethyl 2-pyridyl sulfone: New insights into the Julia-Kocienski reaction

The direct conversion of diaryl ketones and enolizable aliphatic aldehydes into gem-difluoroalkenes has been a long-standing challenge in organofluorine chemistry. Herein, we report efficient strategies to tackle this problem by using difluoromethyl 2-pyridyl sulfone as a general gem-difluoroolefination reagent. The gem-difluoroolefination of diaryl ketones proceeds by acid-promoted Smiles rearrangement of the carbinol intermediate; the gem-difluoroolefination is otherwise difficult to achieve through a conventional Julia-Kocienski olefination protocol under basic conditions due to the retro-aldol type decomposition of the key intermediate. Efficient gem-difluoroolefination of aliphatic aldehydes was achieved by the use of an amide base generated in situ (from CsF and tris(trimethylsilyl)amine), which diminishes the undesired enolization of aliphatic aldehydes and provides a powerful synthetic method for chemoselective gem-difluoroolefination of multi-carbonyl compounds. Our results provide new insights into the mechanistic understanding of the classical Julia-Kocienski reaction. What a gem! The gem-difluoroolefination of diaryl ketones was realized by an acid-promoted Julia-Kocienski olefination reaction at elevated temperatures. The gem-difluoroolefination of aliphatic aldehydes and chemoselective gem-difluoroolefination of dicarbonyl compounds was achieved with the use of an amide base generated in situ (see scheme).

Consecutive cross-coupling reactions of 2,2-difluoro-1-iodoethenyl tosylate with boronic acids: Efficient synthesis of 1,1-diaryl-2,2-difluoroethenes

The cross-coupling reactions of 2,2-difluoro-1-iodoethenyl tosylate (2) with 2 equiv of boronic acids in the presence of catalytic amounts of Pd(OAc)2 and Na2CO3 afforded the mono-coupled products 3 and 5 in high yields. The use of 4 equiv of boronic acid

Copper-catalyzed gem -difluoroolefination of diazo compounds with TMSCF3 via C-F bond cleavage

A novel Cu-catalyzed gem-difluoroolefination of diazo compounds is described. This transformation starts from readily available TMSCF3 and diazo compounds, via trifluoromethylation followed by C-F bond cleavage, to afford the desired 1,1-difluoroalkene products.

Preparation of (2,2-difluoroethenylidene)bis(tributylstannane) and arylation reaction: Efficient approach to 1,1-diaryl-2,2-difluoroethenes

Reaction of 2,2-difluoro-1-tributylstannylethenyl p-toluenesulfonate (1) with bis(tributyltin) in the presence of 5 mol % Pd(PPh3)4 and 30 equiv LiBr in THF at reflux temperature for 7 h afforded (2,2-difluoroethenylidene)bis(tributylstannane) (2) in a 70% yield. Coupling reaction of 2 with aryl iodides in the presence of 5 mol % Pd(PPh 3)4 and 5 mol % CuI in DMF at 80 °C for 3-4 h provided the coupled products 3 in 59-85% yields.