85278-32-6

Upstream product

• 1603-79-8 phenylglyoxylic acid ethyl ester 
• 1219454-89-3 2-((difluoromethyl)sulfonyl)pyridine 
• 22065-57-2 ethyl 2-phenyldiazoacetate 
• 115262-01-6 [bromo(difluoro)methyl]-trimethyl-silane 
• 101-97-3 Ethyl 2-phenylethanoate 
• 81290-20-2 (trifluoromethyl)trimethylsilane 
• 85277-62-9 ethyl 2-(tert-butoxycarbonyl)phenylacetate 
• 16537-09-0 t-butyl phenylacetate 
• 85278-30-4 ethyl 2-(tert-butoxycarbonyl)-2-(bromodifluoromethyl)phenylacetate 

Downstream Products

• 85277-87-8 (E)-3-fluoro-2-phenyl-2-propen-1-ol 
• 85278-33-7 3,3-difluoro-2-phenyl-2-propen-1-ol 
• 879221-61-1 2-((Z)-2-Chloro-3-phenyl-allyl)-isoindole-1,3-dione 
• 85278-37-1 (3,3-Difluoro-2-phenyl-allyl)-carbamic acid tert-butyl ester 
• 85278-35-9 1,1-difluoro-2-phenyl-3-phthalimidopropene 
• 93605-81-3 1,2-dibromo-1-fluoro-2-phenyl-3-phthalimidopropane 
• 85278-38-2 3,3-difluoro-2-phenylprop-2-en-1-aminium chloride 
• 85278-69-9 (E)-2-phenyl-3-fluoroallyl alcohol 
• 93605-75-5 2-phenyl-3-fluoroallylamine 
• 85278-36-0 2-phenyl-3,3-difluoroallylamine 
• 85278-44-0 1-fluoro-2-phenyl-3-phthalimidopropene 
• 85277-96-9 (E)-1-fluoro-2-phenyl-3-phthalimidopropene 
• 85278-05-3 (E)-3-fluoro-2-phenylallylamine hydrochloride 
• 85278-84-8 (Z)-3-fluoro-2-phenyl-2-propenamine hydrochloride 

Relevant academic research and scientific papers

Stereoselective Synthesis of Difluorinated 1,3-Dienes via Palladium-Catalyzed C-F Bond Activation of Tetrasubstituted gem-Difluoroalkenes

A highly diastereoselective Pd(0)-catalyzed synthesis of difluorinated 1,3-dienes is described. Symmetrical 1,3-dienes containing a vicinal difluoro moiety can be obtained as single diastereomers from tetrasubstituted gem-difluoroalkenes. The reaction presumably proceeds through a stereoselective twofold Pd-catalyzed Miyaura borylation/Suzuki-Miyaura cross-coupling of the C-F bond. Moreover, modular synthesis of unsymmetrical difluorinated 1,3-dienes is also achievable by the coupling between gem-difluoroalkenes and borylated monofluoroalkenes.

Palladium-Catalyzed Stereoselective C-F Bond Vinylation and Allylation of Tetrasubstituted gem-Difluoroalkenes via Stille Coupling: Synthesis of Monofluorinated 1,3- And 1,4-Dienes

We herein describe a Pd-catalyzed stereoselective C-F bond vinylation and allylation reaction of tetrasubstituted gem-difluoroalkenes for the synthesis of valuable monofluorinated 1,3- and 1,4-dienes with excellent diastereoselectivities. Different from previously used Pd(PPh3)4, a catalytic system involving Pd(0) and dppe as the ligand was developed for Stille-type cross-coupling between gem-difluoroalkenes and vinyl- and allyltin reagents.

Stereoselective Palladium-Catalyzed C?F Bond Alkynylation of Tetrasubstituted gem-Difluoroalkenes

A stereoselective Pd(PPh3)4-catalyzed C?F bond alkynylation of tetrasubstituted gem-difluoroalkenes with terminal alkynes has been developed. This method gives access to a great variety of conjugated monofluoroenynes bearing a tetrasubstituted alkene moiety with well-defined stereochemistry. Chelation-assisted oxidative addition of Pd to the C?F bond is proposed to account for the high level of stereocontrol. An X-ray crystal structure of a key monofluorovinyl PdII intermediate has been obtained for the first time as evidence for the proposed mechanism.

F- Nucleophilic-Addition-Induced Allylic Alkylation

Herein we present a novel strategy based on palladium-catalyzed allylic alkylation by taking advantage of the nucleophilic addition of external fluoride onto gem-difluoroalkenes as the initiation step. The merit of this protocol is highly appealing, as it enables a formal allylation of trifluoroethylarene derivatives through the in situ generation of β-trifluorocarbanions, which otherwise are deemed to be problematic in deprotonative allylation. Furthermore, this strategy distinguishes itself by high modularity, operational simplicity, and wide substrate scope with respect to allyl carbonates, giving rise to a broad array of homoallyltrifluoromethane derivatives, which otherwise would not be easily obtained using existing synthetic methods.

Cross-Coupling between Difluorocarbene and Carbene-Derived Intermediates Generated from Diazocompounds for the Synthesis of gem-Difluoroolefins

Cross-coupling between difluorocarbene and carbene-derived intermediates generated from diazocompounds was developed to give gem-difluoroolefins, which constitutes a fast practical pathway to achieve hindered gem-difluoroolefins. The cross-coupling between difluorocarbene and aryl diazoacetates proceeded smoothly in the presence of a copper source, whereas its coupling with diaryl diazomethanes occurred well under metal-free conditions. A mechanism involving a copper-difluorocarbene complex was proposed.

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).

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.

Inactivation of bovine plasma amine oxidase by haloallylamines

Various 2- and 3-haloallylamines were synthesized and evaluated as inhibitors of the quinone-dependent bovine plasma amine oxidase (BPAO). 3-Haloallylamines, which were previously found to be good inhibitors of the flavin-dependent mitochondrial monoamine

Enzyme-activated irreversible inhibitors of monoamine oxidase: Phenylallylamine structure-activity relationships

Seventeen 2-aryl-3-haloallylamine derivatives were prepared and evaluated as inhibitors of monoamine oxidase (MAO, EC 1.4.3.4). The synthesis of these compounds was achieved from either α-methylstyrene or ring-substituted phenylacetic acid derivatives. Wi