84750-92-5

Upstream product

• 3132-99-8 m-bromobenzoic aldehyde 
• 19740-19-3 chlorodifluoroacetic acid lithium salt 
• 371-67-5 2,2,2-trifluorodiazoethane 
• 89598-96-9 (3-bromophenyl)boronic acid 
• 120801-75-4 trimethylsilyl-2,2-difluoro-2-(fluorosulphonyl)acetate 
• 66107-31-1 3-bromophenyl trifluoromethanesulfonate 
• 1895-39-2 sodium chlorodifluoroacetate 

Downstream Products

• 1501969-12-5 3,3'-((2RS,3SR)-1,1,1,4,4,4-hexafluorobutane-2,3-diyl)bis(bromobenzene) 
• 1589050-69-0 (E)-1-(2-(3-bromophenyl)-1-fluorovinyl)-1H-benzo[d]imidazole 
• 1589050-75-8 (Z)-1-(2-(3-bromophenyl)-1-fluorovinyl)-1H-benzo[d]imidazole 
• 31938-07-5 (3-bromophenyl)acetonitrile 
• 849015-92-5 3-(2,2-difluoroethenyl)benzaldehyde 

Relevant academic research and scientific papers

Fluoride-Triggered Synthesis of 1-Aryl-2,2-difluoroalkenes via Desilylative Defluorination of (1-Aryl)-2,2,2-trifluoroethyl-silanes

An efficient route for the synthesis of 1-aryl-2,2-difluoroalkenes via 1,2-desilylative defluorination is disclosed. Only a catalytic amount of fluoride source is required to initiate the desilylation and afford gem-difluoroalkenes in very good to quantitative yields, using mild reaction conditions in dimethyl carbonate as a green solvent. This reaction uses (1-aryl)-2,2,2-trifluoroethyl-silanes, which are easily prepared via the insertion reaction of trifluoroethyl diazo alkanes into the Si-H bond of tertiary organosilanes. (1-Aryl)-perfluoroalkyl-silanes cleanly afford the corresponding (Z)-1-benzylideneperfluoroalkanes, which upon hydrodefluorination furnish the (E)-β(perfluoroalkyl)styrene derivatives with excellent yield and complete stereoselectivity. A one-pot system involving sequential insertion and desilylative-defluorination is also suitable for this transformation. This method demonstrates the usefulness of organosilanes toward the preparation of fluorinated alkenes as synthetically useful targets.

-Annulation of gem-Difluoroalkenes and Pyridinium Ylides: Access to Functionalized 2-Fluoroindolizines

A [3 + 2]-annulation of gem-difluoroalkenes and pyridinium ylides was developed employing ambient air as the sole oxidant in an open-vessel manner, affording a series of multifunctionalized 2-fluoroindolizines in moderate to good yields. In this reaction, gem-difluoroalkene acts as a C2 synthon and entirely avoids the competitive addition-elimination process, which provides facile access to 2-fluoroindolizines.

Pd-Catalyzed Selective Carbonylation of gem-Difluoroalkenes: A Practical Synthesis of Difluoromethylated Esters

The first catalyst for the alkoxycarbonylation of gem-difluoroalkenes is described. This novel catalytic transformation proceeds in the presence of Pd(acac)2/1,2-bis((di-tert-butylphosphan-yl)methyl)benzene (btbpx) (L4) and allows for an efficient and straightforward access to a range of difluoromethylated esters in high yields and regioselectivities. The synthetic utility of the protocol is showcased in the practical synthesis of a Cyclandelate analogue using this methodology as the key step.

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.

A versatile difluorovinylation method: Cross-coupling reactions of the 2,2-difluorovinylzinc-TMEDA complex with alkenyl, alkynyl, allyl, and benzyl halides Dedicated to Professor Iwao Ojima on the occasion of his 70th birthday.

A thermally stable 2,2-difluorovinylzinc-TMEDA complex was prepared via a deprotonation-transmetallation sequence starting from commercially available 1,1-difluoroethylene. The complex thus formed was successfully applied to transition metal-catalyzed cross-coupling reactions with a wide range of organic halides, which led to the syntheses of 2,2-difluorovinyl compounds. On treatment with the difluorovinylzinc-TMEDA complex in the presence of an appropriate palladium or copper catalyst, alkenyl, alkynyl, allyl, and benzyl halides effectively underwent difluorovinylation to afford 1,1-difluoro-1,3-dienes, 1,1-difluoro-1,3-enynes, 1,1-difluoro-1,4-dienes, and (3,3-difluoroallyl)arenes, respectively.

Switchable 2,2,2-trifluoroethylation and gem-difluorovinylation of organoboronic acids with 2,2,2-trifluorodiazoethane

The transition-metal-free 2,2,2-trifluoroethylation and gem-difluorovinylation of arylboronic acids were developed. By employing different reaction conditions, these transformations provide both (2,2,2-trifluoroethyl)arenes and gem-difluorovinylarenes fro

Conversion between difluorocarbene and difluoromethylene ylide

The interconversion between difluoromethylene ylide and difluorocarbene is described. The difluoromethylene ylide precursor, Ph3P +CF2CO2-, could be turned into an efficient difluorocarbene reagent, w

Facile synthesis of β,β-difluorostyrenes via the negishi coupling of thermally stable 2,2-difluorovinyl zincTMEDA complex

2,2-Difluorovinylzinc chlorideTMEDA complex, readily prepared from 1,1-difluoroethylene, undergoes the palladiumcatalyzed coupling reaction with aryl halides to afford β,β- difluorostyrenes in high yield. This reaction not only proceeds smoothly with ster

Preparation and 13C NMR study on 1-aryl-3,3-difluoro-2-(phenylethynyl)cyclopropenes: long distance Hammett substituent effect

Coupling of 1-aryl-3,3-difluoro-2-chlorocyclopropenes and phenylacetylene using Sonogashira reaction with Pd(OAc)2 and CuI as the catalyst with K2CO3 as a base yields phenylethynylcyclopropenes in high selectivity and good yields. The 13C chemical shifts of Cε of ～105 ppm on acetylene group significantly different from phenylacetylene (84 ppm) suggest that the acetylene group possesses less sp hybrid character due to an unusual long distance Hammett substituent effect. It is also confirmed by the substituent parameter analysis, while the Cβ and Cε display the strong resonance effect (their values are 6.89 and 3.37, respectively).

Proton-Transfer Reactions. 3. Differences in the Protonation of Localized and Delocalized Carbanion Intermediates

Rates, activation parameters, and product distributions are reported for the reaction of methanolic sodium methoxide with XC6H4CH = CF2 (V) and C6F5CH = CF2 (IX) and compared to previously reported results for C6H5C(CF3) = CF2 (I).A ρ = 3.5 was calculated