87014-33-3

Upstream product

• 420-87-1 sodium 2,2,2-trifluoroethanolate 
• 134-85-0 4-chlorobenzophenone 
• 75-89-8 2,2,2-trifluoroethanol 
• 90-90-4 (4-bromophenyl)(phenyl)methanone 
• 1137-41-3 (4-aminophenyl)(phenyl)methanone 
• 1144-74-7 4-nitrobenzophenone 

Relevant academic research and scientific papers

A general, mild and efficient palladium-catalyzed 2,2,2-trifluoroethoxylation of activated aryl bromides and bromo-chalcones: Bromo-chalcones a new coupling partner in cross-coupling reaction

An efficient protocol for Pd-catalyzed 2,2,2-trifluoroethoxylation of activated aryl bromides and bromo-chalcones has been developed. We unveil a fascinating insight into the Pd-catalyzed C-O cross-coupling reaction. Pd/tBuXPhos (L1) ligand system facilitates the C-O cross-coupling reaction between 2,2,2-trifluoroethanol and activated aryl bromides at both higher (115 °C) and lower temperatures (40 °C). Unprecedentedly, this catalyst system facilitates the C-O cross-coupling reaction in short span of reaction times, generally 5-25 min (at 115 °C). The structurally simple analogue of tBuXPhos ligand so called JohnPhos (L2) ligand is also facilitated the C-O bond formation with activated aryl bromides and bromo-chalcones. Interestingly, under the optimal conditions (L1), methanol is also coupled rapidly with activated aryl bromides. These catalyst systems (L1 and L2) fail to couple electron rich aryl bromides with 2,2,2-trifluoroethanol, thus these catalyst systems allow the reductive elimination through an electronic pathway of reductive elimination. The unusual reactivity of 2,2,2-trifluoroethanol in Pd-catalyzed C-O cross-coupling reaction makes that the chemistry of fluorinated molecules is unique than that of non-fluorinated analogues. The bromo-chalcones can be used as a new coupling partner in the cross-coupling reaction.

BrettPhos ligand supported palladium-catalyzed C-O bond formation through an electronic pathway of reductive elimination: Fluoroalkoxylation of activated aryl halides

We report an unprecedented BrettPhos ligand supported Pd-catalyzed C-O bond-forming reaction of activated aryl halides with primary fluoroalkyl alcohols. We demonstrate that the Phosphine ligand (BrettPhos) possesses the property of altering the mechanistic pathway of reductive elimination from nucleophile to nucleophile. The Pd/BrettPhos catalyst system facilitates the reductive elimination of the oxygen nucleophile through an electronic pathway.

Photolysis of substituted benzenediazonium salts: Spin-selective reactivity of aryl cations

The photolysis of a series of substituted benzenediazonium salts was studied by low-temperature and time-resolved spectral methods and by analysis of products formed in alcohol solutions at room temperature. The spin multiplicity of the ground state aryl cations formed by nitrogen loss from the diazonium salt is known to depend on the nature of the substituent. The low-temperature spectroscopic experiments confirm a triplet ground state when the cation contains a p-amino group. These triplet cations are detected directly in fluid solution for the first time, and their lifetimes are estimated. Analysis of products reveals that these cations react predominantly from the initially formed singlet state rather than their triplet ground state.

Aromatic Fluoroalkoxylation via Direct Displacement of a Nitro or Fluoro Group

Nitro- and fluorobenzenes substituted with a range of electron-withdrawing groups readily undergo fluoroalkoxylation via direct displacement of the nitro or fluoro group.A number of compounds, which cannot be usefully prepared by direct displacement of a chloro group and which are otherwise inaccessible, have been synthesized.Yields and reaction conditions are comparable to those reported by other workers for reactions involving strong nucleophiles.

Aromatic Fluoroalkoxylation via Direct Aromatic Nucleophilic Substitution

The reaction of activated aryl and heteroaryl halides with fluorinated alkoxide anions is described.In all cases, substitution of the halogen by a fluoroalkoxy group was observed.The effect of solvent, time, temperature, the activating group, leaving group, and the nucleophile on this reaction is also discussed.