Catalyst system and application for leading poly-fluorine phenyl in organic synthesis thereof

Abstract

The invention discloses a catalyst system and application for leading poly-fluorine phenyl in organic synthesis thereof. The catalyst system consists of a palladium catalyst, a phosphine ligand and a polarity aprotic solvent. Under the condition that the catalyst system exists, poly-fluoro-aromatic acid salt reacts with electrophilic substrates under the temperature of 80-280 DEG C to generate substitutive poly-fluorine combined aromatic compound; and the poly-fluorine aromatic acid salt reacts with the double electrophilic substrates by two steps to generate unsymmetrical poly-fluoro-triple aromatic compound. Compared with the traditional reaction for leading in the poly-fluorine phenyl, the method avoids the dependence on alkali and has good compatibility for alkali-sensitive groups such as a copper-carbonyl group and the like; the reaction substrates are of the solid, thereby being safe and stable and having low toxicity and convenient operation; bromo-arene and chloro-arene with low price comparatively to iodo-arene can be used, and poly-fluoro-terphenyl can also be used; the amount of the catalyst is small, the catalytic efficiency is high, and the catalyst can be easy to be separated; the unsymmetrical poly-fluoro-terphenyl can be synthesized by dihalogen-arene; the catalyst system has high yield, thereby having industrial value and synthesis value.

Description

technical field [0001] The invention relates to a catalyst system and its application for introducing polyfluorophenyl groups in organic synthesis. Background technique [0002] At present, there are two main methods for synthesizing polyfluorinated biaromatic compounds: [0003] 1. Daugulis et al. used copper-catalyzed carbon-hydrogen bond activation reaction to prepare polyfluorobiphenyls from polyfluorobenzene (Copper-Catalyzed Arylation and Alkenylation of Polyfluoroarene C-HBonds. Hien-Quang Do, and Olafs Daugulis, J. Am. Chem. Soc. 2008, 130, 1128-1129). [0004] Daugulis et al. used polyfluorobenzene as a reagent for introducing pentafluorophenyl, and in the presence of potassium phosphate, copper iodide was used to catalyze, and phenanthroline was used as a ligand to couple with brominated aromatics to obtain substituted polyfluorobiphenyls. . The main disadvantage of this method is: polyfluorobenzene is volatile, generally liquid, inconvenient to operate, and rel...

AI Technical Summary

Problems solved by technology

The main disadvantage of this method is: polyfluorobenzene is volatile, generally liquid, inconvenient to operate, and relatively toxic; it needs the participation of 2 equivalents of alkali, and the economy is not good enough; and this method limits the applicable surface of the substrate, There should be no alkali-sensitive groups such as ketone carbonyl, etc.; it can only be used for brominated aromatic hydrocarbons, and cheaper substrates such as chlorinated aromatic hydrocarbons cannot be used

The limitation of this method is that it can only be applied to iodo-aromatics and bromo-aromatics, and it cannot use low-priced chlorinated aromatics, nor can it use trifluoromethanesulfonate. The catalytic amount is large, which is not conducive to large-scale production.

Moreover, the separate coupling of different halogen atoms cannot be achieved by adjusting the ligand

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