One-Step Synthesis of α-Chloro Acetophenones from Acid Chlorides and Aryl Precursors

Abstract

A direct and efficient method was developed for the preparation of a variety of substituted acetophenone derivatives from readily available arene precursors and acid chlorides. This method has significant generality and affords access to substitution patterns on aryl rings not directly achievable by Friedel-Crafts chemistry. [reaction: see text].

CO2-Mediated ortho-Lithiation of N-Alkylanilines and Its Use for the Construction of Polymerization Catalysts

“…The coordination of lithium ion on the heteroatom brings the reactive butyl carbanion into proximity for the directed deprotonation of the ortho -proton. The ortho -lithiations directed by functional groups such as −F, −OR, −OC(O)NR 2 , −CH(OR) 2 , −CH 2 NR 2 , −C(O)NR 2 , −CO 2 Li, oxazolinyl, imidazolyl, imidazolinyl, and benzimidazolyl were achieved. However, those directed by an amino (−NH 2 ), N -alkylamino (−N(H)R), or N , N -dialkylamino (−NRR′) group have not been reported.…”

Synthesis and Biological Evaluation of an Indazole-Based Selective Protein Arginine Deiminase 4 (PAD4) Inhibitor

“…28 Ortho-directed metalation followed by addition of 4-chlorobutanenitrile then provided ketone 21. 29 Azide displacement of the alkyl chloride followed by hydrazone condensation and S N Ar-mediated cyclization generated azido 4,5,6-trichloroindazole intermediate 22. N-Alkylation with cyclopentylmethyl bromide provided 23.…”

“…Aniline 19 was first converted to aryl fluoride 20 by diazotization and treatment with HBF 4 . Ortho-directed metalation followed by addition of 4-chlorobutanenitrile then provided ketone 21 . Azide displacement of the alkyl chloride followed by hydrazone condensation and S N Ar-mediated cyclization generated azido 4,5,6-trichloroindazole intermediate 22 .…”

One-Step Synthesis of 1-Chloro-3-arylacetone Derivatives from Arylacetic Acids

“…Furthermore, both carbons of this moiety possess potential electrophilic reactivity via either 1,2-addition to the carbonyl or S N 2 displacement of the chloride. Numerous methods have been developed to access these compounds, including but not limited to Friedel–Crafts acylation or Cu-mediated coupling of arylzinc species with chloroacetyl chloride. These methods are suitable for accessing acetophenone derivatives.…”