For 10 years Valium® (2) has been the most frequently prescribed drug. It is a safe, potent anxiolytic with pronounced muscle relaxant properties, and is the best known tranquilizer of its kind. It contains, as active ingredient, diazepam (7-chloro-1,3-dihydro-1-methyl-5-phenyl-2H-1,4-benzodiazepin-2-one).

The benzodiazepine story

Fluorinated heterocycles are prevalent in pharmaceuticals, agrochemicals, and materials. However, reactions that incorporate fluorine into heteroarenes are limited in scope and can be hazardous. We present a broadly applicable and safe method for the site-selective fluorination of a single carbon-hydrogen bond in pyridines and diazines using commercially available silver(II) fluoride. The reactions occur at ambient temperature within 1 hour with exclusive selectivity for fluorination adjacent to nitrogen. The mild conditions allow access to fluorinated derivatives of medicinally important compounds, as well as a range of 2-substituted pyridines prepared by subsequent nucleophilic displacement of fluoride. Mechanistic studies demonstrate that the pathway of a classic pyridine amination can be adapted for selective fluorination of a broad range of nitrogen heterocycles.

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Selective C-H fluorination of pyridines and diazines inspired by a classic amination reaction.

The molecular structures and spectral properties of α-haloketones as well as their syntheses are analyzed and reviewed. Their reactivity towards oxygen, nitrogen, and sulfur nucleophiles, carboxylic acids, carbon nucleophiles, alkenes, and alkynes are discussed.

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The Chemistry of α-Haloketones and Their Utility in Heterocyclic Synthesis

From glucose to aromatics: recent developments in natural products of the shikimic acid pathway

A highly stereoselective and systematic strategy for the introduction of polysulfides in the synthesis of epipolythiodiketopiperazines is described. We report the first total synthesis of dimeric epitri- and epitetrathiodiketopiperazines.

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General Approach to Epipolythiodiketopiperazine Alkaloids: Total Synthesis of (+)-Chaetocins A and C and (+)-12,12′-Dideoxychetracin A

A short synthesis of aromatic analogs of the aranotins

Synthesis of some 2-aminofurans from cyanoacetone enolate and their rearrangement to 3-cyanopyrroles with ammonia

Quinazolines and 1,4-benzodiazepines. LXX. v-Triazolo[1,5-a][1,4]benzodiazepines

Synthese des composes du titre et en particulier de la piquindone a partir d'arecoline ou d'arecolone

David A. Katonak

Papers

A short synthesis of aromatic analogs of the aranotins

Synthesis of some 2-aminofurans from cyanoacetone enolate and their rearrangement to 3-cyanopyrroles with ammonia

Quinazolines and 1,4-benzodiazepines. LXX. v-Triazolo[1,5-a][1,4]benzodiazepines

Syntheses of an antipsychotic pyrrolo[2,3-g]isoquinoline from areca alkaloids

Quinazolines and 1,4-benzodiazepines part 63, preparation and nucleophilic reactions of 7-chloro-5-phenyl-3h-1,4-benzodiazepine