Introduction to the Chemistry of Arynes

Abstract

Arynes are neutral transient intermediates formally derived from aromatic rings by abstraction of two vicinal hydrogen atoms that have been employed as an important tool for the synthesis of carbocycles and heterocycles. This includes a number of natural products and pharmaceutically and agrochemically relevant bioactive molecules. Kobayashi's discovery in 1983, i.e. the convenient and mild generation of arynes from 2-(trimethylsilyl) aryl triflates, has paved the way toward its present developed form. Aryne chemistry, which has been one of the centers of attention of organic chemistry for over 100 years, had witnessed a number of eminent contributions both in the characterization and applications. Organic chemists have exploited the diverse reactivity of arynes and their unparalleled transformations for the total synthesis of over one hundred natural products, which bring to light the unmatchable potential of this intermediate. The introduction of novel and robust methods for their preparation indeed tamed the intermediate from a highly reactive transient one to a valuable synthon in organic synthesis. The historical developments in the chemistry of arynes, various methods of generation, possible modes of reactivity, and other important developments are discussed in brief in this introductory chapter.