New Methods in Aryne Chemistry



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Arynes are important reactive intermediates in the synthesis of bioactive molecules and natural products, organic materials, catalysts, and polyaryl compounds. They are neutral, reactive, aromatic intermediates lacking two adjacent hydrogen atoms on an aromatic ring. They offer the strategic advantage of rapidly functionalizing an aromatic ring by forming multiple carbon−carbon or carbon−heteroatom bonds in a single operation, often in a regioselective manner. This dissertation (1) describes new aryne precursors, (2) discloses a new hindered amide base, and (3) several new reactions involving aryne intermediates. Silyl aryl bromides and iodides can be conveniently prepared on large scale in one step from commercially available starting materials and can be used as aryne precursors under conditions similar to those employed for silyl aryl triflates. Use of silyl aryl halides was demonstrated in multiple transformations such as reaction with 1,2-bistrifluoromethylthioarenes, ortho-arylation of N-tritylanilines, intermolecular addition of arynes to amides, and reaction of ureas with arynes. The synthesis and the use of a new bulky lithium di-1-adamantylamide base was developed. The base did not show any nucleophilic attack on arynes. The parent amine was synthesized in one step on a large scale from cheap and commercially available materials. Additionally, we describe a new method for base-promoted aryne insertion into silicon-phosphorous, sulfur, and nitrogen, as well as sulfur-sulfur bonds by using aryl halide and triflate starting materials.



Aryne, Benzyne