Synthesis and Reactivity of Aryl(alkynyl)iodonium Salts with Carboxylate Nucleophiles to Afford α-Acyloxyketones.
Open Access
Author:
Fardo, Joshua
Area of Honors:
Chemistry
Degree:
Bachelor of Science
Document Type:
Thesis
Thesis Supervisors:
Michael Walter Justik, Thesis Supervisor Alan John Jircitano, Thesis Honors Advisor
Keywords:
Nuclear Magnetic Resonance (NMR) α-Acyloxyketones Alkynyliodonium Salts Green Chemistry Organic Chemistry Hypervalent Iodine Alkynes HBI
Abstract:
The Michael-type reaction of soft nucleophiles with alkynyliodonium species with carboxylate nucleophiles is well known. The utility of these reactions is primarily limited by the moderate yields and difficulty in preparing the alkynyliodonium species themselves rather than any inherent limitations to the nucleophilic reaction itself. In the present study, a series of aliphatic and aryl alkynes were treated with 1H-1-hydroxy-1,2,3-benziodoxathiole 3,3-dioxide (HBI) and trifluoroacetic anhydride in acetonitrile to form the alkynyliodonium species in situ. This was followed by the addition of a buffered mixture of carboxylic acids and their corresponding potassium salts. The products obtained were primarily α-acyloxyketones in moderate to high yields. The reduced 2-iodobenzenesulfonic acid could be readily removed by simple liquid-liquid extraction and recycled and reused at a high rate. This series of experiments expands the current knowledge of multivalent iodine compounds and their usefulness in developing organic frameworks and applications in green chemistry.
