The facile synthesis of stable enynyl- and dienyl(aryl)iodonium salts is achieved from terminal enynes. An X-ray crystal structure of an example of the latter is presented. These compounds are shown to be useful in a range of transformations.

In the presence of sodium bromide and Oxone, a range of alkylbenzene derivatives are brominated and/or oxidized with up to four C-H bonds being functionalized.

The reaction of alkyl sulfinates with alkynyl(aryl)iodonium salts provides a facile access into otherwise difficult to obtain alkyl alkynyl sulfones and cyclic vinyl sulfones via 1,2-rearrangement or 1,5-CH insertion, respectively. In benzyl sulfinates, 1,5-CH insertion is not possible, so addition to the aromatic ring occurs, followed by ring expansion to generate novel bicyclic sulfones.

The cyclization of N-alkenylamides catalyzed by iodoarenes under oxidative conditions is presented. Five-, six-, and seven-membered rings with a range of substitutions can be prepared by this route. Preliminary data from the use of chiral iodoarenes as precatalysts show that enantiocontrol is feasible.

The synthesis of substituted dihydrooxazoles by the CuI-catalyzed cycloisomerization of terminal propargyl amides is reported. The reaction has been shown to have good substrate scope and experiments to delineate the mechanism have been performed. Substrates containing a benzylic methylene were oxidized to the ketone under the reaction conditions.

The majority of alkynyl(aryl)iodonium salts reported in the literature are derived from iodobenzene. This article describes the effects of varying this iodoarene building block on the synthesis, reactivity and stability of these salts. Two procedures to synthesize a variety of known and novel alkynyl(aryl)iodonium tosylates directly from the iodoarene are reported. In the reactions of these salts, those derived from 2-iodoanisole gave superior results than the others tested in every reaction. Isothermal microcalorimetry indicated that these novel salts were significantly more stable and less prone to decomposition than all of the other derivatives.

The study of the reactions of tertiary propargyl alcohols with sodium halides under oxidative conditions is presented. With sodium iodide, α-iodoenones were formed, however, with sodium bromide or chloride the α-haloenones were only formed in low yields under anhydrous conditions. Conversely, upon addition of water to the reaction mixtures, α,α-dibromoketones and α,α-dichloroketones were formed in good yields, but α,α-diiodoketones were not observed.

Total syntheses of the reported structures of piperolein B, isopiperolein B and piperamide C9:1(8E) have been achieved. The analytical data reported for piperolein B and piperamide C9:1(8E) match the synthetic values, however those for isopiperolein B do not. The cytotoxicities of these three structurally similar compounds against cancer cell lines of different tissue origins were evaluated and the results indicated that these compounds show differential effects on cancer cell viability.

In the presence of an oxidant, sodium iodide is converted into hypoiodous acid which effects the rearrangement of tertiary propargylic alcohols to α-iodoenones in good yields.

An unexpected oxidative rearrangement was observed when indoles substituted with 2-hydroxymalonates were subjected to typical iodination conditions. This unusual and unprecedented transformation is successful for a number of derivatives.

The core structures of illioliganones B and C have been made by an oxidative Hosomi-Sakurai reaction of a phenol derivative. The use of a silyl protecting group is shown to be crucial for this reaction to proceed.

AuCl3 efficiently catalyses the cycloisomerisation of readily available β-alkynyl β-ketoesters to generate trisubstituted furans. The substrate scope is wide and the reaction is high yielding and operationally simple.

The synthesis of substituted dihydrooxazoles by the CuI-catalyzed cycloisomerization of terminal propargyl amides is reported. The reaction has been shown to have good substrate scope and experiments to delineate the mechanism have been performed. Substrates containing a benzylic methylene were oxidized to the ketone under the reaction conditions.

In the presence of an oxidant, sodium iodide is converted into hypoiodous acid which effects the rearrangement of tertiary propargylic alcohols to α-iodoenones in good yields.

The majority of alkynyl(aryl)iodonium salts reported in the literature are derived from iodobenzene. This article describes the effects of varying this iodoarene building block on the synthesis, reactivity and stability of these salts. Two procedures to synthesize a variety of known and novel alkynyl(aryl)iodonium tosylates directly from the iodoarene are reported. In the reactions of these salts, those derived from 2-iodoanisole gave superior results than the others tested in every reaction. Isothermal microcalorimetry indicated that these novel salts were significantly more stable and less prone to decomposition than all of the other derivatives.