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A facile synthesis of biologically important S -aryl dithiocarbamates has been demonstrated by the aryne three-component coupling involving CS 2 and aliphatic amines. This transition-metal-free and mild reaction is scalable and operates with good functional group compatibility. Preliminary mechanistic experiments, including density functional theory studies, are also provided. Moreover, with 3-triflyloxybenzynes, a unique four-component coupling incorporating tetrahydrofuran was observed.

An oxa-[2,3] sigmatropic rearrangement involving arynes is reported featuring the umpolung of ketones, where the C═O bond polarity is reversed. The in situ-generated sulfur ylides from β-keto thioethers and arynes undergo efficient rearrangement allowing the facile and robust synthesis of functionalized enol ethers in high yields and excellent functional group compatibility. Preliminary mechanistic studies rule out the possibility of Pummerer-type rearrangement operating in this case.

W3C standardized Web Services are becoming an increasingly popular middleware technology used to facilitate the open exchange of chemical data. While several projects in existence use Web Services to wrap existing commercial and open-source tools that mine chemical structure data, no Web Service infrastructure has yet been developed to compute thermochemical properties of substances. This work presents an infrastructure of Web Services for thermochemical data retrieval. Several examples are presented to demonstrate how our Web Services can be called from Java, through JavaScript using an AJAX methodology, and within commonly used commercial applications such as Microsoft Excel and MATLAB for use in computational work. We illustrate how a JANAF table, widely used by chemists and engineers, can be quickly reproduced through our Web Service infrastructure.