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Since 1988, we have pursued enabling technologies and methods as tools for 'green' synthetic chemistry. The devel- oped technologies comprise hardware including catalytic membranes and continuous and batch microwave reactors that have established global markets, as well as interactive, predictive software for optimization of yields and translation of conditions. New methods include 'green' reactions such as a catalytic symmetrical etherification, Pd-catalyzed cou- pling processes and a multi-component cascade for aniline derivatives. Reactions and workup were facilitated through solvent-free conditions, aqueous media at high temperature and dimethylammonium dimethylcarbamate (dimcarb) as a 'distillable' protic ionic liquid, as well as by non-extractive techniques for product isolation. The technologies and methods were designed for use alone or in various combinations as desired. Consolidation of individual operations or processes into unit steps was achieved through multi-tasking: media, reactants, catalysts, and conditions were selected to serve several purposes at various stages of a reaction. The tools were used to establish a technology platform comprising structurally diverse oligomers, macrocycles, and rod-like molecules supplementary to those available through phenol- formaldehyde chemistry. Dienone precursors were assembled from versatile building blocks containing complementary 'male' or 'female' fittings that were connected through inherently 'green' Claisen-Schmidt-type reactions. Isoaromati- zation afforded Horning-crowns, macrocyclic phenolic derivatives that were hybrids of calixarenes and crown ethers. Preliminary studies of organic substrates in salt water, with and without CO2, called into question proposals for disposal of anthropogenic CO2 by deep-sea dispersal.

A Strategic, 'Green' Approach to Organic Chemistry with Microwave Assistance and Predictive Yield Optimization as Core, Enabling Technologies