The Huisgen 1,3-dipolar cycloaddition reaction of organic azides and alkynes has gained considerable attention in recent years due to the introduction in 2001 of Cu(1) catalysis by Tornoe and Meldal, leading to a major improvement in both rate and regioselectivity of the reaction, as realized independently by the Meldal and the Sharpless laboratories. The great success of the Cu(1) catalyzed reaction is rooted in the fact that it is a virtually quantitative, very robust, insensitive, general, and orthogonal ligation reaction, suitable for even biomolecular ligation and in vivo tagging or as a polymerization reaction for synthesis of long linear polymers. The triazole formed is essentially chemically inert to reactive conditions, e.g. oxidation, reduction, and hydrolysis, and has an intermediate polarity with a dipolar moment of ∼5 D. The basis for the unique properties and rate enhancement for triazole formation under Cu(1) catalysis should be found in the high ∆G of the reaction in combination with the low character of polarity of the dipole of the noncatalyzed thermal reaction, which leads to a considerable activation barrier. In order to understand the reaction in detail, it therefore seems important to spend a moment to consider the structural and mechanistic aspects of the catalysis. The reaction is quite insensitive to reaction conditions as long as Cu(1) is present and may be performed in an aqueous or organic environment both in solution and on solid support.

Cu-catalyzed azide-alkyne cycloaddition.

The Medicinal Chemist’s Toolbox: An Analysis of Reactions Used in the Pursuit of Drug Candidates

The Medicinal Chemist's Toolbox: An Analysis of Reactions Used in the Pursuit of Drug Candidates

The world is confronted with the twin crises of fossil fuel depletion and environmental degradation. The indiscriminate extraction and consumption of fossil fuels have led to a reduction in petroleum reserves. Petroleum based fuels are obtained from limited reserves. These finite reserves are highly concentrated in certain region of the world. Therefore, those countries not having these resources are facing a foreign exchange crisis, mainly due to the import of crude petroleum oil. Hence it is necessary to look for alternative fuels, which can be produced from materials available within the country. Although vegetative oils can be fuel for diesel engines, but their high viscosities, low volatilities and poor cold flow properties have led to the investigation of its various derivatives. Among the different possible sources, fatty acid methyl esters, known as Biodiesel fuel derived from triglycerides (vegetable oil and animal fates) by transesterification with methanol, present the promising alternative substitute to diesel fuels and have received the most attention now a day. The main advantages of using Biodiesel are its renewability, better quality exhaust gas emission, its biodegradability and the organic carbon present in it is photosynthetic in origin. It does not contribute to a rise in the level of carbon dioxide in the atmosphere and consequently to the green house effect. This paper reviews the source of production and characterization of vegetable oils and their methyl ester as the substitute of the petroleum fuel and future possibilities of Biodiesel production.

Biodiesel production through the use of different sources and characterization of oils and their esters as the substitute of diesel: A review

Flow chemistry involves the use of channels or tubing to conduct a reaction in a continuous stream rather than in a flask Flow equipment provides chemists with unique control over reaction parameters enhancing reactivity or in some cases enabling new reactions This relatively young technology has received a remarkable amount of attention in the past decade with many reports on what can be done in flow Until recently, however, the question, “Should we do this in flow?” has merely been an afterthought This review introduces readers to the basic principles and fundamentals of flow chemistry and critically discusses recent flow chemistry accounts

The Hitchhiker's Guide to Flow Chemistry

2.3. [4 + 4] Cycloadditions 1058 2.4. Photocycloadditions of Aromatic Compounds 1058 2.4.1. Benzene Derivatives 1058 2.4.2. Condensed Aromatic Compounds 1060 3. Photochemical Rearrangements 1061 4. Cyclizations 1064 4.1. Pericyclizations 1064 4.2. Norrish−Yang Reaction 1066 5. Photochemical Extrusion of Small Molecules 1067 6. Photochemical Electron Transfer 1068 6.1. Photochemical Electron-Transfer Reactions with a Catalytic Sensitizer 1068

Photochemical Reactions as Key Steps in Organic Synthesis

Greener approaches to organic synthesis using microreactor technology.

Improving Solid-Supported Catalyst Productivity by Using Simplified Packed-Bed Microreactors†

A new strategy for supporting catalysts based on the microencapsulation of linear polymers is presented. In this paper, we present a DMAP capsule that is capable of catalyzing acylation reactions. The catalyst is compared to DMAP on cross-linked and linear polystyrene, as well as small molecule DMAP. Rapid optimization through modification of encapsulation conditions is demonstrated. The optimization provides a dynamic range of catalysis from 90 to 300% of the rate of DMAP on polystyrene.

Microencapsulated linear polymers: "soluble" heterogeneous catalysts.

The rate of the proline-catalyzed alpha-aminoxylation of aldehydes is significantly increased in the presence of a bifunctional urea. Structure-activity relationship data indicate that both an amine and a urea are crucial for rate enhancement. The evidence presented herein suggests that this rate enhancement originates from the hydrogen bonding interaction between the bifunctional urea and an oxazolidinone intermediate to increase the rate of enamine formation. Proline derivatives that are incapable of forming oxazolidinones exhibit no rate enhancement in the presence of the bifunctional urea. The rate enhancement is general for a variety of aldehydes, and the faster reactions do not reduce yields or selectivities.

Brian P. Mason

Papers

Greener approaches to organic synthesis using microreactor technology.

Improving Solid-Supported Catalyst Productivity by Using Simplified Packed-Bed Microreactors†

Microencapsulated linear polymers: "soluble" heterogeneous catalysts.

Use of Bifunctional Ureas to Increase the Rate of Proline-Catalyzed α-Aminoxylations

Terahertz absorption spectra of 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX) polymorphs