Active metal template synthesis is a powerful new strategy for the construction of rotaxanes, catenanes and other mechanically interlocked molecular structures. The key feature is that the metal plays a dual role during the assembly of the interlocked architecture, acting as both a template for entwining or threading the components and as a catalyst for capturing the interlocked final product by covalent bond formation. Unlike traditional "passive" metal template methods to rotaxanes and catenanes, permanent recognition motifs are not required on each of the components to be interlocked (i.e., the assembly can be traceless) and the template can often be used in sub-stoichiometric quantities. Since its inception in 2006, a rapidly growing number of different metal-catalysed reactions have proven suitable for the active metal template synthesis of both rotaxanes and catenanes, including the copper(i)-catalysed terminal alkyne-azide cycloaddition (the CuAAC "click" reaction), palladium- and copper-catalysed alkyne homocouplings and heterocouplings, and palladium-catalysed oxidative Heck couplings and Michael additions. In addition to simple rotaxanes and catenanes, the synthetic strategy has been used to construct switchable molecular shuttles with weak intercomponent interactions (a requirement for fast shuttling) and to provide insight into the mechanisms of transition metal-catalysed reactions. In this tutorial review we highlight the utility and potential of the early examples of the active metal template strategy in mechanically interlocked molecule synthesis.
Novel gold(I) "click" carbene(1,2,3-triazolylidene) complexes have been synthesised, characterised and exploited for the self-assembly of a metallomacrocycle and as precatalysts for gold(I)-catalysed reactions.
Contrary to the accepted convention, this work shows that Minisci-type C−H alkylation does not require any metal, photocatalyst, light, or prefunctionalization of the readily available and inexpensive carboxylic acids to proceed well under mild conditions. These mild conditions can be utilized for late-stage alkylations of complex molecules, including pharmaceutical compounds and light-sensitive compounds which degrade under photocatalytic conditions.
The synergy between photocatalysis and continuous flow chemical reactors has shifted the paradigms of photochemistry, opening new avenues of research with safer and scalable processes that can be readily implemented in academia and industry. Current state-of-the-art photocatalysts are homogeneous transition metal complexes that have favourable photophysical properties, wide electrochemical redox potentials, and photostability. However, these photocatalysts present serious drawbacks, such as toxicity, limited availability, and the overall cost of rare transition metal elements. This reduces their long-term viability, especially at an industrial scale. Heterogeneous photocatalysts (HPCats) are an attractive alternative, as the requirement for the separation and purification is largely removed, but typically at the cost of efficiency. Flow chemical reactors can, to a large extent, mitigate the loss in efficiency through reactor designs that enhance mass transport and irradiation. Herein, we review some important developments of heterogeneous photocatalytic materials and their application in flow reactors for sustainable organic synthesis. Further, the application of continuous flow heterogeneous photocatalysis in environmental remediation is briefly discussed to present some interesting reactor designs that could be implemented to enhance organic synthesis.
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