Active metal template synthesis of rotaxanes, catenanes and knots
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Date
2011Author
McGonigal, Paul R.
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Abstract
The use of a chemical template to control the spatial arrangement of reactants
revolutionized the synthesis of mechanically interlocked molecules. The recently
developed ‘active metal template’ strategy, in which transition metal ions act as both
the template to guide interlocking and as the catalyst for the covalent bond forming
reaction that captures the interlocked structure, has several advantages in comparison
with traditional ‘passive template’ approaches.
In contrast with passive template approaches the active template strategy is more
efficient, completing the assembly of the interlocked structure in one step instead of
two and in some cases requiring only a substoichiometric amount of metal template.
In addition, fewer permanent recognition sites are required and in certain cases the
active template reaction can shed light on mechanistic details of related metalcatalyzed
processes and act as a conduit for reaction discovery. This Thesis will discuss the expansion of this new methodology in two main
directions: firstly, exploration of new active metal template reactions, specifically the
application of a novel Ni catalyzed sp3–sp3 C–C bond forming reaction, and
secondly, the application of previously developed active template reactions to the
synthesis of agrochemical-based [2]rotaxanes and other architectures, macrobicyclic
[3]rotaxanes, [2]catenanes and a trefoil knot.