Supramolecular chemistry focuses on the design of molecular architectures by relying on the complementary recognition and assembly of well-defined subunits.  Molecular recognition stems from biology, wherein systems must balance a panoply of intermolecular interactions to achieve targeted properties.  In an effort to mimic Nature, chemists employ noncovalent interactions to direct self-assembly.  Specifically, small molecule 'templates' have been designed to influence the packing of olefins, so as to facilitate a [2+2] photocycloaddition.  To expand the applicability of our approach, we pursued the photoreaction of trisubstitued olefins.  Trisubstituted olefins are known building blocks of natural products, and are well-studied in the context of biosynthesis, wherein subtle changes in molecular structure can affect properties.  In this contribution, we will present a series of trisubstituted olefins that prefer twisted geometries and discuss the impact of the methyl group on solid-state reactivity.  We will discuss the difficulties encountered in achieving reactive assemblies with sterically-congested systems.

Emerging rules in hydrogen-bond and coordination-driven self-assembly to direct solid-state reactivity:  Quantitative photocycloaddition of conformationally-frustrated olefins

243rd National Meeting (2012)

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