Significant advancements in the syntheses of cyclobutane containing small molecules and polymers are described in the last 15 years. Small molecule cyclobutanes are under investigation for their diverse pharmacological activities, while polymers with cyclobutane backbones are emerging as novel mechanophores, stress-responsive materials, and sustainable plastics. Within these chemistries, [2 + 2] photocycloadditions to yield truxinates and truxillates are highly efficient offering a versatile strategy to access complex scaffolds. This article provides a comprehensive review on the synthetic methodologies, properties, and applications of polymer truxinates and truxillates, providing the background necessary to understand current developments and envision future applications. Additionally, we highlight the links between the development, discoveries, and synthetic methodologies of small molecules and cyclobutane polymers. We emphasize structure property relationships and discuss methods to control composition and structure for desired applications. We begin with a discussion of synthetic techniques for small molecule and polymer cyclobutanes followed by their greater applications, including pharmacological and material properties with examples including sustainable plastics and stimuli-responsive systems.

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http://www.ncbi.nlm.nih.gov/pmc/articles/PMC11414186PMC
http://dx.doi.org/10.1039/d4py00548aDOI Listing

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Significant advancements in the syntheses of cyclobutane containing small molecules and polymers are described in the last 15 years. Small molecule cyclobutanes are under investigation for their diverse pharmacological activities, while polymers with cyclobutane backbones are emerging as novel mechanophores, stress-responsive materials, and sustainable plastics. Within these chemistries, [2 + 2] photocycloadditions to yield truxinates and truxillates are highly efficient offering a versatile strategy to access complex scaffolds.

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Counting the truxillines-11 or more, the question is now.

Chirality

June 2024

Division of Organic Chemistry and Biochemistry, Ruđer Bošković Institute, Zagreb, Croatia.

Truxillines are a group of tropane alkaloids present in coca leaves that are formed by photochemical dimerization of cinnamoylcocaine(s). Proportion of different truxilline forms present in cocaine serves as its geographical, manufacture, and storage "fingerprint"; thus, the quantitative determination of truxilline content represents one of the powerful methods of analysis and characterization of cocaine samples. Contrary to the statements repeatedly presented in the literature, namely, that there exist exactly 11 truxillines and that every single truxilline is diastereomer of any other, here we show that, in fact, a total of 15 truxillines exist, which can be divided in two structurally isomeric groups-five mutually diastereomeric truxillates and 10 mutually diastereomeric truxinates.

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