Photocycloaddition of S,S-dioxo-benzothiophene-2-methanol. Reactivity in the solid-state and in solution: Mechanistic studies and formation of cyclobutyl rings.

08:00 EDT 12th July 2019 | BioPortfolio

Summary of "Photocycloaddition of S,S-dioxo-benzothiophene-2-methanol. Reactivity in the solid-state and in solution: Mechanistic studies and formation of cyclobutyl rings."

The formation of cyclobutane rings is a promising strategy in the development of potential drugs and/or synthetic intermediates, typically challenging to obtain due to their constrained nature. In this work, the [2+2] photocycloaddition reaction of S,S-dioxobenzothiophene-2-methanol was explored in microcrystalline powders and its outcome was compared to that observed in solution. It was found that the molecular constraints inherited within the crystal lattice provide an optimal environment that leads to photodimer 4 as the major product in ca. 9.6:0.4 diastereomeric ratios (dr) with conversions > 95 %. The photoreaction was analyzed via X-ray, displaying a crystalline-to-amorphous transformation and showing that units of monomer 2 align to generate the corresponding dimer with a syn-head-to-tail regio- and diastereoselectivity. This result contrasted with those obtained in solution, where the diastereomeric ratio varied as a function of the excited state that is generated, to yield mixtures of dimers 4 and 5 (anti-head-to-tail); or exclusively 5 in the triplet sensitized photoreaction, in the presence of benzophenone. Density Functional Theory (DFT) was used to elucidate a plausible detailed mechanism for the phototransformation, which aided in justifying the results that led to the corresponding dimers. x-Ray crystallography allowed us to establish the stereochemical assignment of the obtained cyclobutyl rings. Thus, the use of solid-state or solution photochemistry can be used to gain control of diastereo- and regioselectivity in the formation of this important moiety.


Journal Details

This article was published in the following journal.

Name: The Journal of organic chemistry
ISSN: 1520-6904


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