Synthesis of Cycloheptatriene-Containing Azetidine Lactones

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Issue Date
2022-05-23Author
Singh, Manvendra
Gaskins, Bryce
Johnson, Daniel R.
Elles, Christopher G.
Boskovic, Zarko
Publisher
American Chemical Society
Type
Article
Article Version
Scholarly/refereed, author accepted manuscript
Rights
© 2022 American Chemical Society
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Show full item recordAbstract
We prepared a collection of complex cycloheptatriene-containing azetidine lactones by applying two key photochemical reactions: “aza-Yang” cyclization and Buchner carbene insertion into aromatic rings. While photolysis of phenacyl amines leads to a rapid charge transfer and elimination, we found that a simple protonation of the amine enables the formation of azetidinols as single diastereomers. We provide evidence, through ultrafast spectroscopy, for the electron transfer from free amines in the excited state. Further, we characterize the aza-Yang reaction by establishing the dependence of the initial reaction rates on the rates of photon absorption. An unanticipated change in reactivity in morpholine analogues is explained through interactions with the tosylate anion. The Buchner reaction proceeds with a slight preference for one diastereomer over the other, and successful reaction requires electron-donating carbene-stabilizing substituents. Overall, 16 compounds were prepared over seven steps. Guided by an increase in structural complexity, efforts such as this one extend the reach of chemists into unexplored chemical space and provide useful quantities of new compounds for studies focused on their properties.
Description
This document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Organic Chemistry, copyright © 2022 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.joc.2c00367.
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Citation
Singh, M., Gaskins, B., Johnson, D. R., Elles, C. G., & Boskovic, Z. (2022). Synthesis of Cycloheptatriene-Containing Azetidine Lactones. The Journal of organic chemistry, 87(22), 15001–15010. https://doi.org/10.1021/acs.joc.2c00367
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