Visible Light Mediated Generation of trans-Arylcyclohexenes and Their Utilization in the Synthesis of Cyclic Bridged Ethers

While accessible via UV-irradiation of cis-cyclohexene, trans-cyclohexene has thus far been an investigation driven by curiosity, and due primarily to its short lifespan, has until recently not been employed for productive synthesis. Herein, we present straightforward conditions that provide access...

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Published inJournal of the American Chemical Society Vol. 140; no. 31; pp. 9934 - 9941
Main Authors Day, Jon I, Singh, Kamaljeet, Trinh, Winston, Weaver, Jimmie D
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 08.08.2018
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Multidisciplinary
Physical Sciences
Science & Technology
STYRENES
ELECTRON
DIELS-ALDER REACTIONS
CIS-CYCLOOCTENE
PHOTOCHEMISTRY
BATCH
FACILE
Z ISOMERIZATION
PHOTOCATALYST
TRIFLUOROMETHYLATION
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Summary:While accessible via UV-irradiation of cis-cyclohexene, trans-cyclohexene has thus far been an investigation driven by curiosity, and due primarily to its short lifespan, has until recently not been employed for productive synthesis. Herein, we present straightforward conditions that provide access to a class of trans-arylcyclohexenes and demonstrate their utility in the formation of oxabicyclic ethers, which are otherwise inaccessible from the corresponding cis-cyclohexene. A key challenge to utilizing the incredible ca. 52 kcal/mol strain energy of trans-cyclohexene to drive synthesis was overcoming its short lifetime. Herein, we show that preorganization via hydrogen bonding between the substrate and the reaction partner prior to isomerization is a viable strategy to overcome the inherently short lifetime of trans-cyclohexene.
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ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.8b04642