Photomechanical Behavior of Photochromic Diarylethene Crystals

Kobatake, Seiya; Kitagawa, Daichi

doi:10.1002/9783527822201.ch1

Cited by 3 publications

(1 citation statement)

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“…One of the important challenges in this chemistry is the design of reactive, polarized DVKs, a strategy that makes the reaction more practical, efficient, and selective . Therefore, careful design and study of appropriately activated aryl-substituted DVKs should not only enable investigation of electronic and steric effects on reactivity but also provide access to useful polyaromatic frameworks for medicinal and material chemistry …”

Section: Introductionmentioning

confidence: 99%

Divergent Reactivity of Triaryldivinyl Ketones: Competing 4π and Putative 6π Electrocyclization Pathways

et al. 2022

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This work describes an acid-promoted cyclization of triaryldivinyl ketones containing a thiophene moiety in the α-position. Two cyclization pathways are accessible: one a 4π-Nazarov cyclization and the other we propose to proceed through a 6π electrocyclic mechanism. The relative proportion of products from these divergent pathways is affected by reaction conditions and steric bulk in the substrate. We present experimental and computational evidence that when using HCl in dioxane, the 4π-conrotatory electrocyclization is more favorable, whereas GaCl3 in methylene chloride shifts the chemoselectivity toward a putative 6π-disrotatory electrocyclization. DFT calculations suggest that a complex interplay between kinetic and thermodynamic factors is implicated in the chemodivergent behavior.

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Section: Introductionmentioning

confidence: 99%