Lewis Acid Catalyzed Rearrangement of Furylcarbinols: The Aza- and Oxa-Piancatelli Cascade Reaction

Palmer, Leoni I.; Alaniz, Javier Read de

doi:10.1055/s-0033-1340157

Cited by 6 publications

(1 citation statement)

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“…Polarization of the carbon-oxygen bond that is to be cleaved following nucleophile addition is pivotal to furan ring-opening rearrangements. As such, Lewis acids are commonly employed as catalysts to facilitate Piancatelli rearrangements 29 . Despite the extensive use of lanthanide (III) catalysts for various Piancatelli rearrangements, it was discovered that Dy(OTf) 3 only increases DASA production by 10% yield 7 .…”

Section: Resultsmentioning

confidence: 99%

Development and characterization of amino donor-acceptor Stenhouse adducts

Reyes,

Lee,

Karanovic

et al. 2024

Nat Commun

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Donor-acceptor Stenhouse adducts (DASAs) are molecular photoswitches spurring wide interest because of their dynamic photophysical properties, complex photoswitching mechanism, and diverse applications. Despite breakthroughs in modularity for the donor, acceptor, and triene compartments, the backbone heteroatom remains static due to synthetic challenges. We provide a predictive tool and sought-after strategy to vary the heteroatom, introduce amino DASA photoswitches, and analyze backbone heteroatom effects on photophysical properties. Amino DASA synthesis is enabled by aza-Piancatelli rearrangements on pyrrole substrates, imparting an aromaticity-breaking rearrangement that capitalizes on nitrogen’s additional bonding orbital and the inductive properties of sulfonyl groups. Amino DASA structure is confirmed by single crystal X-ray diffraction, the photochromic properties are characterized, and the photoswitch isomerization is investigated. Overall, the discovered pyrrole rearrangement enables the study of the DASA backbone heteroatom compartment and furthers our insight into the structure-property relationship of this complex photoswitch.

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Section: Resultsmentioning

confidence: 99%