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Efficiency of Functional Group Caging with Second-Generation Green- and Red-Light-Labile BODIPY Photoremovable Protecting Groups.
Shrestha, Pradeep; Mukhopadhyay, Atreyee; Dissanayake, Komadhie C; Winter, Arthur H.
Affiliation
  • Shrestha P; Department of Chemistry, Iowa State University, 1608 Gilman Hall, Ames, Iowa50010, United States.
  • Mukhopadhyay A; Department of Chemistry, Iowa State University, 1608 Gilman Hall, Ames, Iowa50010, United States.
  • Dissanayake KC; Department of Chemistry, Iowa State University, 1608 Gilman Hall, Ames, Iowa50010, United States.
  • Winter AH; Department of Chemistry, Iowa State University, 1608 Gilman Hall, Ames, Iowa50010, United States.
J Org Chem ; 87(21): 14334-14341, 2022 11 04.
Article in En | MEDLINE | ID: mdl-36255274
BODIPY-based photocages release substrates by excitation with wavelengths in the visible to near-IR regions. The recent development of more efficient BODIPY photocages spurred us to evaluate the scope and efficiency of these second-generation boron-methylated green-light and red-light-absorbing BODIPY photocages. Here, we show that these more photosensitive photocages release amine, alcohol, phenol, phosphate, halides, and carboxylic acid derivatives with much higher quantum yields than first-generation BODIPY photocages and excellent chemical yields. Chemical yields are near-quantitative for the release of all functional groups except the photorelease of amines, which react with concomitantly photogenerated singlet oxygen. In these cases, high chemical yields for photoreleased amines are restored by irradiation under an inert atmosphere. The photorelease quantum yield has a weak relationship with the leaving group pKa of the green-absorbing BODIPY photocages but little relationship with the red-absorbing derivatives, suggesting that factors other than leaving group quality impact the quantum yield. For the photorelease of alcohols, in all cases a carbonate linker (that loses CO2 upon photorelease) significantly increases both the quantum yield and the chemical yield compared to those for direct photorelease via the ether.
Subject(s)

Full text: 1 Collection: 01-internacional Database: MEDLINE Main subject: Boron Compounds / Light Language: En Journal: J Org Chem Year: 2022 Document type: Article Affiliation country: Estados Unidos Country of publication: Estados Unidos

Full text: 1 Collection: 01-internacional Database: MEDLINE Main subject: Boron Compounds / Light Language: En Journal: J Org Chem Year: 2022 Document type: Article Affiliation country: Estados Unidos Country of publication: Estados Unidos