title: Sequential Photochemistry of Dibenzo[a,e]dicyclopropa[c,g][8]annulene-1,6-dione: Selective Formation of Didehydrodibenzo[a,e][8]annulenes with Ultrafast SPAAC Reactivity.
abstract: An order of magnitude difference in photoreactivity between bis- (photo-DIBOD, 1) and mono-cyclopropenone-caged dibenzocyclooctadiynes (MC-DIBOD, 5) allows for selective monodecarbonylation of 1. Alternatively, 5 is prepared by selective mono-cyclopropanation of dibenzo[a,e]cyclooctadiyne (DIBOD). MC-DIBOD (5) permits efficient sequential SPAAC cross-linking of azide-derivatized substrates. Cycloaddition to 5 converts an azide moiety into a photocaged form of triazole-fused dibenzo[a,e]cyclooctyne (3). While the azide reactivity of MC-DIBOD (5) and DIBOD is similar to that of other dibenzocyclooctynes, fusion of triazole to the dibenzocyclooctyne system in 3 results in a 3 orders of magnitude enhancement in SPAAC rates. In methanol, 3 reacts with butyl azide at an astonishing rate of 34 M-1s-1, thus representing the most reactive cyclooctyne analogue reported so far. MC-DIBOD (5) was utilized in the preparation of mixed bis-triazoles and derivatization of the protein BSA with fluorescent dye and polyethylene glycol.
authors.affiliation: Department of Chemistry, University of Georgia , Athens, Georgia 30602, United States.
authors.forename: Dewey A
authors.initials: DA
authors.lastname: Sutton
authors.affiliation: Department of Chemistry, University of Georgia , Athens, Georgia 30602, United States.
authors.forename: Vladimir V
authors.initials: VV
authors.lastname: Popik