Aerobic catalytic photooxidation of olefins by an electron-deficient Pacman bisiron(III) mu-oxo porphyrin.
The synthesis and oxygen atom transfer (OAT) photoreactivity of a diiron(III) mu-oxo meso-tripentafluorophenyl bisporphyrin appended to a dibenzofuran spacer are presented. Reaction of 4,6-diformyldibenzofuran under standard Lindsey conditions furnishes the parent cofacial porphyrin architecture in a single step. These cofacial porphyrins photocatalyze the oxidation of sulfides and olefins using visible light and molecular oxygen as the terminal oxidant. High turnover numbers reflect the enhanced stability of the electron-deficient diiron(III) mu-oxo bisporphyrin core appended to a dibenzofuran spacer under aerobic conditions.
Rosenthal
Joel
J
Department of Chemistry, 6-335, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139-4307, USA.
Pistorio
Bradford J
BJ
Chng
Leng Leng
LL
Nocera
Daniel G
DG
D000475:Alkenes / Q000138:chemical synthesis / Q000737:chemistry*; D002384:Catalysis; D004583:Electrons; D007501:Iron / Q000737:chemistry*; D008665:Metalloporphyrins / Q000138:chemical synthesis / Q000737:chemistry*; D008956:Models, Chemical; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D010777:Photochemistry
D000475:Alkenes; D008665:Metalloporphyrins; D007501:Iron; D010100:Oxygen