Photoredox radical conjugate addition of dithiane-2-carboxylate promoted by an iridium(iii) phenyl-tetrazole complex: a formal radical methylation of Michael acceptors.

نویسندگان

  • Andrea Gualandi
  • Elia Matteucci
  • Filippo Monti
  • Andrea Baschieri
  • Nicola Armaroli
  • Letizia Sambri
  • Pier Giorgio Cozzi
چکیده

A readily accessible iridium(iii) phenyl-tetrazole complex ([Ir(ptrz)2(tBu-bpy)]+, 2; Hptrz = 2-methyl-5-phenyl-tetrazole; tBu-bpy = 4,4'-di-tert-butyl-2,2'-bipyridine) is shown to be a versatile catalyst for a new photocatalytic Michael reaction. Under light irradiation in the presence of 2, a dithiane 2-carboxylic acid, obtained by simple hydrolysis of a commercially available ethyl ester, generates a 1,3-dithiane radical capable of performing addition to a variety of Michael acceptors (e.g., unsaturated ketones, esters, amides and malonates). This broad scope reaction with high yields is a formal photo-redox addition of the elusive methyl radical and the adducts obtained can be starting materials for a variety of functionalized products. The excited-state oxidation potential of catalyst 2 allows selective formation of radicals only from α-heterosubstituted carboxylates. Chemical modification of this metal complex can tune the electrochemical properties, opening a route to new highly selective catalytic photo-oxidation reactions.

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عنوان ژورنال:
  • Chemical science

دوره 8 2  شماره 

صفحات  -

تاریخ انتشار 2017