Energy transfer (EnT) photocatalysis enabled by gold-N-heterocyclic carbene (NHC) complexes

Abstract

We present the use of gold sensitizers [Au(SIPr)(Cbz)] (PhotAu 1) and [Au(IPr)(Cbz)] (PhotAu 2) as attractive alternatives to state-of-the-art iridium-based systems. These novel photocatalysts are deployed in [2 + 2] cycloadditions of diallyl ethers and <i>N</i>-tosylamides. The reactions proceed in short reaction times and in environmentally friendly solvents. [Au(SIPr)Cbz] and [Au(IPr)(Cbz)] have higher triplet energy (<i>E</i> _T) values (66.6 and 66.3 kcal mol^-1, respectively) compared to commonly used iridium photosensitizers. These <i>E</i> _T values permit the use of these gold complexes as sensitizers enabling energy transfer catalysis involving unprotected indole derivatives, a substrate class previously inaccessible with state-of-the-art Ir photocatalysts. The photosynthesis of unprotected tetracyclic spiroindolines <i>via</i> intramolecular [2 + 2] cycloaddition using our simple mononuclear gold sensitizer is readily achieved. Mechanistic studies support the involvement of triplet-triplet energy transfer (TTEnT) for both [2 + 2] photocycloadditions.