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[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
Published on: May 21, 2019
Photo-Lewis Acid Generator Based on Radical-Free 6π Photo-Cyclization Reaction
Ryo Mizutsu1, Ryosuke Asato1,2, Colin J Martin1,2
1Division of Materials Science , Nara Institute of Science and Technology (NAIST) , Ikoma , Nara 630-0192 , Japan.
Abstract:
We present here a new photo-active molecule which acts as a photo-Lewis acid generator (PLAG) based on photo-chemical 6π-percyclization. Photo-illumination of the PLAG molecule produces a condensed aromatic carbocation with a triflate counteranion, which exhibits Lewis acid chemical catalytic reactivity such as initiation of the polymerization of epoxy monomers and catalysis of Mukaiyama-aldol reactions. The terminal-end structure in the epoxy polymerization was modified with the Lewis acid fragment. The carbocation induced the Mukaiyama-aldol reaction as a new photo-gated system with remarkably high catalytic reactivity and turnover numbers higher than 60. The photo-chemical quantum yield of the carbocation generation is 50%, which is considerably higher than obtained with most Brønsted photo-acid generators.
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