Photoinduced Asymmetric Catalysis with Chiral Metal Complexes

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Our group has contributed to the development of photoinduced asymmetric catalysis by using chiral-at-metal bis-cyclometalated iridium and rhodium complexes as lightactivatable chiral Lewis acid catalysts. In many cases, catalyst/substrate complexes served as the photoactive reaction intermediates. This proposal will investigate new modes of reactivity of photoexcited catalyst/substrate complexes and interface them with asymmetric catalysis. The first specific aim will develop visible-light-induced inner-sphere electron transfer between the catalyst and coordinated substrates. This metal-to-ligand-charge-transfer generates reduced substrates whose reactivities (bond formation or fragmentation chemistry) will be exploited in the context of asymmetric catalysis. The second specific aim will develop hydrogen-atom-transfer reactions from photoexcited catalyst/substrate complexes and combine them with asymmetric catalysis. It is expected that this research plan will provide new insights into design strategies to exploit photoexcited states of catalyst/substrate complexes and will ultimately lead to novel visible-light-activated catalytic asymmetric transformations.