In the past decades, the Cu-catalyzed asymmetric organic reactions have been well-developed. By contrast, the potential of Cu to serve as a chiral photocatalyst remains underexplored. We here report the visible-lightinduced, Cu-catalyzed photoredox enantioselective cyanofluoroalkylation of alkenes. In the reaction, the Cu-based single catalyst played a dual role, as both the photoredox catalyst for the outer-sphere electron transfer and the asymmetric cross-coupling catalyst for enantioselective C− CN bond formation.

The first visible-light-promoted dearomative fluoroalkylation of β-naphthols was realized without the assistance of any transition-metal catalysts or external photosensitizers. Inexpensive fluoroalkyl iodides were directly used as efficient fluoroalkylation reagents under very mild reaction conditions. The scope of this process was found to be general and broad, and both trifluoromethyl and perfluoroalkyl groups (-C F , -C F , and -C F ) were installed in excellent yields. Preliminary mechanistic studies suggest that visible-light-promoted intermolecular charge transfer within the naphtholate-fluoroalkyl iodide electron donor-acceptor (EDA) complex induces a single electron transfer in the absence of photocatalysts.

The first asymmetric decarboxylative [4 + 3] annulation of propargylic carbamates with C,N-cyclic azomethine imines has been developed successfully by a copper−N-heterocyclic carbine system. This strategy led to a series of optically active isoquinoline-fused triazepine derivatives in good yields and with excellent enantio-and diastereoselectivities. Remarkably, Cu−allenylidene intermediates play a crucial role in this transformation.

In the past few years, Ru and Ir catalyzed photoredox radical coupling reactions have been widely applied in organic synthesis. In contrast, the applications of Cu catalysts in photoredox organic transformations were limited. We here report the first example of photoinduced, Cu-catalyzed three component cyanofluoroalkylation of alkenes by directly using fluoroalkyl iodides as fluoroalkylation reagents.

The visible light induced, photocatalysts or photoabsorbing EDA complexes mediated cleavage of pyridinium C-N bond were reported in the past years. Here, we report an ionic compound promote homolytic cleavage of pyridinium C-N bond by exploiting the photonic energy from visible light. This finding is successfully applied in deaminative hydroalkylation of a series of alkenes including naturally occurring dehydroalanine, which provides an efficient way to prepare β-alkyl substituted unnatural amino acids under mild and photocatalyst-free conditions. Importantly, by using this protocol, the deaminative cyclization of peptide backbone N-terminals is realized. Furthermore, the use of Et3N or PPh3 as reductants and H2O as hydrogen atom source is a practical advantage. We anticipate that our protocol will be useful in peptide synthesis and modern peptide drug discovery.