C.K. acknowledges the HPC resources of CINES and IDRIS under the allocations 2016- [x2016080649] made by GENCI.International audienceNear-infrared two-photon (TP)-induced photorelease (uncaging) of bioactive molecules such as drugs has attracted considerable attention because of its ability to elucidate mechanistic aspects of biological processes. This short review summarizes recent developments in the design and synthesis of TP-responsive chromophores

Alkoxyl radicals play important roles in various fields of chemistry. Understanding their reactivity is essential to applying their chemistry for industrial and biological purposes. Hydrogen-atom transfer and C−C β-scission reactions have been reported from alkoxyl radicals. The ratios of these two processes were investigated using cumyloxyl (CumO • ) and tert-butoxyl radicals (t-BuO • ), respectively. However, the products generated from the pair of radicals have not been investigated in detail. In this study, CumO • and t-BuO • were simultaneously generated from the photolysis of tert-butyl cumyl peroxide to understand the chemical behavior of the pair of radicals by analyzing the products and their distribution. Electron paramagnetic resonance and/or transient absorption spectroscopy analyses of radicals, including CumO • and t-BuO • , provide more information about the radicals generated during the photolysis of tert-butyl cumyl peroxide. Furthermore, the photoproducts of (3-(tert-butylperoxy)pentane-3yl)benzene demonstrated that the ether products were formed in in-cage reactions. The triplet-sensitized reaction induced by acetophenone, which is produced from CumO • , clarified that the spin state did not affect the product distribution.

A metal-free and operationally simple strategy for generation of various α-monofluoroalkyl radicals has been developed. A combination of 1,4-bis(diarylamino)naphthalene photocatalyst and sulfoximine-based fluoroalkylating reagents is a key to success. The...

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