02612nas a2200241   4500008004100000022001400041245017200055210006900227260000800296300001000304490000800314520171100322653001702033653001902050653003002069653002402099653002702123653002902150100001802179700002502197700002002222856012802242       2021                        eng d  a0021-951700aDual-catalyst engineered porous organic framework for visible-light triggered, metal-free and aerobic sp(3) C-H activation in highly synergistic and recyclable fashion0 aDualcatalyst engineered porous organic framework for visibleligh  cFEB  a40-490 v3943 a<p>Photoredox and organo-catalysis denote powerful construction tools for new classes of carbon-carbon bonds, where incisive amalgamation of both the approaches over a single, recyclable platform can bring about synergic and eco-friendly reactions under mild conditions. Aiming at enamine-based photoredox catalysis for atom-economic and metal-free sp(3 )C-H activation, an amide-based two-dimensional (2D) porous organic framework (POF) is devised. The pendent -NH2 groups are judiciously anchored with two catalytic stations viz. Rose Bengal and L-proline, through stepwise variation of solid phase peptide synthesis. The dual-catalyst engineered POF represents a fully organic material that synergistically performs visible-light triggered oxidative Mannich reaction to produce biorelevant heterocycle beta-amino ketone in excellent yield at room temperature, using oxygen as clean and selective oxidant. Importantly, activity of this bi-functionalized catalyst compares favorably well to individual homogeneous counterparts. The covalently modified framework demonstrates economic viability via gram-scale synthesis besides admirable reusability, and proves to be effective for nineteen varieties of substrates. The photocatalytic path is detailed from efficient energy transfer from host polymer to substrate in light of experimental and theoretical studies, which provides proof-of-concept to the photo-organo combined mechanism. The material benefits heterogenising two homogeneous catalysts, besides excluding additional steps of conventional Mannich reactions, and offers a step-forward to smart and green cross-dehydrogenative coupling reactions. (C) 2020 Elsevier Inc. All rights reserved.</p>
10aAtom-economy10aC-H activation10aDual-catalyst engineering10aMetal-free reaction10aPhoto-organo catalysis10aPorous organic framework1 aKumar, Gaurav1 aDash, Soumya, Ranjan1 aNeogi, Subhadip  uhttps://library.ncl.res.in/content/dual-catalyst-engineered-porous-organic-framework-visible-light-triggered-metal-free-and