Tuning light-driven oxidation of styrene inside water-soluble nanocages

Souvik Ghosal, Ankita Das, Debojyoti Roy and Jyotishman Dasgupta ()
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Souvik Ghosal: Tata Institute of Fundamental Research
Ankita Das: Tata Institute of Fundamental Research
Debojyoti Roy: Tata Institute of Fundamental Research
Jyotishman Dasgupta: Tata Institute of Fundamental Research

Nature Communications, 2024, vol. 15, issue 1, 1-16

Abstract: Abstract Selective functionalization of innate sp2 C-H bonds under ambient conditions is a grand synthetic challenge in organic chemistry. Here we combine host-guest charge transfer-based photoredox chemistry with supramolecular nano-confinement to achieve selective carbonylation of styrene by tuning the dioxygen concentration. We observe exclusive photocatalytic formation of benzaldehyde under excess O2 (>1 atm) while Markovnikov addition of water produced acetophenone in deoxygenated condition upon photoexcitation of confined styrene molecules inside a water-soluble cationic nanocage. Further by careful tuning of the nanocage size, electronics, and guest preorganization, we demonstrate rate enhancement of benzaldehyde formation and a complete switchover to the anti-Markovnikov product, 2-phenylethan-1-ol, in the absence of O2. Raman spectroscopy, 2D 1H-1H NMR correlation experiments, and transient absorption spectroscopy establish that the site-selective control on the confined photoredox chemistry originates from an optimal preorganization of styrene molecules inside the cavity. We envision that the demonstrated host-guest charge transfer photoredox paradigm in combination with green atom-transfer reagents will enable a broad range of sp2 carbon-site functionalization.

Date: 2024
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DOI: 10.1038/s41467-024-45991-9

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