Oxygenation is a fundamental transformation in synthesis. Herein, we describe the selective late‐stage oxygenation of sulfur‐containing complex molecules with ground‐state oxygen under ambient conditions. The high oxidation potential of the active uranyl cation (UO22+) enabled the efficient synthesis of sulfones. The ligand‐to‐metal charge transfer process (LMCT) from O 2p to U 5f within the O=U=O group, which generates a UV center and an oxygen radical, is assumed to be affected by the solvent and additives, and can be tuned to promote selective sulfoxidation. This tunable strategy enabled the batch synthesis of 32 pharmaceuticals and analogues by late‐stage oxygenation in an atom‐ and step‐efficient manner.
Uranyl-photocatalyzed
hydrolysis of diaryl ethers has been established
to achieve two types of phenols at room temperature under normal pressure.
The single electron transfer process was disclosed by a radical quenching
experiment and Stern–Volmer analysis between diphenyl ether
and uranyl cation catalyst, followed by oxygen atom transfer process
between radical cation of diphenyl ether and uranyl peroxide species.
The
18
O-labeling experiment precisely demonstrates that
the oxygen source is water. Further application in template substrates
of 4-O-5 linkages from lignin and 30-fold efficiency of flow operation
display the potential application for phenol recovery via an ecofriendly
and low-energy consumption protocol.
The unconventional Z-selective halosulfonylation of terminal alkynes has been achieved by using CuX (X = Cl, Br, I)/sulfonohydrazides at rt, providing a practical and new route for the synthesis of diverse halogenated vinyl sulfones.
Carbon-nitrogen bond activation, via uranyl photoredox catalysis with water, enabled the conversion from 40 protogenetic anilines, 8 N-substituted anilines, and 9 aniline-containing natural products/pharmaceuticals to the corresponding phenols at ambient environment. Single electron transfer process between protonated aniline and uranyl catalyst, which was disclosed by radical quenching experiments and Stern-Volmer analysis, facilitated the following oxygen atom transfer process between radical cation of protonated anilines and uranyl peroxide originating from water-splitting. 18O labelling and 15N tracking unambiguously depicted that the oxygen came from water and amino group leaved as ammonium salt. Hundredfold efficiency of flow operation demonstrated the great potential of the conversion process in industrial synthetic application.
A bright future for triazoles: The recent breakthrough in the synthesis of 1,2,3‐triazoles is highlighted for its significance as a new tool in the chemistry of 1,2,3‐triazoles following the classical CuAAC and metal‐free protocols.
Oxygenation is af undamental transformation in synthesis.H erein, we describe the selective late-stage oxygenation of sulfur-containing complex molecules with groundstate oxygen under ambient conditions.T he high oxidation potential of the active uranyl cation (UO 2 2+ )e nabled the efficient synthesis of sulfones.T he ligand-to-metal charge transfer process (LMCT) from O2ptoU5f within the O=U=O group,w hich generates aU V center and an oxygen radical, is assumed to be affected by the solvent and additives,and can be tuned to promote selective sulfoxidation. This tunable strategy enabled the batch synthesis of 32 pharmaceuticals and analogues by late-stage oxygenation in an atom-and step-efficient manner.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.
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