In the presence of molecular oxygen, a {001}-faceted nanocrystalline anatase TiO catalyst enabled the selective oxidation of nonactivated aliphatic alcohols to the corresponding aldehydes or ketones under visible light. The reaction shows excellent conversion and selectivity towards the formation of the carbonyl products without over-oxidation to the corresponding carboxylic acids. The exceptional reactivity of the catalyst is possibly due to the absorption of visible light originating from a stronger interaction of alcohol with the {001} facet, which facilitates the modification of the band structure of TiO , thus facilitating the photogenerated hole transfer and subsequent oxidation processes. The experimental results have also been corroborated by first-principles quantum chemical DFT calculations.
An
efficient photocatalytic method was developed for the remote
C5-H bond carboxylation of 8-aminoquinoline amide and sulfonamide
derivatives. This methodology uses in situ generated •CBr3 radical as a carboxylation agent with alcohol and
is further extended to a variety of arenes and heteroarenes to synthesize
the desired carboxylated product in moderate-to-good yields. The reaction
proceeding through a single electron transfer pathway was established
by a control experiment, and a butylated hydroxytoluene-trapped aryl
radical cation intermediate in high-resolution mass spectrometry was
identified.
A simple and practical heterogeneous Cu‐MnO catalyzed regioselective halogenation of anilides and quinolines under irradiation with household 40 W incandescent lamp was developed. This method uses a recyclable Cu‐MnO catalyst, acetonitrile as an industrially friendly solvent, and economic N‐halo succinimides as a halogenating source. The reaction is scalable and well tolerated with a broad range of functional groups.
We developed a straightforward, atom-economical and scalable route for the synthesis of alkynylphosphonates and ynamides using a reusable Cu–MnO catalyst.
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