A visible-light, single-electron-transfer (SET), photoredox cross-coupling for the synthesis of α-alkoxyketones has been developed. In this method, various aliphatic and aromatic acyl chlorides were successfully coupled with structurally diverse potassium alkoxymethyltrifluoroborates, producing the corresponding α-alkoxyketones with high yields. In this operationally simple and mild cross-coupling protocol, the desired ketones are obtained in one step from bench stable starting materials by a bond connection that is unique to both alkylboron chemistry and photoredox/Ni catalysis.
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http://dx.doi.org/10.1021/acs.orglett.5b03705 | DOI Listing |
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January 2025
Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui, 230026, P. R. China.
The ligands in metal-organic framework (MOF) play as light absorption center and transfer photogenerated electrons to metal node through ligand-to-metal charge transfer (LMCT) during photocatalysis, and energy utilization efficiency is strongly restricted by the light inertness of ligands. Herein, a ligand updating strategy is proposed by inserting energy centers to MOFs to activate the inherent ligands, realizing boosting hot electron generation and photocatalytic activities via the cascaded proceeding of energy transfer and charge transfer. By taking PCN-777 (a zeotype mesoporous Zr-containing MOF) as an example, this study shows that the embedded energy center of 1-pyrenecarboxylic acid (PCA) can activate the inherent ligand of PCN-777 through triplet-triplet energy transfer, where triplet excitons would dissociate into photocarriers migrating to the Zr metal cluster via LMCT process.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
Zhengzhou University, College of Chemistry, and Pingyuan Laboratory, CHINA.
Transition-metal-regulated radical cross coupling enables the selective bonding of two distinct transient radicals, whereas the catalytic method for sorting two almost identical transient radicals, especially similar benzyl radicals, is still rare. Herein, we show that leveraging dual photoredox/cobalt catalysis can selectively couple two similar benzyl radicals. Using easily accessible methylarenes and phenylacetates (benzyl N-hydroxyphthalimide (NHPI) esters) as benzyl radical sources, a range of unsymmetrical 1,2-diarylethane classes via the 1°-1°, 1°-2°, 1°-3°, 2°-2°, 2°-3° and 3°-3° couplings were obtained with broad functional group tolerance.
View Article and Find Full Text PDFOrg Lett
December 2024
Key Laboratory of Synthetic and Natural Functional Molecule of the Ministry of Education, College of Chemistry & Materials Science, Northwest University, Xi'an 710127, China.
The installation of -difluoromethylene groups into two adjacent aryl groups is a formidable synthetic challenge despite their attractive structural, physical, and biochemical properties. Herein, we disclose a photoredox-catalyzed selective defluoroarylation of heteroarenes through inert C(sp)-F and C(sp)-H selective cleavage, which provides a straightforward route to access medicinally relevant aryl-heteroaryl or heteroaryl-heteroaryl difluoromethane scaffolds. Salient features of this reaction include readily accessible starting materials, metal-free conditions, and broad substrate scope.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2024
IISER Kolkata, Chemistry, INDIA.
An established concept to create radical intermediates is photoexcitation of a catalyst to a higher energy intermediate, subsequently leading to a photoinduced electron transfer (PET) with a reaction partner. The known concept of consecutive photoinduced electron transfer (con-PET) leads to catalytically active species even higher in energy by the uptake of two photons. Generally speaking, increased photon uptake leads to a more potent reductant.
View Article and Find Full Text PDFChemistry
December 2024
State Key Laboratory of Organometallic Chemistry, Center for Excellence in Molecular Synthesis, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai, 200032, P. R. China.
Nickel/photoredox dual catalyzed cross-coupling of aryl halides with alkylboron compounds is one of the effective methodologies for the construction of C(sp)-C(sp) bonds. Although elegant results have been achieved by using alkyl trifluoroborates as alkyl radical precursors, the generation of alkyl radicals from readily available alkyl boronic esters is still limited due to their high oxidation potential. We disclosed here that activation of alkyl boronic esters by MeOLi is highly efficient for the generation of alkyl radicals under photocatalysis conditions.
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