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| Open AccessCatalytic 4-exo-dig carbocyclization for the construction of furan-fused cyclobutanones and synthetic applications
Aromatic ring fused cyclobutanone is a strained motif with broad applications. Here, the authors report a catalytic 4- exo-dig process, which proved successful to access furan-fused cyclobutanones that can serve as versatile synthetic blocks.
- Kemiao Hong
- , Yi Zhou
- & Xinfang Xu
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Article
| Open Access3-sulfonyloxyaryl(mesityl)iodonium triflates as 1,2-benzdiyne precursors with activation via ortho-deprotonative elimination strategy
Preparation of functionalized analogues of 1,2-benzdiyne, from heavily substituted as well as benzofused scaffolds, is challenging. Here, the authors develop an array of 3-sulfonyloxyaryl(mesityl)iodonium triflates as 1,2-benzdiyne precursors, triggered from ortho-deprotonative elimination.
- Haoyin Yuan
- , Wenhao Yin
- & Yang Li
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Article
| Open AccessA practical fluorosulfonylating platform via photocatalytic imidazolium-based SO2F radical reagent
Sulfonyl fluorides have potential application in chemical biology, materials science, and drug discovery, but their preparation remains challenging. Here, the authors report an air-stable fluorosulfonylating reagent that enables the radical fluorosulfonylation, hydrofluorosulfonylation and migratory SO2F-difunctionalization of unsaturated hydrocarbons to construct a variety of sulfonyl fluoride compounds.
- Weigang Zhang
- , Heyin Li
- & Yi Wang
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Article
| Open AccessPhotoredox catalytic radical fluorosulfonylation of olefins enabled by a bench-stable redox-active fluorosulfonyl radical precursor
Sulfonyl fluorides are compounds with potential application in chemical biology and drug discovery, but their preparation can be challenging. Here, the authors present a type of bench-stable fluorosulfonyl radical reagents that enable radical fluorosulfonylation reactions via photoredox catalysis.
- Peng Wang
- , Honghai Zhang
- & Saihu Liao
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Article
| Open AccessTopotactic fluorination of intermetallics as an efficient route towards quantum materials
Insertion of light elements in intermetallics has been explored to synthesize functional materials. Here the authors report topotactic intercalation of fluorine atoms into intermetallics using a perfluorocarbon reactant with covalent C-F bonds to obtain quantum materials.
- Jean-Baptiste Vaney
- , Baptiste Vignolle
- & Sophie Tencé
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Article
| Open AccessPreparative-scale synthesis of nonacene
Acenes, or linearly fused benzene rings, have both fundamental scientific interest and potential for electronic and material utility, but synthesis of acenes with more than six rings are difficult due to dimerization and degradation. Here the authors prepare nonacene and demonstrate that it is stable in inert conditions.
- Andrej Jančařík
- , Jan Holec
- & Andre Gourdon
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Article
| Open AccessSelective deoxygenative alkylation of alcohols via photocatalytic domino radical fragmentations
The generation of alkyl radicals through deoxygenation of abundant alcohols via photoredox catalysis is of interest. In this study, the authors report a one-pot strategy for visible-light-promoted photoredox coupling of alcohols with electron-deficient alkenes, assisted by carbon disulfide and triphenylphosphine.
- Hong-Mei Guo
- & Xuesong Wu
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Article
| Open AccessSynthetic exploration of sulfinyl radicals using sulfinyl sulfones
Sulfinyl radicals are an underexplored synthon in organic chemistry due to the fact that they reversibly add to pi systems and undergo homodimerization. Here the authors synthesize sulfonyl sulfones, previously thought to be unstable, and demonstrate their broad use as sulfinyl radical precursors in disulfurizations of alkenes and alkynes.
- Zikun Wang
- , Zhansong Zhang
- & Xihe Bi
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Article
| Open AccessTransition-metal-free allylation of 2-azaallyls with allyl ethers through polar and radical mechanisms
Allylation of nucleophiles with less reactive electrophiles, such as carbonates, usually requires a transition-metal catalyst. Here, the authors show a transition-metal-free allylation strategy with allyl ether electrophiles to form homoallylic amine derivatives in up to 92% yield.
- Guogang Deng
- , Shengzu Duan
- & Patrick J. Walsh
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Article
| Open AccessProgrammable site-selective labeling of oligonucleotides based on carbene catalysis
The methods for investigation of DNA-binding proteins require site-selective chemical modifications to be introduced into oligonucleotides. Here, the authors report a chemo- and regioselective method for the modification of unpaired guanosines in single- and double-stranded oligonucleotides, based on Rh(I)-carbene catalysis.
- Yang-Ha Lee
- , Eunsoo Yu
- & Cheol-Min Park
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Article
| Open AccessOxidation of difluorocarbene and subsequent trifluoromethoxylation
Difluorocarbene is a versatile and efficient intermediate for fluorine incorporation. Here, the authors show that difluorocarbene can be oxidized to carbonyl fluoride and this process is confirmed in 18O-trifluoromethoxylation reactions, by observation of AgOCF3 species and theory.
- Jiao Yu
- , Jin-Hong Lin
- & Ji-Chang Xiao
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Article
| Open AccessRegioselective radical α-borylation of α,β-unsaturated carbonyl compounds for direct synthesis of α-borylcarbonyl molecules
α-Borylcarbonyl compounds are versatile synthons in organic synthesis, however their preparation is often tedious. Here, the authors report a regioselective radical α-borylation of α,β-unsaturated carbonyl compounds to afford α-borylcarbonyl molecules with high selectivity and functional group compatibility.
- Shi-Chao Ren
- , Feng-Lian Zhang
- & Yi-Feng Wang
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Article
| Open AccessFrom stable Sb- and Bi-centered radicals to a compound with a Ga=Sb double bond
Radicals of heavy main-group elements represent important intermediates in chemical synthesis, yet few have been isolated. Here the authors stabilize neutral stibinyl and bismuthinyl radicals using gallium-based ligands, and reduce the former to afford a Ga=Sb double bond-containing complex.
- Chelladurai Ganesamoorthy
- , Christoph Helling
- & Stephan Schulz
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Article
| Open AccessStacked antiaromatic porphyrins
It has been proposed that stacking antiaromatic molecules can build three-dimensional aromaticity, but this claim has lacked experimental validation. Here the authors report that π–π stacked antiaromatic porphyrins display significantly reduced antiaromaticity in solid state and in solution.
- Ryo Nozawa
- , Hiroko Tanaka
- & Hiroshi Shinokubo