Bicyclo[1.1.0]butanes (BCBs) have gained growing popularity in "strain release" chemistry for the synthesis of four-membered-ring systems and - and -disubstituted arene bioisosteres as well as applications in chemoselective bioconjugation. However, functionalization of the bridge position of BCBs can be challenging due to the inherent strain of the ring system and reactivity of the central C-C bond. Here we report the first late-stage bridge cross-coupling of BCBs, mediated by directed metalation/palladium catalysis.
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http://dx.doi.org/10.1021/acs.orglett.3c04030 | DOI Listing |
Angew Chem Int Ed Engl
December 2024
Institute of Organic Chemistry, University of Vienna, Währinger Str. 38, 1090, Vienna, Austria.
An enantioconvergent palladium-catalyzed Negishi cross-coupling with racemic secondary organozinc reagents has been developed, enabling access to enantioenriched 1,1-diarylalkane motifs in high yields and enantioselectivities. Computational data indicates that the racemization of organozinc compounds most likely occurs through a bridged bimolecular mechanism.
View Article and Find Full Text PDFOrg Lett
November 2024
School of Chemical Sciences, National Institute of Science Education and Research (NISER), Bhubaneswar, 752050, Odisha, India.
A Ni-catalyzed C-N bond activation of 2-pyridylpyridone and 1-(9-alkyl 9-purin-6-yl)pyridin-2(1)-one and coupling with arylboronic acid have been achieved. A unique feature of this reaction is the strategic activation of the bridging C-N bond and replacement of the pyridone unit with aryl groups using nickel catalyzed Suzuki-Miyaura coupling. This provides an exciting new tool to build C-C bonds in the place of pyridones.
View Article and Find Full Text PDFJ Am Chem Soc
October 2024
Tata Institute of Fundamental Research Hyderabad, Gopanpally, Hyderabad 500046, India.
Herein, we report nickel(0)-catalyzed cross-coupling reactions of NHC/CAAC-based carbodicarbene (NHC = -heterocyclic carbene and CAAC = cyclic(alkyl)(amino)carbene) with different aryl chlorides, bromides, and iodides. The resulting aryl-substituted cationic carbodicarbene derivatives are prone to one-electron oxidation yielding radical-dications, which, depending on the aryl motif employed, follow different modes of radical-radical dimerization and constitute an entry point to carbon/nitrogen- and nitrogen/nitrogen-centered diradicaloids. Subsequently, this coupling strategy was strategically applied to the synthesis of -phenylene- and ,-biphenylene-bridged carbon/carbon-centered electron-deficient diradicaloids.
View Article and Find Full Text PDFChembiochem
December 2024
Organic and Bioorganic Chemistry, Department of Chemistry, Bielefeld University, Universitätsstraße 25, 33615, Bielefeld, Germany.
Flavin-dependent halogenases (FDHs) are the most extensively researched halogenases and show great potential for biotransformation applications. These enzymes use chloride, bromide, or iodide ions as halogen donors to catalyze the oxygen-dependent halogenation of electron-rich aryl moieties, requiring stochiometric amounts of FADH in the process. This makes FDH-catalyzed aryl halogenation a highly selective and environmentally friendly tool for the synthesis of aryl halides.
View Article and Find Full Text PDFAnal Chem
September 2024
Department of Chemistry, Washington University in St. Louis, St. Louis, Missouri 63130, United States.
DNA-aptamer-functionalized electrode arrays can provide an intriguing method for detecting pathogen-derived exometabolites. This work addresses the limitations of previous aptamer-based pathogen detection methods by introducing a novel surface design that bridges the gap between initial efforts in this area and the demands of a point-of-care device. Specifically, the use of a diblock copolymer coating on a high-density microelectrode array and Cu-mediated cross coupling reactions that allow for the exclusive functionalization of that coating by any electrode or set of electrodes in the array provides a device that is stable for 1 year and compatible with the multiplex detection of small-molecule targets.
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