The prevalence of the biaryl structural motif in biologically interesting and synthetically important molecules has inspired considerable interest in the development of methods for aryl-aryl bond formation. Herein we describe a novel strategy for this process involving the fluoride-free, palladium-catalysed cross-coupling of readily accessible aryldisiloxanes and aryl bromides. Using a statistical-based optimisation process, preparatively useful reaction conditions were formulated to allow the cross-coupling of a wide range of different substrates. This methodology represents an attractive, cost-efficient, flexible and robust alternative to the traditional transition-metal-catalysed routes typically used to generate molecules containing the privileged biaryl scaffold.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1002/chem.201102285 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Nickel Catalyzed Aryl-Aryl Bridging C-N Bond Activation of 2-Pyridylpyridones and 6-Purinylpyridones.
Org 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 PDFInherently chiral nor-heteracalixarenes: design and synthesis enantioselective intramolecular Suzuki-Miyaura reaction.
Chem Sci
August 2024
Key Laboratory of Bioorganic Phosphorus Chemistry and Chemical Biology (Ministry of Education), Department of Chemistry, Tsinghua University Beijing 100084 China http://mascl.group.
There has been a recent upsurge in research aimed at synthesizing inherently chiral molecules devoid of point, axial, planar and helical chiralities. We present herein our design and enantioselective synthesis of a series of inherently chiral macrocycles. These compounds, termed nor-heteracalixaromatics, feature a biaryl bond that replaces one of the aryl-heteroatom-aryl linkages found in classic heteracalix[4]aromatics.
View Article and Find Full Text PDFConformational Locking Induced Enantioselective Diarylcarbene Insertion into B-H and O-H Bonds Using a Cationic Rh(I)/Diene Catalyst.
Angew Chem Int Ed Engl
November 2024
Shenzhen Grubbs Institute and Department of Chemistry, Southern University of Science and Technology, Shenzhen, 518055, China.
Transition-metal-catalyzed enantioselective transformations of aryl/aryl carbene are inherently challenging due to the difficulty in distinguishing between two arene rings in the reaction process thus remain largely less explored. The few successful examples reported so far, without exception, have all been catalyzed by Rh(II)-complexes. Herein, we describe our successful development of a novel cationic Rh(I)/chiral diene catalytic system capable of efficient enantioselective B-H and O-H insertions with diaryl diazomethanes, allowing the access to a broad range of gem-diarylmethine boranes and gem-diarylmethine ethers in good yields with high enantioselectivities.
View Article and Find Full Text PDFNickel-Catalyzed Electrochemical Cross-Electrophile C(sp)-C(sp) Coupling via a Ni Aryl Amido Intermediate.
Angew Chem Int Ed Engl
September 2024
Department of Chemistry and Biochemistry, Utah State University, 0300 Old Main Hill, Logan, Utah, 84322, United States.
Cross-electrophile coupling (XEC) between aryl halides and alkyl halides is a streamlined approach for C(sp)-C(sp) bond construction, which is highly valuable in medicinal chemistry. Based on a key Ni aryl amido intermediate, we developed a highly selective and scalable Ni-catalyzed electrochemical XEC reaction between (hetero)aryl halides and primary and secondary alkyl halides. Experimental and computational mechanistic studies indicate that an amine secondary ligand slows down the oxidative addition process of the Ni-polypyridine catalyst to the aryl bromide and a Ni aryl amido intermediate is formed in situ during the reaction process.
View Article and Find Full Text PDFα-Diimine-mediated C-H functionalization of arenes for aryl-aryl cross-coupling reactions.
Org Biomol Chem
March 2024
Department of Chemistry & Biochemistry, University of California Merced, Merced, CA 95343, USA.
Easily accessible methods for direct C-H arylation of arenes have been explored in the presence of transition metal catalysts to facilitate C-C bond formation; however, the absence of transition-metal impurities is a significant concern in the preparation of active pharmaceutical ingredients (APIs). Herein, we examine the use of bis(imino)acenaphthene (BIAN) as a potential single-electron transfer initiator in transition metal-free C-C bond-forming reactions. Using this approach, arenes are coupled to several aryl and heteroaryl halides.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!