Hydroarylation is an effective strategy to rapidly increase the complexity of organic structures by transforming flat alkene moieties into three-dimensional frameworks. Many strategies have already been developed to achieve the hydroarylation of styrenes, however most of these reports examine the hydroarylation of unpolar, β-mono- or β-unsubstituted styrenes, while exploring mainly electron-rich benzene nucleophiles. Herein, we report a mild and general catalytic system for the selective hydroheteroarylation of multiply substituted styrenes and heteroaromatic styrenes. Mechanistic analysis of the reaction led to the discovery of commercially available 2,2':5',2''-terthiophene as a key reagent.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1002/anie.202016268 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Assembly of Pyrenes through a Quadruple Photochemical Cascade: Blocking Groups Allow Diversion from the Double Mallory Path to Photocyclization at the Bay Region.
J Am Chem Soc
December 2024
Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, United States.
We present a six-step cascade that converts 1,3-distyrylbenzenes (-stilbenes) into nonsymmetric pyrenes in 40-60% yields. This sequence merges photochemical steps, ,-alkene isomerization, a 6π photochemical electrocyclization (Mallory photocyclization); the new bay region cyclization, with two radical iodine-mediated aromatization steps; and an optional aryl migration. This work illustrates how the inherent challenges of engineering excited state reactivity can be addressed by logical design.
View Article and Find Full Text PDFHeteroaryl-Directed Iridium-Catalyzed Enantioselective C-H Alkenylations of Secondary Alcohols.
J Am Chem Soc
December 2024
Department of Chemistry, University of Liverpool, Crown Street, Liverpool L69 7ZD, United Kingdom.
Under iridium-catalyzed conditions, 2-aza-aryl-substituted secondary alcohols undergo C(sp)-H addition reactions to alkynes to provide alkenylated tertiary alcohols. The processes occur with very high regio- and enantioselectivity. An analogous addition to styrene is shown to provide a prototype C(sp)-H alkylation process.
View Article and Find Full Text PDFRegio- and diastereoselective synthesis of cyclobutylated phenothiazines [2 + 2] photocycloaddition: demonstrating wavelength-gated cycloreversion inside live cells.
Chem Sci
December 2024
Department of Chemistry, Indian Institute of Science Education and Research (IISER) Bhopal Academic Building - 2, Bhopal By-pass Road, Bhauri Bhopal-462066 India
Herein, we unveiled a regio- and diastereoselective synthesis of cyclobutylated phenothiazines, a unique class of structural congeners of phenothiazines visible-light-irradiated intermolecular [2 + 2]-cycloaddition reaction, from readily available naphthoquinones, 2-aminothiophenols, and styrenes, either in a two-step or three-component coupling process. By varying substitutions in all three coupling partners, a library of cyclobutylated phenothiazines, including late-stage derivatization with five commercial drugs, has been realized with up to 97% isolated yield. In contrast to the reported pathways, the developed [2 + 2]-photocycloaddition seems to proceed a 'photoinduced-electron-transfer' (PET) mechanism, which is well corroborated with the experimental observations, Rehm-Weller equation, and computation studies.
View Article and Find Full Text PDFB(CF)-Catalyzed Regiodivergent Thioetherifications of Alkenes via Thiiranium Intermediates: Experimental and Computational Insights.
Chemistry
December 2024
Cardiff Catalysis Institute, School of Chemistry, Cardiff University, Translational Research Hub, Maindy Road, Cathays, Cardiff, Cymru/Wales, CF24 4HQ, UK.
Precise control of selective alkene functionalization is a continuing challenge in the chemical community. In this study, we develop a substitution-controlled regiodivergent thioetherification of di- or trisubstituted alkenes using 10 mol % tris(pentafluorophenyl)borane [B(CF)] as a catalyst and N-thiosuccinimide as a sulfenylating reagent. This metal-free borane catalyzed C-S bond forming method is utilized for a Csp-H sulfenylation reaction to synthesize an array of diphenylvinylsulfide derivatives with good to excellent yields (25 examples, up to 91 % yield).
View Article and Find Full Text PDFBoryl Radical Mediated Hydro(-diboryl)alkylation of Alkenes with Sterically Hindered NHC Boranes.
Org Lett
December 2024
College of Chemistry, Zhengzhou University, Zhengzhou 450001, P. R. China.
NHC boryl radical mediated halogen atom transfer (XAT) is useful in organic synthesis. Yet, most of the reaction ends only with reducing the halogen to hydrogen, that is, the C-X to C-H. This is especially dominant for electron-deficient alkyl halides, where the formed electrophilic radical reacts rapidly with NHC boranes.
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!