Unprecedented aryl-to-aryl 1,5-rhodium migration is involved in decyanative silylation of aryl cyanides bearing a tethered arene. The 1,5-migration proceeds through remote C-H bond activation. 1,5-Migration also occurs in other rhodium-catalyzed reactions, including borylation and oxidative Mizoroki-Heck reactions.
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http://dx.doi.org/10.1039/c2cc36601k | DOI Listing |
Molecules
January 2025
Department of Chemistry, Fudan University, Shanghai 200438, China.
This review highlights significant advances in iron-catalyzed cross-dehydrogenative coupling (CDC), a method pivotal for forming carbon-carbon (C-C) bonds directly from C-H bonds. This technique uses iron-a naturally abundant, inexpensive, and environmentally benign transition metal-as a catalyst to facilitate the coupling of two unfunctionalized C-H bonds. This method stands out for avoiding pre-functionalized substrates, reducing both waste and cost in organic synthesis.
View Article and Find Full Text PDFMolecules
January 2025
Instituto de Síntesis Química y Catálisis Homogénea, ISQCH (CSIC-Universidad de Zaragoza), Pedro Cerbuna 12, 50009 Zaragoza, Spain.
Orthopalladated derivatives from substituted phenylglycines [Pd(μ-Cl)(CHRC(R)(R)N(R)] () react with halogenating reagents (PhICl, Br, I) () to give the corresponding o-halogenated amino acids CH(X)RC(R)(R)N(R) (). The reaction is general and tolerates a variety of functional groups (R to R) at the aryl ring, the Cα, and the N atom. On the other hand, the reaction of [Pd(μ-Cl)(CHRC(R)(R)N(R)] () with PhI(OAc) in the presence of a variety of alcohols ROH () gives the o-alkoxylated phenylglycines CH(OR)RC(R)(R)N(R) (), also as a general process.
View Article and Find Full Text PDFInorg Chem
January 2025
Department of Chemistry, Virginia Tech, Blacksburg, Virginia 24061, United States.
Herein, we investigate the effects of ligand design on the nuclearity and reactivity of metal-ligand multiply bonded (MLMB) complexes to access an exclusively bimetallic reaction pathway for C-H bond functionalization. To this end, the diiron alkoxide [Fe(Dbf)] () was treated with 3,5-bis(trifluoromethyl)phenyl azide to access the diiron imido complex [Fe(Dbf)(μ-NCHF)] () that promotes hydrogen atom abstraction (HAA) from a variety of C-H and O-H bond containing substrates. A diiron bis(amide) complex [Fe(Dbf)(μ-NHCHF)(NHCHF)] () was generated, prompting the isolation of the analogous bridging amide terminal alkoxide [Fe(Dbf)(μ-NHCHF)(OCH)] () and the asymmetric pyridine-bound diiron imido [Fe(Dbf)(μ-NCHF)(NCH)] ().
View Article and Find Full Text PDFAngew Chem Int Ed Engl
January 2025
Anhui Normal University, School of Chemistry and Materials Science, 189 Jiuhua South Road, 241002, Wuhu, CHINA.
Achieving axially chiral biaryl dialdehydes through asymmetric catalysis remains significantly challenging due to the lack of efficient strategies. In this report, we developed a rhodium-catalyzed enantioselective C-H amidation through chiral transient directing group strategy. With this new approach, a series of axially chiral amido dialdehydes were achieved in up to 86% yields with 99.
View Article and Find Full Text PDFLangmuir
January 2025
Surface Science Laboratory, Graduate School of Engineering, Toyota Technological Institute, 2-12-1, Hisakata, Tempaku, Nagoya, Aichi 468-8511, Japan.
Hydrogen-substituted graphdiyne (HsGDY) is a two-dimensional material with an sp-sp carbon skeleton featuring a band gap and a porous structure that enhances ion diffusion. In previous reports, HsGDY growth was limited to metal substrates such as Cu, which then required transfer. Here, we developed a sandwich method that allows HsGDY to be grown directly on the target substrate.
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