Cross-Coupling of Acrylamides and Maleimides under Rhodium Catalysis: Controlled Olefin Migration

The rhodium­(III)-catalyzed direct cross-coupling reaction of electron-deficient acrylamides with maleimides is described. This protocol displays broad functional group tolerance and high efficiency, which offers a new opportunity to access highly substituted succinimides. Dependent on the substituent positions of acrylamides and reaction conditions, olefin migrated products were obtained with high regio- and stereoselectivity

Synthesis of 2‑Benzazepines from Benzylamines and MBH Adducts Under Rhodium(III) Catalysis via C(sp²)–H Functionalization

The rhodium­(III)-catalyzed cross-coupling reaction between commercially available benzylamines and Morita–Baylis–Hillman (MBH) adducts is described. This protocol provides a facile access to various 2-benzazepine derivatives via the C­(sp²)–H activation of <i>N</i>-allylated benzylamines and subsequent intramolecular olefin insertion followed by <i>N</i>-allylation reaction. A range of substrates has been used, and a high level of chemoselectivity as well as functional group tolerance was observed. To gain mechanistic insight of this transformation, DFT calculations were also performed

Ru(II)-Catalyzed C–H Aminocarbonylation of <i>N</i>‑(Hetero)aryl-7-azaindoles with Isocyanates

The ruthenium­(II)-catalyzed C–H aminocarbonylation of <i>N</i>-(hetero)­aryl-7-azaindoles with isocyanates is described. The excellent site selectivity at the <i>ortho</i>-position within the <i>N</i>-(hetero)­aryl ring was observed to provide <i>ortho</i>-amidated <i>N</i>-(hetero)­aryl-7-azaindoles under the mild reaction conditions. The resulting 7-azaindole derivatives can be readily transformed into 7-azaindoles containing carboxylic acid and alkyl amine functional groups

Synthesis of TMPA Derivatives through Sequential Ir(III)-Catalyzed C–H Alkylation and Their Antidiabetic Evaluation

The synthesis and antidiabetic evaluation of ethyl 2-[2,3,4-trimethoxy-6-(1-octanoyl)­phenyl]­acetate (TMPA) and its structural analogs are described. The construction of TMPA derivatives has been successfully achieved in only two steps, which involve the iridium­(III)-catalyzed α-alkylation of acetophenones with alcohols and the ketone-directed iridium­(III)- or rhodium­(III)-catalyzed redox-neutral C–H alkylation of α-alkylated acetophenones using Meldrum’s diazo compounds. This synthetic protocol efficiently provides a range of TMPA derivatives with site selectivity and functional group compatibility. In addition, the site-selective demethylation of TMPA derivative affords the naturally occurring phomopsin C in good yield. Moreover, all synthetic compounds were screened for in vitro adenosine 5′-monophosphate-activated protein kinase (AMPK) activation using HepG2 cells. Furthermore, TMPA (<b>5ac</b>) and <b>5cd</b> showing the most potent AMPK activation were treated for the in vivo antidiabetic experiment. Notably, our synthetic compound <b>5cd</b> was found to display the powerful antidiabetic effect, stronger than that of metformin and TMPA (<b>5ac</b>)