Reversible C=C Bond Activation by an Intramolecularly Coordinated Antimony(I) Compound

The reaction of N,C,N-chelated stibinidene ArSb ( 1 ) (Ar=C₆H₃-2,6-(CH=NtBu)₂) with selected N-alkyl/aryl-maleimides RN(C(O)CH)₂ (R=Me, tBu, Ph) gave the addition products with bridged bicyclic [2.2.1] structure containing an antimony atom at the bridgehead position, fused with a 6-membered benzene and a 5-membered N-alkyl/aryl-pyrrolidine ring. These compounds were completely characterized. More importantly, additional studies showed that these reactions are reversible in solution, thereby representing an unprecedented reversible activation of a C=C bond by an antimony(I) compound.     

Lewis Acid Transition-Metal-Catalyzed Hydrogen Activation: Structures,Mechanisms, and Reactivities

As a new type of bifunctional catalyst, the Lewis acid transition-metal (LA-TM) catalysts have been widely applied for hydrogen activation. This study presents a mechanistic framework to understand the LA-TM-catalyzed H₂ activation through DFT studies. The mer(trans)-homolytic cleavage, the fac(cis)-homolytic cleavage, the synergetic heterolytic cleavage, and the dissociative heterolytic cleavage should be taken as general mechanisms for the field of LA-TM catalysis. Four typical LA-TM catalysts, the Z-type κ⁴-L₃B-Rh complex tri(azaindolyl)borane-Rh, the X-type κ³-L₂B-Co complex bis-phosphino-boryl (PBP)-Co, the η²-BC-type κ³-L₂B-Pd complex diphosphine-borane (DPB)-Pd, and the Z-type κ²-LB-Pt complex (boryl)iminomethane (BIM)-Pt are selected as representative models to systematically illustrate their mechanistic features and explore the influencing factors on mechanistic variations. Our results indicate that the tri(azaindolyl)borane-Rh catalyst favors the synergetic heterolytic mechanism; the PBP-Co catalyst prefers the mer(trans)-homolytic mechanism; the DPB-Pd catalyst operates through the fac(cis)-homolytic mechanism, whereas the BIM-Pt catalyst tends to undergo the dissociative heterolytic mechanism. The mechanistic variations are determined by the coordination geometry, the LA-TM bonding nature, the electronic structure of the TM center, and the flexibility or steric effect of the LA ligands. The presented mechanistic framework should provide helpful guidelines for LA-TM catalyst design and reaction developments.     

Evaluation of Polyphenols in Wine by Voltammetric Techniques with Screen Printed Carbon Electrodes

The electrochemical oxidation processes that occur during a voltammetric assay in wine samples lead to the formation of species that obstructs the surface and reduce their active area. This effect is critical for screen printed carbon electrodes (SPCE) and leads to abnormal low values of the total polyphenols content of wines, ca. 72 % lower than those obtained with glassy carbon electrodes. This effect was examined using 10 red and Port wine samples. Mechanical polishing and electrochemical‐based treatments for the removal of this fouling layer were tested. The best results were obtained by electrochemical activation in at a constant potential of 1.2 V during 100 s Na₂CO₃ saturated solution, and by polishing. The success of some of these treatments brings an added value to SPCE, as it opens the possibility of their reuse in the wine analysis. This outcome is particularly relevant for quality control where a huge number of analysis is performed and the reduction of cost may dictates the choice of the analytical method.     

Divergent Synthesis of Bioactive Dithiodiketopiperazine Natural Products Based on a Double C(sp3)−H Activation Strategy

This article provides a detailed report of our efforts to synthesize the dithiodiketopiperazine (DTP) natural products (−)-epicoccin G and (−)-rostratin A using a double C(sp³)−H activation strategy. The strategy's viability was first established on a model system lacking the C8/C8’ alcohols. Then, an efficient stereoselective route including an organocatalytic epoxidation was secured to access a key bis-triflate substrate. This bis-triflate served as the functional handles for the key transformation of the synthesis: a double C(sp³)−H activation. The successful double activation opened access to a common intermediate for both natural products in high overall yield and on a multigram scale. After several unsuccessful attempts, this intermediate was efficiently converted to (−)-epicoccin G and to the more challenging (−)-rostratin A via suitable oxidation/reduction and protecting group sequences, and via a final sulfuration that occurred in good yield and high diastereoselectivity. These efforts culminated in the synthesis of (−)-epicoccin G and (−)-rostratin A in high overall yields (19.6 % over 14 steps and 12.7 % over 17 steps, respectively), with the latter being obtained on a 500 mg scale. Toxicity assessments of these natural products and several analogues (including the newly synthesized epicoccin K) in the leukemia cell line K562 confirmed the importance of the disulfide bridge for activity and identified dianhydrorostratin A as a 20x more potent analogue.     

Transition Metal-Catalyzed Enantioselective C−H Functionalization via Chiral Transient Directing Group Strategies

Transition metal-catalyzed enantioselective functionalization of C−H bond, the most abundant functionality in organic molecules, has emerged as an expedient synthetic approach to streamline the synthesis of complex chiral molecules. Despite significant progress, traditional directing group-enabled strategies require additional steps for the installation and removal of directing groups from the target molecule. The recently developed asymmetric C−H functionalization using chiral transient directing groups (cTDGs) offers a promising alternative that can circumvent this obstacle and therefore simplify the process. In this Minireview, we briefly discuss the advent and recent advances of this emerging concept, with an emphasis on discussing the creation of various stereogenic centers and the developments of cTDGs. Applications in natural product synthesis and ligand derivatizations are also discussed. We hope this Minireview will highlight the great potential of this strategy and help to inspire further endeavors.     

Synthesis of Amides and Esters by Palladium(0)-Catalyzed Carbonylative C(sp3)−H Activation

The 1,4-palladium shift strategy allows the functionalization of remote C−H bonds that are difficult to reach directly. Reported here is a domino reaction proceeding by C(sp³)−H activation, 1,4-palladium shift, and amino- or alkoxycarbonylation, which generates a variety of amides and esters bearing a quaternary β-carbon atom. Mechanistic studies showed that the aminocarbonylation of the σ-alkylpalladium intermediate arising from the palladium shift is fast using PPh₃ as the ligand, and leads to the amide rather than the previously reported indanone product.     

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Pd-PEPPSI type complexes are widely used as precatalyst in a variety of organic reactions, including the Negishi, Kumada and Suzuki-Miyaura cross-coupling reactions. The aim of this research is to determine potential proposed reaction pathways 1, 2, or 2′ (See Schemes 1 and S1–S4 ) for Pd-PEPPSI precatalyst activation in the presence of ethylene glycol as a solvent also in the gas phase at Cam-B3LYP-D3 method nominated among eight DFT methods examined. There is also investigation into the impact of promoter bases (NaOEt, NaOⁱPr, NaO^tBu) on precatalyst activation of Pd-PEPPSI. Eventually, the most favorable proposed reaction pathway and promoter base for reducing Pd(II) to Pd(0) are predicted computationally. Notably, our findings are consistent with the organ Pd-PEPPSI type complexes that offer increased catalytic activity and provide basic information in the presence of solvents designing the monoligated Pd(0)-solvent.     

Cobalt(II)-Catalyzed [4+2] Annulation of Picolinamides with Alkynes via C−H Bond Activation

A cobalt(II)-catalyzed [4+2] annulation of picolinamides with alkynes via C−H bond activation has been developed. The operationally simple annulation reaction allows for the synthesis of acyl-substituted 1H-benzoquinoline bearing multiple aromatic rings (up to 96 % yield) without co-oxidant or other oxidation factors under mild conditions. Several control experiments were carried out. This practical [4+2] annulation provides an efficient route to access highly functionalized compounds.     

Iridium-Catalyzed Regioselective B(3)-Alkenylation/B(3,6)-Dialkenylation of o-Carboranes by Direct B−H Activation

Iridium-catalyzed formal alkyne hydroboration with cage B−H of o-carborane has been achieved, leading to the controlled synthesis of a series of 3,6-[trans-(AlkCH=CH)]₂-o-carboranes (Alk=alkyl), 3-cis-(ArCH=CH)-o-carboranes (Ar=aryl), and 3-cis-(ArCH=CH)-6-trans-(AlkCH=CH)-o-carboranes in high yields with excellent regio- and very good cis–trans selectivity. The most electron-deficient B(3,6)−H vertices favor oxidative addition on electron-rich metal centers, which is responsible for the regioselectivity. On the other hand, the configuration of the resultant olefinic units is dominated by alkyne substituents. Alkyl groups lead to a trans-configuration whereas bulky aryl substitutions result in cis-configuration.