J. Org. Chem.

Mechanistic Insight into the Ni-Catalyzed Kumada Cross-Coupling: Alkylmagnesium Halide Promotes C–F Bond Activation and Electron-Deficient Metal Center Slows Down β-H Elimination

The Ni-catalyzed Kumada–Tamao–Corriu (KTC) cross-coupling between aryl fluorides and alkyl Grignard reagents has been used to achieve a highly selective Csp2–Csp3 bond construction via the carbon–fluorine (C–F) bond activation. However, the detailed mechanism of this groundbreaking KTC reaction remains unclear. Herein, we perform a series of analyses by density functional theory (DFT) calculations in order to understand the reaction mechanisms for the selective activation of a highly inert C–F bond by Ni catalysts with bidentate phosphorus ligands.

Antiaromaticity-Promoted Radical Stability in α-Methyl Heterocyclics

Aromaticity is a fundamental and important concept in chemistry, and usually, the enhancement of aromaticity brings additional thermodynamic stability to a compound. Moreover, since radicals can act as intermediates in chemical reactions, they have attracted considerable attention from both experimental and theoretical chemists for a long time. However, it remains unclear whether there is a relationship between the thermodynamic stability of cyclic planar radicals and their aromaticity.

Bonded to Carbon or Nitrogen? This is a Question on the Regioselectivity in Hyperconjugative Aromaticity

In chemistry, regioselectivity is the preference of one direction of chemical bond making or breaking over all other possible directions. Although it has been extensively investigated in various reactions, the regioselectivity of hyperconjugative aromaticity on either main group systems or transition metal ones remains elusive due to the challenge of synthesizing the target products. Here we report a joint theoretical and experimental study on this issue.

Mechanism of Nickel-Catalyzed Selective C–N Bond Activation in Suzuki-Miyaura Cross-Coupling of Amides: A Theoretical Investigation

In textbooks, the low reactivity of amides is attributed to the strong resonance stability. However, Garg and co-workers recently reported the Ni-catalyzed activation of robust amide C–N bonds, leading to conversions of amides into esters, ketones, and other amides with high selectivity. Among them, the Ni-catalyzed Suzuki-Miyaura coupling (SMC) of N-benzyl-N-tert-butoxycarbonyl (N-Bn-N-Boc) amides with pinacolatoboronate (PhBpin) was performed in the presence of K3PO4 and water. Water significantly enhanced the reaction.

Stability, Reactivity, Selectivity, Catalysis, and Predictions of 1,3,2,5-Diazadiborinine: Computational Insight into a Boron–Boron Frustrated Lewis Pair

Recent progress in frustrated Lewis pairs (FLPs) has attracted increasing attention. However, most of the FLPs are composed of Lewis basic phosphines and Lewis acidic boranes. In 2015, Kinjo and co-workers reported the first intramolecular boron–boron FLP, namely, 1,3,2,5-diazadiborinine (1), which showed high regioselectivity in the reactions with methyl trifluoromethansulfonate, phenylacetylene, and CO2. More interestingly, the activation of CO2 was found to be reversible when the temperature was elevated to 90 °C.

Mechanistic Insight into the Copper-Catalyzed Phosphorylation of Terminal Alkynes: A Combined Theoretical and Experimental Study

The reaction mechanism of copper-catalyzed phosphorylation of terminal alkynes under different conditions has been investigated experimentally and theoretically. The important role of dioxygen has been elucidated, including the formation of η1-superoxocopper(II), η2-superoxocopper(III), μ-η2:η2-peroxodicopper(II), and bis(μ-oxo)dicopper(III) complexes.

Mechanism, Reactivity, and Selectivity in Rh(III)-Catalyzed Phosphoryl-Directed Oxidative C–H Activation/Cyclization: A DFT Study

Density functional theory calculations (DFT) have been performed on Rh(III)-catalyzed phosphoryl-directed oxidative C–H activation/cyclization to investigate the detailed mechanism, including four basic steps: C–H activation, alkyne insertion, reductive elimination, and catalyst recycling, each of which consists of different steps. Interestingly, the Rh(III)–AgOAc catalyst system was found to be more favorable in the C–H activation step in comparison with the Rh(III)–Ag2CO3 system, whereas the Rh(I)–Ag2CO3 catalyst system was more efficient for catalyst recycling.

Double Role of the Hydroxy Group of phosphoryl in Palladium(II)-catalyzed ortho-Olefination: A Combined Experimental and Theoretical Investigation

Density functional theory (DFT) calculations have been carried out on Pd-catalyzed phosphoryl-directed ortho-olefination to probe the origin of the significant reactivity difference between methyl hydrogen benzylphosphonates and dialkyl benzylphosphonates. The overall catalytic cycle is found to include four basic steps: C−H bond activation, transmetalation, reductive elimination and recycling of catalyst, each of which is constituted from different steps.

Requirement for an oxidant in Pd/Cu co-catalyzed terminal alkyne homocoupling give symmetrical 1,4-disubstituted 1,3-diynes

Palladium-catalyzed terminal alkyne dimerization, through oxidative homocoupling, is a useful approach to the synthesis of symmetrical 1,4-diynes. Recent investigations have suggested that this reaction might be accomplished in the absence of intentionally added stoichiometric oxidants (to reoxidize Pd(0) to Pd(II)). In this paper, we have fully addressed the question of whether oxygen (or added oxidant) is required to facilitate this process. The presence of a stoichiometric quantity of air (or added oxidant such as I2) is essential for alkyne dimerization.