Organic Process Research & Development, Год журнала: 2024, Номер unknown
Опубликована: Дек. 7, 2024
As the field of nonprecious metal catalysis continues to expand, we pursue a review series covering selected transformations in this area over short time interval highlight practical advancements. We seek raise awareness both current art and need continue development toward broader applications earth-abundant metals chemical pharmaceutical industries.
Язык: Английский
Chemical Communications, Год журнала: 2024, Номер unknown
Опубликована: Янв. 1, 2024
Nickel-catalysed chlorination of aryl halides and triflates has been developed with magnesium chloride, which promoted the challenging reductive elimination from Ni( ii ) intermediates.
Язык: Английский
Процитировано
1
Journal of the American Chemical Society, Год журнала: 2024, Номер 146(46), С. 32135 - 32146
Опубликована: Ноя. 11, 2024
This manuscript details the development of an asymmetric variant for Ni-photoredox α-arylation tetrahydrofuran (THF), which was originally reported in a racemic fashion by Doyle and Molander. Leveraging enantioselectivity data that we obtained, complex mechanistic scenario different from those proposed is uncovered. Specifically, unexpected dependence product enantiomeric ratio observed on both halide identity (aryl chloride vs bromide substrates) Ni source. Stoichiometric experiments time course analyses evolution with revealed initial behavior reactions carried out Ni(II) Ni(0) precatalysts later converge into common mechanism. For studying predominant pathway, this paper describes rare example syntheses chiral bisoxazoline aryl complexes, proved essential probing via stochiometric experiments. These identify as primary species involved key THF radical trapping event. A multivariate linear regression model presented further validates dominant mechanism delineates structure-selectivity relationships between ligand properties enantioselectivity. EPR analysis Ni(0)/aryl mixtures highlights fast access to variety complexes 0, +1, +2 oxidation states are be responsible divergence when using precatalysts. More broadly, beyond advancing understanding arylation protocol, work underscores potential leveraging unravel intricate manifolds within catalysis.
Язык: Английский
Процитировано
1
Angewandte Chemie, Год журнала: 2024, Номер 136(48)
Опубликована: Сен. 12, 2024
Abstract Bidentate N ‐ligands are paramount to recent advances in nickel‐catalyzed cross‐coupling reactions. Through comprehensive organometallic, spectroscopic, and computational studies on bi‐oxazoline imidazoline ligands, we reveal that a square planar geometry enables redox activity of these ligands stabilizing nickel radical species. This finding contrasts with the prior assumption lacks due strong mesomeric donation. Moreover, conducted systematic cyclic voltammetry (CV) analyses bidentate pyridyl, oxazoline, nitrogen along their corresponding complexes. Complexation shifts reduction potentials more positive region narrows differences among ligands. Additionally, various led different degrees bromide dissociation from singly reduced (L)Ni(Ar)(Br) complexes, reflecting varying reactivity subsequent activation alkyl halides, crucial step cross‐electrophile coupling. These insights highlight significant electronic effects stability metalloradical species potentials, which interplay coordination geometry. Quantifying electron‐donating, π‐accepting properties as well effect catalyst speciation, provides benchmarks for controlling catalytic enhancing stability.
Язык: Английский
Процитировано
0
Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(48)
Опубликована: Сен. 12, 2024
Abstract Bidentate N ‐ligands are paramount to recent advances in nickel‐catalyzed cross‐coupling reactions. Through comprehensive organometallic, spectroscopic, and computational studies on bi‐oxazoline imidazoline ligands, we reveal that a square planar geometry enables redox activity of these ligands stabilizing nickel radical species. This finding contrasts with the prior assumption lacks due strong mesomeric donation. Moreover, conducted systematic cyclic voltammetry (CV) analyses bidentate pyridyl, oxazoline, nitrogen along their corresponding complexes. Complexation shifts reduction potentials more positive region narrows differences among ligands. Additionally, various led different degrees bromide dissociation from singly reduced (L)Ni(Ar)(Br) complexes, reflecting varying reactivity subsequent activation alkyl halides, crucial step cross‐electrophile coupling. These insights highlight significant electronic effects stability metalloradical species potentials, which interplay coordination geometry. Quantifying electron‐donating, π‐accepting properties as well effect catalyst speciation, provides benchmarks for controlling catalytic enhancing stability.
Язык: Английский
Процитировано
0
ACS Catalysis, Год журнала: 2024, Номер 14(21), С. 16297 - 16312
Опубликована: Окт. 21, 2024
Ligand engineering is one of the most important, but labor-intensive processes in development transition metal catalysis. Historically, this process has been guided by ligand descriptors such as Tolman's electronic parameter and cone angle. Analyzing reaction outcomes terms these parameters enabled chemists to identify important properties for controlling catalytic pathways thus designing better ligands. However, typical strategies analyses rely on regression approaches, which often require extensive experimental studies trends across chemical space understand outliers. Here, we introduce virtual ligand-assisted optimization (VLAO) method, a computational approach reactivity-directed engineering. In features ligands are identified simple mathematical operations equilibrium structures and/or states interest, derivative values arbitrary objective functions with respect obtained. These then used guiding principle optimize within space. The VLAO method was demonstrated monodentate bidentate phosphine including asymmetric quinoxaline-based addition, successfully found an optimal α-selective hydrogermylation terminal ynamide, applying design suggested method. results highlight practical utility potential directed wide variety
Язык: Английский
Процитировано
0
The Chemical Record, Год журнала: 2024, Номер unknown
Опубликована: Ноя. 5, 2024
Abstract Advancements in synthetic organic chemistry are closely related to understanding substrate and catalyst reactivities through detailed mechanistic studies. Traditional investigations labor‐intensive rely on experimental kinetic, thermodynamic, spectroscopic data. Linear free energy relationships (LFERs), exemplified by Hammett relationships, have long facilitated reactivity prediction despite their inherent limitations when using constants or incorporating comprehensive Data‐driven modeling, which integrates cheminformatics with machine learning, offers powerful tools for predicting interpreting mechanisms effectively handling complex multiparameter strategies. This review explores selected examples of data‐driven strategies investigating reaction mechanisms. It highlights the evolution application computational descriptors inference.
Язык: Английский
Процитировано
0
Organic Process Research & Development, Год журнала: 2024, Номер unknown
Опубликована: Дек. 7, 2024
As the field of nonprecious metal catalysis continues to expand, we pursue a review series covering selected transformations in this area over short time interval highlight practical advancements. We seek raise awareness both current art and need continue development toward broader applications earth-abundant metals chemical pharmaceutical industries.
Язык: Английский
Процитировано
0