Predicting Small Molecule Activation including Catalytic Hydrogenation of Dinitrogen Promoted by a Dual Lewis Acid DOI
Shicheng Dong, Jun Zhu

Chemistry - An Asian Journal, Journal Year: 2022, Volume and Issue: 18(1)

Published: Nov. 10, 2022

For decades, N2 activation and functionalization have required the use of transition metal complexes. Thus, it is one most challenging projects to activate abundant dinitrogen through metal-free systems under mild conditions. Here, we demonstrate a proof-of-concept study on catalytic hydrogenation (with energy as low 15.3 kcal mol-1 ) initiated by dual Lewis acid (DLA) via density functional theory (DFT) calculations. In addition, such DLA could be also used series small molecules including carbon dioxide, formaldehyde, N-ethylenemethylamine, acetonitrile. It found that aromaticity plays an important role in stabilizing intermediates products. Our findings provide alternative approach functionalization, highlighting great potential for molecule activation.

Language: Английский

Rhodium(I) Carbene‐Promoted Enantioselective C−H Functionalization of Simple Unprotected Indoles, Pyrroles and Heteroanalogues: New Mechanistic Insights DOI

Tian‐Yi Wang,

Xiao‐Xuan Chen,

Dong‐Xing Zhu

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(34)

Published: June 17, 2022

A rhodium(I)-diene catalyzed highly enantioselective C(sp2 )-H functionalization of simple unprotected indoles, pyrroles, and their common analogues such as furans, thiophenes, benzofurans with arylvinyldiazoesters has been developed for the first time. This transformation features unusual site-selectivity exclusively at vinyl terminus arylvinylcarbene enables a reliable rapid synthetic protocol to access distinctive class diarylmethine-bearing α,β-unsaturated esters containing one or two heteroarene-attached tertiary carbon stereocenter in high yields excellent enantioselectivities under mild reaction conditions. Mechanistic studies DFT calculations suggest that, compared aniline substrate, more electron-rich indole substrate lowers C-C addition barrier alters rate-determining step reductive elimination, leading different isotope effect.

Language: Английский

Citations

23
ReNeGate: A Reaction Network Graph-Theoretical Tool for Automated Mechanistic Studies in Computational Homogeneous Catalysis DOI Creative Commons
Ali Hashemi, Sana Bougueroua, Marie‐Pierre Gaigeot

et al.

Journal of Chemical Theory and Computation, Journal Year: 2022, Volume and Issue: 18(12), P. 7470 - 7482

Published: Nov. 2, 2022

Exploration of the chemical reaction space transformations in multicomponent mixtures is one main challenges contemporary computational chemistry. To remove expert bias from mechanistic studies and to discover new chemistries, an automated graph-theoretical methodology proposed, which puts forward a network formalism homogeneous catalysis reactions utilizes analysis tool for studies. The method can be used analyzing trajectories with single multiple catalytic species provide unique conformers catalysts including multinuclear catalyst clusters along other mixture components. presented three-step approach has integrated ability handle systems arbitrary complexity (mixtures reactants, precursors, ligands, additives, solvents). It not limited predefined rules, does require prealignment components consistent coordinate, agnostic nature transformations. Conformer exploration, reactive event identification, are steps taken identifying pathways given starting precatalytic as input. Such allows us efficiently explore realistic conditions either previously observed or completely unknown events context representing different intermediates. Our workflow exploration exclusively focuses on identification thermodynamically feasible conversion channels, representative (secondary) deactivation inhibition paths, usually most difficult anticipate based solely knowledge. Thus, sought removed at all steps, intuition choice thermodynamic constraint imposed by applicable experimental terms threshold energy values allowed capabilities proposed have been tested exploring reactivity Mn complexes relevant hydrogenation chemistry verify postulated activation mechanisms unravel unexpected channels rare events.

Language: Английский

Citations

23
Molecular Dynamics of Iron Porphyrin-Catalyzed C–H Hydroxylation of Ethylbenzene DOI
Zhang Ya-Ling,

Chaoqin Cao,

Yuanbin She

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(26), P. 14446 - 14455

Published: June 17, 2023

Quasi-classical molecular dynamics (MD) simulations were carried out to study the mechanism of iron porphyrin-catalyzed hydroxylation ethylbenzene. The hydrogen atom abstraction from ethylbenzene by iron-oxo species is rate-determining step, which generates radical pair iron-hydroxo and benzylic radical. In subsequent rebound recombine form hydroxylated product, barrierless on doublet energy surface. gas-phase quasi-classical MD surface, 45% reactive trajectories lead directly this increases 56% in implicit solvent model simulations. percentage leading separated 98-100% high-spin (quartet/sextet) surfaces. low-spin state reactivity dominates ethylbenzene, dynamically both concerted stepwise, since time gap between C-H bond cleavage C-O formation ranges 41 619 fs. By contrast, catalysis an energetically stepwise process, has a negligible contribution products.

Language: Английский

Citations

13
Electron-rich benzofulvenes as effective dipolarophiles in copper(i)-catalyzed asymmetric 1,3-dipolar cycloaddition of azomethine ylides DOI Creative Commons
Xin Chang,

Xue‐Tao Liu,

Fangfang Li

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(20), P. 5460 - 5469

Published: Jan. 1, 2023

A series of benzofulvenes without any electron-withdrawing substituents were employed as 2π-type dipolarophiles for the first time to participate in Cu(i)-catalyzed asymmetric 1,3-dipolar cycloaddition (1,3-DC) reactions azomethine ylides. An intrinsic non-benzenoid aromatic characteristic from serves a key driving force activation electron-rich benzofulvenes. Utilizing current methodology, wide range multi-substituted chiral spiro-pyrrolidine derivatives containing two contiguous all-carbon quaternary centers formed good yield with exclusive chemo-/regioselectivity and high excellent stereoselectivity. Computational mechanistic studies elucidate origin stereochemical outcome chemoselectivity, which thermostability these products is major factor.

Language: Английский

Citations

11
Asymmetric Cyclopropanation of Primary N-Vinylamides via Carbene Transfer Catalyzed by Cationic Rh(I)/Diene Complexes: An Unexpected Outer-Sphere Mechanism DOI
Junyou Zhang, Zhifeng Ma,

Weici Xu

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(12), P. 9385 - 9396

Published: June 6, 2024

A highly enantioselective intermolecular [2 + 1] cycloaddition of primary N-vinylamides with carbene intermediates was developed by taking advantage cationic rhodium(I)/diene catalysis under mild conditions at room temperature. This cyclopropanation method facilitates rapid access to enantioenriched cyclopropylamides, an important motif in drug discovery, generally good yields and high stereoselectivities (>20:1 dr, up 99% ee). approach employs a rhodium(I) catalyst form pre-equilibrium complex enamide substrate. Kinetic experiments comprehensive density functional theory (DFT) calculations were performed elucidate the reaction mechanism. The kinetic data DFT results support existence resting-state between two substrates. computational studies show that involves interesting, unexpected outer-sphere mechanistic pathway involving sole Rh(I) catalytic cycle major product reveal diazo decomposition step is rate-determining step.

Language: Английский

Citations

4
Structural and Computational Insights into the Noncanonical Aromatization in Fungal Polyketide Biosynthesis DOI
Hang Wang, Chao Peng, Xiaoxuan Chen

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(14), P. 10796 - 10805

Published: July 3, 2024

Language: Английский

Citations

4
Experimental and computational journey on transition-metal-catalyzed C H functionalization with fluorinated π-systems DOI
Zhongyi Zeng, Huiying Xu, Hui Gao

et al.

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 522, P. 216244 - 216244

Published: Sept. 24, 2024

Language: Английский

Citations

4
Asymmetric Synthesis of Vicinal Tetrasubstituted Diamines via Reductive Coupling of Ketimines Templated by Chiral Diborons DOI

Mingkang Zhou,

Yaodong Lin,

Xiao‐Xuan Chen

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(17)

Published: March 2, 2023

Abstract We herein describe the chiral diboron‐templated asymmetric homocoupling of aryl alkyl ketimines, providing for first time a series vicinal tetrasubstituted diamines with excellent ee values and good to high yields. The powerful efficient diboron‐participated [3,3]‐sigmatropic rearrangement is successfully demonstrated by variety ketimines thanks rational design engineering diborons. Systematic DFT studies suggest that two diborons adopt different conformational assembling strategies couple diboron template ketimine substrates in their tight concerted transition states ensure enantioselectivities. synthetic value α‐bromination aliphatic aldehydes employing diamine‐based organocatalyst.

Language: Английский

Citations

10
Catalytic Regio- and Enantioselective Hydroformylation of Trisubstituted Alkenes to Construct α-Quaternary Lactams DOI
Dequan Zhang,

Jianqiang Zheng,

Cai You

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: 147(9), P. 7886 - 7896

Published: Feb. 24, 2025

Developing novel stereoselective methods for α-quaternary lactams is of significant importance advancing structure-activity studies, discovering new antibiotics, and synthesizing diverse functional compounds synthetic materials research. Herein, we have successfully developed a Rh-catalyzed asymmetric hydroformylation (AHF) trisubstituted olefins, overcoming both the inherent inertness olefins in such reactions Keulemans' rule, efficiently generating β- γ-lactams bearing an stereocenter with exceptional regio- enantioselectivities (up to >20:1 rr, 99% ee). This mild operationally simple reaction proceeds atom-economic manner broad substrate scope, along excellent functional-group tolerance, scalability, product diversification. Computational studies suggest that enantio- and/or regioselectivity may originate from Rh-C bonding noncovalent interactions between Boc group on Ph groups ligand.

Language: Английский

Citations

0
Cheminformatic Analysis of Core-Atom Transformations in Pharmaceutically Relevant Heteroaromatics DOI
G. Logan Bartholomew, Lucas J. Karas,

Reilly M. Eason

et al.

Journal of Medicinal Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 7, 2025

Heteroaromatics are the basis for many pharmaceuticals. The ability to modify these structures through selective core-atom transformations, or "skeletal edits", can dramatically expand landscape drug discovery and development. However, despite importance of modifications, quantitative impact such transformations on accessible chemical space remains undefined. Here, we report a cheminformatic platform analyze which skeletal edits would most increase access novel space. This study underscores significance emerging single multiple heteroaromatics in enhancing diversity, example, at late-stage campaign. Our findings provide framework prioritizing modifications heteroaromatic structural motifs, calling development new methods achieve types transformations.

Language: Английский

Citations

0