Modulation of metal species as control point for Ni-catalyzed stereodivergent semihydrogenation of alkynes with water

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: March 24, 2023

A base-assisted metal species modulation mechanism enables Ni-catalyzed stereodivergent transfer semihydrogenation of alkynes with water, delivering both olefinic isomers smoothly using cheap and nontoxic catalysts additives. Different from most precedents, in which E-alkenes derive the isomerization Z-alkene products, were formed orthogonal catalytic pathways. Mechanistic studies suggest base as a key early element reaction pathways: by adding different bases, nickel disparate valence states could be accessed to initiate two cycles toward stereoisomers. The practicability method is showcased nearly 70 examples, including internal terminal triple bonds, enynes diynes, affording semi-hydrogenated products high yields selectivity.

Language: Английский

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Testing Differently Substituted Quinoxaline‐2,3‐Dithiolate Ligands in Z‐Stereoretentive Olefin Metathesis Leading to Pheromone of Rice Yellow Stem Borer (Scirpophaga incertulas)

European Journal of Lipid Science and Technology, Journal Year: 2025, Volume and Issue: unknown

Published: March 23, 2025

ABSTRACT Stereoselective olefin metathesis offers access to geometrically well‐defined C–C double bonds and is considered a promising new method for transforming plant oils valuable chemicals. A set of Z ‐stereoretentive catalysts bearing quinoxaline‐2,3‐dithiolate ligands functionalized with halogens, electron‐withdrawing (EWG), electron‐donating (EDG), π‐altered were obtained characterized. New tested in model ‐stereoselective cross‐metathesis (CM) the synthesis pheromone rice yellow stem borer ( Scirpophaga incertulas ). Although none surpassed parent catalyst Ru5a —featuring non‐substituted ligand—the ester‐substituted complex Ru5h offered similarly high level ‐selectivity (>95:5) productivity, whereas carboxylic ester function can open perspectives future immobilization or polar‐tagging. Practical Applications : Decreasing availability fossil organic feedstock current policies European Union drive scientists look alternative sustainable sources fine In this context, preferential One them sex pheromones various insects—biodegradable non‐toxic chemical substances—used small amounts lure insects into traps. present work, female ) was yield selectivity, showing possible application newly field modern environmentally conscious farming.

Language: Английский

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Renaissance in Alkyne Semihydrogenation: Mechanism, Selectivity, Functional Group Tolerance, and Applications in Organic Synthesis

Chemical Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: April 25, 2025

Alkenes constitute a significant class of chemical compounds with applications in the bulk, pharmaceutical, or perfume industry. Among known methods olefin production, semihydrogenation C-C triple bond seems to be most straightforward one. Nonetheless, success this reaction requires full control over diastereoselectivity, eradication parasitic process over-reduction migration double formed, and achieving satisfactory functional-group compatibility. The review demonstrates developments field alkyne period 2010-2022, selected papers published 2023 2024, emphasizing solutions above-mentioned limitations. We discuss mechanistic aspects transformation, including those related unconventional systems. includes examples organic synthesis, confirming considerable utility process. Finally, strategies enhance catalyst selectivity are summarized. For reader's convenience, we provided graphical guidebook catalytic systems, illustrating efficiency particular method.

Language: Английский

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Efficient (Z)-selective semihydrogenation of alkynes catalyzed by air-stable imidazolyl amino molybdenum cluster sulfides

Inorganic Chemistry Frontiers, Journal Year: 2023, Volume and Issue: 10(6), P. 1786 - 1794

Published: Jan. 1, 2023

Efficient protocols for the semihydrogenation of internal alkynes and terminal alkynols are reported using new [Mo 3 S 4 Cl (ImNH 2 ) ] + complex as catalyst.

Language: Английский

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Unraveling the Role of Silyl and Silane in Si–Ni Catalysts for Hydrogenation

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(19), P. 13008 - 13020

Published: Sept. 21, 2023

Transition-metal complexes with Si–M bonds are important catalysts for hydrosilylation and hydrogenation reactions. However, the function of ligated silicon atom in organosilicon metal remains unknown. Herein, we unravel intriguing role silyl silane types active modes Si–Ni complex-catalyzed selective alkyne. Comprehensive density functional theory calculations were performed to investigate nickel hydride insertion, migration, H2 metathesis, oxidative addition mechanisms. The results suggest that species display distinct catalytic properties reaction. During alkyne, Ni–H insertion heavily relies on highly silyl–nickel intermediate. Conversely, stilbene, driving force is oxidation Ni(0) center silane–nickel revealed roles as during catalysis well explained E/Z stereoselectivity chemoselectivity between olefin product alkane Si–Ni-catalyzed Furthermore, explored structure–activity relationship bifunctional sites incorporate group IVA elements (C, Si, Ge, Sn). Hydrogenation both alkynes olefins can be accomplished via analogous silyl– silane–metal transformations. Our theoretical study provides valuable insights into mechanism would helpful future catalyst design ligands containing elements.

Language: Английский

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Prediction of Catalytic Performance of Metal Oxide Catalysts for Alkyne Hydrogenation Reaction Based on Machine Learning

Applied Catalysis A General, Journal Year: 2024, Volume and Issue: unknown, P. 119969 - 119969

Published: Sept. 1, 2024

Language: Английский

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CO₂ promoted photoredox/Ni-catalyzed semi-reduction of alkynes with H₂O

Green Chemistry, Journal Year: 2023, Volume and Issue: 25(20), P. 7978 - 7982

Published: Jan. 1, 2023

CO 2 -promoted photoredox/Ni dual catalyzed semi-reduction of alkynes with water has been developed, which provides a method for the synthesis Z -alkenes in high yields stereoselectivity under mild conditions.

Language: Английский

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From trials on rosuvastatin production waste valorization to development of new catalytic methods for Z → E isomerization of alkenes

New Journal of Chemistry, Journal Year: 2024, Volume and Issue: 48(11), P. 4976 - 4981

Published: Jan. 1, 2024

A convenient method for Z → E geometry isomerization of aryl–aryl (stilbenes), alkyl–aryl, and alkyl–alkyl alkenes was developed.

Language: Английский

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Solvent-controlled diastereoselectivity of alkyne semihydrogenation

Chem Catalysis, Journal Year: 2024, Volume and Issue: 4(9), P. 101114 - 101114

Published: Sept. 1, 2024

Language: Английский

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Never too late: Stereoselective alkyne semi-hydrogenation by Ir catalysis

Chem Catalysis, Journal Year: 2022, Volume and Issue: 2(6), P. 1245 - 1246

Published: June 1, 2022

Language: Английский

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