CS2/KOH System-Promoted Stereoselective Synthesis of (E)-Alkenes from Diarylalkynes and a “Hidden” Zinin-Type Reduction of Nitroarenes into Arylamines DOI
Douglas B. Paixão,

Eduardo G. O. Soares,

Caren Daniele Galeano da Silva

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(24), P. 17037 - 17046

Published: Nov. 27, 2023

In this work, we present the CS2/KOH system as a practical and efficient reductive medium for obtaining (E)-alkenes from alkynes through highly stereoselective semireduction reaction. This cost-effective enabled successful reactions of diverse using water hydrogen source, yielding moderate to excellent yields. The versatility protocol is further demonstrated synthesis relevant compounds such pinosylvin resveratrol precursors, along with notable anticancer agent DMU-212. Furthermore, during reaction scope investigation, serendipitously disclosed that was also able promote Zinin-type reduce nitroarenes into arylamines.

Language: Английский

Metal–organic frameworks for organic transformations by photocatalysis and photothermal catalysis DOI
Hong‐Guang Jin, Pengcheng Zhao, Yunyang Qian

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(18), P. 9378 - 9418

Published: Jan. 1, 2024

Organic transformation by light-driven catalysis, especially, photocatalysis and photothermal denoted as photo(thermal) is an efficient, green, economical route to produce value-added compounds. In recent years, owing their diverse structure types, tunable pore sizes, abundant active sites, metal-organic framework (MOF)-based catalysis has attracted broad interest in organic transformations. this review, we provide a comprehensive systematic overview of MOF-based for First, the general mechanisms, unique advantages, strategies improve performance MOFs are discussed. Then, outstanding examples transformations over introduced according reaction type. addition, several representative advanced characterization techniques used revealing charge kinetics intermediates presented. Finally, prospects challenges field proposed. This review aims inspire rational design development materials with improved catalysis.

Language: Английский

Citations

51

Single‐Atom Nickel on Carbon Nitride Photocatalyst Achieves Semihydrogenation of Alkynes with Water Protons via Monovalent Nickel DOI
Tongtong Jia, Di Meng, Ran Duan

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(9)

Published: Jan. 10, 2023

Prospects in light-driven water activation have prompted rapid progress hydrogenation reactions. We describe a Ni2+ -N4 site built on carbon nitride for catalyzed semihydrogenation of alkynes, with supplying protons, powered by visible-light irradiation. Importantly, the photocatalytic approach developed here enabled access to diverse deuterated alkenes D2 O excellent deuterium incorporation. Under irradiation, evolution four-coordinate species into three-coordinate Ni+ was spectroscopically identified. In combination theoretical calculations, photo-evolved is posited as HO-Ni+ -N2 an uncoordinated, protonated pyridinic nitrogen, formed coupled reduction and dissociation. The paired Ni-N prompts hydrogen liberation from water, it renders desorption alkene preferred over further alkane, ensuring selectivity.

Language: Английский

Citations

39

Stereoselective Semi‐Hydrogenations of Alkynes by First‐Row (3d) Transition Metal Catalysts DOI Creative Commons
Bernhard J. Gregori, Mattis‐Ole W. S. Schmotz, Axel Jacobi von Wangelin

et al.

ChemCatChem, Journal Year: 2022, Volume and Issue: 14(20)

Published: Aug. 26, 2022

The chemo- and stereoselective semi-hydrogenation of alkynes to alkenes is a fundamental transformation in synthetic chemistry, for which the use precious 4d or 5d metal catalysts well-established. In mankind's unwavering quest sustainability, research focus has considerably veered towards 3d metals. Given their high abundancy availability as well lower toxicity noxiousness, they are undoubtedly attractive from both an economic environmental perspective. Herein, we wish present noteworthy groundbreaking examples diastereoselective alkyne embark on journey through first-row transition

Language: Английский

Citations

30

Cooperative H2 activation at a nickel(0)–olefin centre DOI
María L. G. Sansores‐Paredes, Martin Lutz, Marc‐Etienne Moret

et al.

Nature Chemistry, Journal Year: 2023, Volume and Issue: 16(3), P. 417 - 425

Published: Dec. 5, 2023

Language: Английский

Citations

16

Recent advances in the selective semi-hydrogenation of alkyne to (E)-olefins DOI

Motahar Sk,

Shuvojit Haldar,

Sourajit Bera

et al.

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(12), P. 1517 - 1533

Published: Jan. 1, 2024

This article highlights the recent advances on newer technologies and important methodologies directed to ( E )-olefins from alkynes.

Language: Английский

Citations

5

Spin-Crossing in the (Z)-Selective Alkyne Semihydrogenation Mechanism Catalyzed by Mo3S4 Clusters: A Density Functional Theory Exploration DOI Creative Commons
María Gutiérrez‐Blanco, Andrés G. Algarra, Eva Guillamón

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(2), P. 1000 - 1009

Published: Jan. 4, 2024

Semihydrogenation of internal alkynes catalyzed by the air-stable imidazolyl amino [Mo

Language: Английский

Citations

4

Single‐Atom Nickel on Carbon Nitride Photocatalyst Achieves Semihydrogenation of Alkynes with Water Protons via Monovalent Nickel DOI
Tongtong Jia, Di Meng, Ran Duan

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(9)

Published: Jan. 10, 2023

Abstract Prospects in light‐driven water activation have prompted rapid progress hydrogenation reactions. We describe a Ni 2+ −N 4 site built on carbon nitride for catalyzed semihydrogenation of alkynes, with supplying protons, powered by visible‐light irradiation. Importantly, the photocatalytic approach developed here enabled access to diverse deuterated alkenes D 2 O excellent deuterium incorporation. Under irradiation, evolution four‐coordinate species into three‐coordinate + was spectroscopically identified. In combination theoretical calculations, photo‐evolved is posited as HO−Ni an uncoordinated, protonated pyridinic nitrogen, formed coupled reduction and dissociation. The paired Ni−N prompts hydrogen liberation from water, it renders desorption alkene preferred over further alkane, ensuring selectivity.

Language: Английский

Citations

10

New reactivity of late 3d transition metal complexes in catalytic reactions of alkynes DOI
Shenghan Teng,

Peiyao Liang,

Jianrong Steve Zhou

et al.

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

Published: Jan. 1, 2025

This review summarizes seven types of new reactivities found in late 3d metal complexes and catalytic examples recent years.

Language: Английский

Citations

0

Electrochemical cobalt-catalyzed semi-deuteration of alkynes to access deuterated Z-alkenes DOI Creative Commons

Wen-Jie Feng,

Zhe Chang, Xi Lu

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: March 10, 2025

Abstract Deuterium labeling has found extensive applications across various research fields, including organic synthesis, drug design, and molecular imaging. Electrocatalytic semi-hydrogenation of alkynes offers a viable route for the synthesis Z -alkenes, yet it falls short in achieving semi-deuteration these compounds. In this study, we report an electrochemical cobalt-catalyzed transfer deuteration reaction that proficiently accomplishes alkynes, yielding -configuration deuterated alkene products. This utilizes cost-effective cobalt salts as catalysts employs D 2 O AcOD (acetic acid- d ) economical efficient deuterium sources, underscoring its practicality feasibility. The demonstrates broad alkyne substrate scope, high efficiency, good functional group compatibility, excellent -selectivity, remarkable degree rate.

Language: Английский

Citations

0

Selective Semi‐Hydrogenation of Acetylene using a Single‐Atom Cobalt on Carbon Nitride Photocatalyst with Water as a Proton Source DOI Creative Commons
Anna Fortunato, Daniele Perilli,

Alexandru Dron

et al.

Small Methods, Journal Year: 2025, Volume and Issue: unknown

Published: May 19, 2025

Abstract Light‐powered strategies for the semi‐hydrogenation of acetylene to ethylene are rapidly emerging as sustainable alternatives traditional thermochemical processes. The development a robust, selective, well recyclable, non‐noble catalyst that can be powered by visible light and uses water proton source accomplish this important reaction remains key challenge. Here first demonstration cobalt single‐atom supported on carbon‐nitride (Co−CN) an all‐in‐one photocatalyst is reported using source, offering advantages over current hydrogenation technologies. Carbon nitride hosts individual catalytic active sites thus combining photosensitizer cocatalyst in one unit, line with first‐principles modelling. Under irradiation, Co−CN reduces stable activity 40 days continuous operation, ≥99.9% selectivity, provides means coupling organic upgrading produce valuable oxidation products. heterogeneous easily recovered reused repeatedly without loss structural integrity. Thereby, integrated recyclable platform overcomes need separate catalyst, noble metal catalysts external H 2 gas feed.

Language: Английский

Citations

0