Sustainable catalysis with fluxional acridine-based PNP pincer complexes DOI Creative Commons
Sayan Kar, David Milstein

Chemical Communications, Journal Year: 2022, Volume and Issue: 58(23), P. 3731 - 3746

Published: Jan. 1, 2022

Because of the widespread use fossil fuels and resulting global warming, development sustainable catalytic transformations is now more important than ever to obtain our desired building materials with least carbon footprint waste production. Many (de)hydrogenation reactions, including CO2 reduction, H2 carrier systems, others, have been reported using molecular pincer complexes. A specific subset complexes containing a central acridine donor flanking CH2PR2 ligands, known as acridine-based PNP complexes, exhibit special reactivities that are not imitable by other such pyridine-based or (R2PCH2CH2)2NH type ligands. The goal this article highlight unique then investigate how these allow catalyse many reactions traditional cannot catalyse. To end, we will initially go over synthesis structural features labile coordination N observed fac-mer fluxionality. Following that, distinct reactivity patterns their acids water be discussed. Finally, discuss reaction systems developed thus far, notable selective primary alcohols amines ammonia, N-heteroaromatic from oxidation liberation, conclude future possible directions. We hope systemic study presented here aid researchers in developing further based on

Language: Английский

Strategies and mechanisms of metal–ligand cooperativity in first-row transition metal complex catalysts DOI
Matthew R. Elsby, R. Tom Baker

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(24), P. 8933 - 8987

Published: Jan. 1, 2020

The use of metal–ligand cooperation (MLC) by transition metal bifunctional catalysts has emerged at the forefront homogeneous catalysis science.

Language: Английский

Citations

240
First-Row d-Block Element-Catalyzed Carbon–Boron Bond Formation and Related Processes DOI
Shubhankar Kumar Bose, Lujia Mao,

Laura Kuehn

et al.

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(21), P. 13238 - 13341

Published: Oct. 7, 2021

Organoboron reagents represent a unique class of compounds because their utility in modern synthetic organic chemistry, often affording unprecedented reactivity. The transformation the carbon–boron bond into carbon–X (X = C, N, and O) stereocontrolled fashion has become invaluable medicinal agrochemistry, natural products chemistry as well materials science. Over past decade, first-row d-block transition metals have increasingly widely used catalysts for formation bond, traditionally catalyzed by expensive precious metals. This recent focus on alternative enabled growth fundamental methods organoboron chemistry. review surveys current state-of-the-art use element-based bonds.

Language: Английский

Citations

238
Development of a practical non-noble metal catalyst for hydrogenation of N-heteroarenes DOI
Veronica Papa, Yi-Xuan Cao,

Anke Spannenberg

et al.

Nature Catalysis, Journal Year: 2020, Volume and Issue: 3(2), P. 135 - 142

Published: Jan. 6, 2020

Language: Английский

Citations

155
Cobalt‐Catalyzed Asymmetric Hydrogenation of C=N Bonds Enabled by Assisted Coordination and Nonbonding Interactions DOI
Yanhua Hu, Zhenfeng Zhang, Jian Zhang

et al.

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(44), P. 15767 - 15771

Published: Aug. 29, 2019

An efficient cobalt-catalyzed asymmetric hydrogenation of C=N bonds has been realized. Chiral hydrazines were obtained in high yields and with excellent enantioselectivities (95-98 % ee). The went smoothly at up to 2000 substrate/catalyst on a gram scale. success this reaction relies the presence an NHBz group substrates, reactivity enantioselectivity improved by assisted coordination cobalt atom nonbonding interaction ligand. Furthermore, practical applications for synthesis several useful chiral nitrogen-containing compounds.

Language: Английский

Citations

100
Recent Progress with Pincer Transition Metal Catalysts for Sustainability DOI Open Access
Luca Piccirilli, Danielle L. J. Pinheiro, Martin Nielsen

et al.

Catalysts, Journal Year: 2020, Volume and Issue: 10(7), P. 773 - 773

Published: July 11, 2020

Our planet urgently needs sustainable solutions to alleviate the anthropogenic global warming and climate change. Homogeneous catalysis has potential play a fundamental role in this process, providing novel, efficient, at same time eco-friendly routes for both chemicals energy production. In particular, pincer-type ligation shows promising properties terms of long-term stability selectivity, as well allowing mild reaction conditions low catalyst loading. Indeed, pincer complexes have been applied plethora chemical processes, such hydrogen release, CO2 capture conversion, N2 fixation, biomass valorization synthesis high-value fuels. work, we show main advances last five years use transition metal key catalytic processes aiming more

Language: Английский

Citations

97
Emergence and Applications of Base Metals (Fe, Co, and Ni) in Hydroboration and Hydrosilylation DOI Creative Commons

Sem Raj Tamang,

Michael Findlater

Molecules, Journal Year: 2019, Volume and Issue: 24(17), P. 3194 - 3194

Published: Sept. 3, 2019

Base metal catalysis offers an alternative to reactions, which were once dominated by precious metals in hydrofunctionalization reactions. This review article details the development of some base (Fe, Co, and Ni) hydroboration hydrosilylation reactions concomitant with a brief overview recent advances field. Applications both commercially available salts well-defined complexes opportunities further advance field is discussed as well.

Language: Английский

Citations

92
Cobalt‐Catalyzed Aqueous Dehydrogenation of Formic Acid DOI Creative Commons
Wei Zhou, Zhihong Wei,

Anke Spannenberg

et al.

Chemistry - A European Journal, Journal Year: 2019, Volume and Issue: 25(36), P. 8459 - 8464

Published: April 2, 2019

Among the known liquid organic hydrogen carriers, formic acid attracts increasing interest in context of safe and reversible storage hydrogen. Here, first molecularly defined cobalt pincer complex is disclosed for dehydrogenation aqueous medium under mild conditions. Crucial catalytic activity use specific 3. Compared to related ruthenium manganese complexes 7 8, this optimal showed improved performance. DFT computations support an innocent non-classical bifunctional outer-sphere mechanism on triplet state potential energy surface.

Language: Английский

Citations

77
Cobalt-catalyzed dehydrogenative functionalization of alcohols: Progress and future prospect DOI
Ishani Borthakur,

Anirban Sau,

Sabuj Kundu

et al.

Coordination Chemistry Reviews, Journal Year: 2021, Volume and Issue: 451, P. 214257 - 214257

Published: Oct. 28, 2021

Language: Английский

Citations

77
Selective Catalytic Synthesis of α-Alkylated Ketones and β-Disubstituted Ketones via Acceptorless Dehydrogenative Cross-Coupling of Alcohols DOI

Dipanjan Bhattacharyya,

Bikash Kumar Sarmah,

Sekhar Nandi

et al.

Organic Letters, Journal Year: 2021, Volume and Issue: 23(3), P. 869 - 875

Published: Jan. 21, 2021

Herein, a phosphine-free pincer ruthenium(III) catalyzed β-alkylation of secondary alcohols with primary to α-alkylated ketones and two different β-branched are reported. Notably, this transformation is environmentally benign atom efficient H2O H2 gas as the only byproducts. The protocol extended gram-scale reaction for functionalization complex vitamin E cholesterol derivatives.

Language: Английский

Citations

58
Divergent Synthesis of Alcohols and Ketones via Cross‐Coupling of Secondary Alcohols under Manganese Catalysis DOI

Feixiang Sun,

Jiamin Huang,

Zhihong Wei

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(26)

Published: April 21, 2023

A homogeneous manganese-catalyzed cross-coupling of two secondary alcohols for the divergent synthesis γ-disubstituted and β-disubstituted ketones is reported. Employing well-defined Mn-MACHOPh as catalyst, this novel protocol has a broad substrate scope with good functional group tolerance affords diverse library valuable disubstituted in moderate to yields. The strong influence reaction temperature on selective formation alcohol products was theorized preliminary DFT studies. Studies have shown that Gibbs free energy thermodynamically more favourable than corresponding at lower temperature.

Language: Английский

Citations

31