Impact of the Methylene Bridge Substitution in Chelating NHC‐Phosphine Mn(I) Catalyst for Ketone Hydrogenation DOI Creative Commons

Ekaterina S. Gulyaeva,

Ruqaya Buhaibeh, Mohamed Boundor

et al.

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(22)

Published: Feb. 7, 2024

Abstract Systematic modification of the chelating NHC‐phosphine ligand (NHC = N ‐heterocyclic carbene) in highly efficient ketone hydrogenation Mn(I) catalyst fac ‐[(Ph 2 PCH NHC)Mn(CO) 3 Br] has been performed and catalytic activity resulting complexes was evaluated using acetophenone as a benchmark substrate. While variation phosphine NHC moieties led to inferior results than for parent system, incorporation phenyl substituent into methylene bridge improved performance by ca . times providing maximal TON values range 15000–20000. Mechanistic investigation combining experimental computational studies allowed rationalize this beneficial effect an enhanced stabilization reaction intermediates including anionic hydride species PC(Ph)NHC)Mn(CO) H] − playing crucial role process. These highlight interest such carbon substitution strategy being rarely employed design chemically non‐innocent ligands.

Language: Английский

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
Manganese(I)-catalyzed asymmetric (transfer) hydrogenation of ketones: An insight into the effect of chiral PNN and NN ligands DOI
Jitao Yang,

Lijun Yao,

Zheng Wang

et al.

Journal of Catalysis, Journal Year: 2023, Volume and Issue: 418, P. 40 - 50

Published: Jan. 7, 2023

Language: Английский

Citations

26
Unleashing the potentiality of metals: synergistic catalysis with light and electricity DOI
Zhengjia Shen, Jia‐Lin Tu, Binbin Huang

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(14), P. 4024 - 4040

Published: Jan. 1, 2024

This review provides a comprehensive overview of metal catalysis in photo-electrochemical systems, discussing reaction mechanisms and offering prospects for this triadic catalytic mode.

Language: Английский

Citations

13
Recent advances and emerging opportunities in mechanism and applications of earth abundant manganese-catalysts for sustainable organic transformations DOI

Naseem Ahmed

Journal of Organometallic Chemistry, Journal Year: 2024, Volume and Issue: 1009, P. 123071 - 123071

Published: Feb. 23, 2024

Language: Английский

Citations

12
Organometallic Mn(I) Complexes in Asymmetric Catalytic (Transfer) Hydrogenation and Related Transformations DOI Creative Commons
Dexin Fu, Zheng Wang, Qingbin Liu

et al.

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(14)

Published: March 7, 2024

Abstract Direct asymmetric hydrogenation (AH) and transfer (ATH) are among the most efficient approaches to produce chiral building blocks. Recently, these types of transformations have witnessed a shift towards use molecular catalysts based on earth‐abundant transition metals due their ready availability, economic advantage, novel properties. With particular regard manganese, catalyst development has seen both efficiency substrate scope in AH ATH greatly improved, with emergence large number well‐defined Mn‐complexes employed this field. The reaction includes C=O bonds, reduction C=N bonds reductive C=C bonds. Herein, our survey area focuses catalytic activity such complexes, versatility routes convert substrates target molecules. We consider collected findings article will be helpful reader by providing an insight into ligand design, thereby aiding future development. Moreover, review is aimed at highlighting remarkable progress made last seven years manganese complexes for enantioselective reduction.

Language: Английский

Citations

11
Cycloheptyl-fused-PNN-manganese catalyzed asymmetric transfer hydrogenation of ketones DOI
Zechen Wang, Shuo Zhang, Zhifeng Ma

et al.

Molecular Catalysis, Journal Year: 2024, Volume and Issue: 564, P. 114274 - 114274

Published: June 8, 2024

Language: Английский

Citations

11
Designing Cobalt(II) Complexes for Tandem Dehydrogenative Synthesis of Quinoline and Quinazoline Derivatives DOI

Debjyoti Pal,

Avijit Mondal,

Rajashri Sarmah

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(2), P. 514 - 518

Published: Jan. 9, 2024

In this work, we have constructed three new Co(II) complexes in which steric features govern their structural geometry. The metal ligand-cooperation behavior of the alkoxy arm is utilized to explore catalytic activities these with respect dehydrogenation. A wide range C-3-substituted quinoline and quinazoline derivatives were synthesized high yields. developed protocol's usefulness enhanced by chemoselective transformation different fatty alcohols synthesize heterocycles having distal unsaturation. Various kinetic, mechanistic, control studies conducted comprehend reaction route.

Language: Английский

Citations

10
Manganese‐Catalyzed Mono‐N‐Methylation of Aliphatic Primary Amines without the Requirement of External High‐Hydrogen Pressure DOI

Jiale Ji,

Yinghao Huo,

Zhaowen Dai

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(13)

Published: Feb. 1, 2024

Abstract The synthesis of mono‐ N ‐methylated aliphatic primary amines has traditionally been challenging, requiring noble metal catalysts and high‐pressure H 2 for achieving satisfactory yields selectivity. Herein, we developed an approach the selective coupling methanol amines, without hydrogen, using a manganese‐based catalyst. Remarkably, up to 98 % with broad substrate scope were achieved at low catalyst loadings. Notably, due weak base‐catalyzed alcoholysis formamide intermediates, our novel protocol not only obviates addition but also prevents side secondary ‐methylation, supported by control experiments density functional theory calculations.

Language: Английский

Citations

10
Chemoselective Hydrogenation of α,β-Unsaturated Ketones Catalyzed by a Manganese(I) Hydride Complex DOI Creative Commons
Kartick Dey, Graham de Ruiter

Organic Letters, Journal Year: 2024, Volume and Issue: 26(20), P. 4173 - 4177

Published: May 13, 2024

Here, we report the chemoselective hydrogenation of α,β-unsaturated ketones catalyzed by a well-defined Mn(I) PCNHCP pincer complex [(PCNHCP)Mn(CO)2H] (1). The reaction is compatible with wide variety functional groups that include halides, esters, amides, nitriles, nitro, alkynes, and alkenes, for most substrates occurs readily at ambient hydrogen pressure (1–2 bar). Mechanistic studies deuterium labeling experiments reveal non-cooperative mechanism, which further discussed in this report.

Language: Английский

Citations

10
Manganese Alkyl Carbonyl Complexes: From Iconic Stoichiometric Textbook Reactions to Catalytic Applications DOI Creative Commons
Stefan Weber, Karl Kirchner

Accounts of Chemical Research, Journal Year: 2022, Volume and Issue: 55(18), P. 2740 - 2751

Published: Sept. 8, 2022

ConspectusThe activation of weakly polarized bonds represents a challenging, yet highly valuable process. In this context, precious metal catalysts have been used as reliable compounds for the rather inert last several decades. Nevertheless, base-metal complexes including cobalt, iron, or nickel are currently promising candidates substitution noble metals in order to develop more sustainable processes. past few years, manganese(I)-based were heavily employed efficient (de)hydrogenation reactions. However, vast majority these operate via metal–ligand bifunctionality already well implemented decades ago. Although high reactivity can be achieved various reactions, concept is often not applicable certain transformations due outer-sphere mechanisms. Account, we outline potential alkylated Mn(I)-carbonyl nonpolar and moderately polar E–H (E = H, B, C, Si) disclose our successful approach utilization field homogeneous catalysis. This involves rational design manganese hydrogenation reactions involving ketones, nitriles, carbon dioxide, alkynes. addition that, reduction alkenes by dihydrogen could series well-defined which was possible before. Furthermore, elucidate Mn-based hydrofunctionalization carbon–carbon multiple bonds. Our investigations unveiled novel insights into reaction pathways dehydrogenative silylation trans-1,2-diboration terminal alkynes, reported transition metals. Due catalyst design, under mild conditions. Delightfully, all bench-stable compounds. We took advantage fact that Mn(I) alkyl known undergo migratory insertion group CO ligand, yielding an unsaturated acyl intermediate. Hydrogen atom abstraction ligand then paves way active species variety catalytic proceed inner-sphere textbook well-known decades, application still its infancy. A brief historical overview manganese(I)–carbonyl provided, covering synthesis especially iconic stoichiometric transformations, e.g., carbonylation, intensively examined Calderazzo, Moss, others. An future applications defined will given, may inspire researchers development (base-)metal catalysts.

Language: Английский

Citations

32