Room temperature chemoselective hydrogenation of CC, CO and CN bonds by using a well-defined mixed donor Mn(<scp>i</scp>) pincer catalyst

Shabade, Anand B.; Sharma, Dipesh M.; Bajpai, Priyam; Gonnade, Rajesh G.; Vanka, Kumar; Punji, Benudhar

doi:10.1039/d2sc05274a

Cited by 18 publications

(12 citation statements)

References 70 publications

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“…Importantly, the latter was found as a precondition for the double hydrogenation to saturated alcohols by appropriate Ir‐ligand constellations. A very similar conclusion can be drawn from a very recent study of the hydrogenation from a wealth of CHL derivatives by using Mn(I)‐pincer ligands [19] …”

Section: Introductionsupporting

confidence: 76%

“…A very similar conclusion can be drawn from a very recent study of the hydrogenation from a wealth of CHL derivatives by using Mn(I)-pincer ligands. [19] During intensive research on biomass conversion, γ-valerolactone (GVL) has been identified by Horváth in 2008, [20] as a promising renewable platform molecule, which has several useful and innovative applications. For example, GVL can be used for the production of alkanes and alkenes, [21] transportation fuels, [22] lighter fluids, [23] and feedstock for polymer industry.…”

Section: Introduction (E)-chalconesmentioning

confidence: 99%

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Kinetic and Mechanistic Studies of the Selective Hydrogenation of (E)‐Chalcones in Biomass‐Derived γ‐Valerolactone Catalyzed by Rh−PPh₃ Complexes

2023

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γ‐Valerolactone as a renewable, polar aprotic solvent was evaluated in the selective hydrogenation of carbon‐carbon double bond of chalcones from both catalytic and mechanistic aspects. By using triphenylphosphine‐modified cationic rhodium catalyst systems reasonably high activities (TOFinitial∼1200 h−1) were achieved in the selective hydrogenation of (E)‐chalcone (CHL), as a common model substrate for α,β‐unsaturated ketones, to dihydrochalcone (DHC). Various derivatives of CHL, which were substituted on the styryl phenyl groups also showed exclusive selectivity for the hydrogenation of the C=C double bond. The optimal PPh3/Rh ratio was between 2.5 to 3, but higher ratios were advantageously also tolerated, which is beneficial for the process chemistry. The solvent GVL proved to stable enough under the reaction conditions for waste‐free recycling. Kinetic studies and NMR spectra from the analogous deuteration of chalcone by using the cationic Rh‐PPh3 system clearly show the olefin insertion as the rate‐determining step with definite irreversibility. By investigating the substituent effect on the phenyl ring of the styryl moiety of chalcone, a quasi‐linear correlation was found between the electronic parameters of the para‐substituents and the activity with electron donor groups being favorable for the reaction rate. In summary, an environmentally friendly and feasible method is presented for the production of valuable DHC intermediates in view of their pharmaceutical importance.

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Section: Introductionsupporting

confidence: 76%

Section: Introduction (E)-chalconesmentioning

confidence: 99%

Kinetic and Mechanistic Studies of the Selective Hydrogenation of (E)‐Chalcones in Biomass‐Derived γ‐Valerolactone Catalyzed by Rh−PPh₃ Complexes

2023

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“…Based on our preliminary findings and literature reports, [10f,11b,12b,17] we have proposed a catalytic cycle for the chemoselective C=C bond hydrogenation of chalcones using [ Mn1 ] (Figure 1). At first, the active Mn−H [ Mn−A ] species will be generated by the reaction of the Mn−Br complex with H 3 N−BH 3 .…”

Section: Resultsmentioning

confidence: 79%

Manganese(I)‐Catalyzed Chemoselective Transfer Hydrogenation of the C=C Bond in Conjugated Ketones at Room Temperature

Sharma

Shabade

Gonnade

et al. 2023

Chemistry A European J

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Chemoselective transfer hydrogenation of C=C bond in α,β-unsaturated ketones is demonstrated at room temperature employing a manganese(I) catalyst and half an equivalent of ammonia-borane (H 3 NÀ BH 3 ). A series of mixeddonor pincer-ligated Mn(II) complexes, X=Br (Mn3), X=I (Mn4)} were synthesized and characterized. Amongst the Mn(II) complexes, (Mn2, Mn3, Mn4) and Mn(I) complex, ( tBu2 PN 3 N Pyz )Mn(CO) 2 Br (Mn1) screened; the Mn1 acts as an efficient catalyst for the chemoselective C=C bond reduction in α,β-unsaturated ketones. Various synthetically important functionalities like halides, methoxy, trifluoromethyl, benzyloxy, nitro, amine, and unconjugated alkene and alkyne groups, including heteroarenes, were compatible and provided saturated ketones in excellent yields (up to 97 %). A preliminary mechanistic study highlighted the crucial role of metal-ligand (M-L) cooperation through the dearomatization-aromatization process in catalyst Mn1 for the chemoselective C=C bond transfer hydrogenation.

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“…To facilitate and control such hydrogenations, generally noble-metal-based catalysts are required. However, due to their limited availability and high cost, the current trend is to replace noble-metal catalysts by more abundant, economical, environmentally friendly catalysts based on earth-abundant metals, e.g., manganese, iron and cobalt. ,− …”

Section: Catalytic Hydrogenationsmentioning

confidence: 99%

Hydrogenation and Cross-Coupling Reactions Catalyzed by Mn, Fe, and Co Aromatic Pincer Complexes

González-Sebastián,

Reyes-Sanchez,

Morales-Morales

2023

Organometallics

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Currently, the development of environmentally benign and effective catalytic reactions for organic synthesis based on low-cost and abundant metals is one of the central research goals in modern chemistry. This review covers the advancements in homogeneously catalyzed reactions using pincer complexes of manganese, iron, and cobalt featuring aryl and pyridine central backbones. Specifically, C–C coupling reactions and hydrogenation reactions of alkenes, alkynes, aldehydes, ketones, esters, nitriles, CO2, carbamates, ureas, cyclic imides and azo compounds are described, including their scope and mechanistic insights. Overall, this review emphasizes that the combination of inexpensive and readily available metals, such as Mn, Fe, and Co, with pincer ligands that are capable of ligand–metal cooperation may lead to the creation of innovative, versatile, and effective catalysts, some of which can even exceed the activity of state-of-the-art noble-metal systems for green chemistry processes.

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Room temperature chemoselective hydrogenation of CC, CO and CN bonds by using a well-defined mixed donor Mn(i) pincer catalyst

Abstract: Chemoselective hydrogenation of C=C, C=O and C=N bonds in α,β-unsaturated ketones, aldehydes and imines is accomplished at room temperature (27 oC) using the well-defined Mn(I) catalyst and 5.0 bar H2....

Cited by 18 publications

References 70 publications

Kinetic and Mechanistic Studies of the Selective Hydrogenation of (E)‐Chalcones in Biomass‐Derived γ‐Valerolactone Catalyzed by Rh−PPh₃ Complexes

Kinetic and Mechanistic Studies of the Selective Hydrogenation of (E)‐Chalcones in Biomass‐Derived γ‐Valerolactone Catalyzed by Rh−PPh₃ Complexes

Manganese(I)‐Catalyzed Chemoselective Transfer Hydrogenation of the C=C Bond in Conjugated Ketones at Room Temperature

Hydrogenation and Cross-Coupling Reactions Catalyzed by Mn, Fe, and Co Aromatic Pincer Complexes

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Room temperature chemoselective hydrogenation of CC, CO and CN bonds by using a well-defined mixed donor Mn(i) pincer catalyst

Abstract: Chemoselective hydrogenation of C=C, C=O and C=N bonds in α,β-unsaturated ketones, aldehydes and imines is accomplished at room temperature (27 oC) using the well-defined Mn(I) catalyst and 5.0 bar H2....

Cited by 18 publications

References 70 publications

Kinetic and Mechanistic Studies of the Selective Hydrogenation of (E)‐Chalcones in Biomass‐Derived γ‐Valerolactone Catalyzed by Rh−PPh3 Complexes

Kinetic and Mechanistic Studies of the Selective Hydrogenation of (E)‐Chalcones in Biomass‐Derived γ‐Valerolactone Catalyzed by Rh−PPh3 Complexes

Manganese(I)‐Catalyzed Chemoselective Transfer Hydrogenation of the C=C Bond in Conjugated Ketones at Room Temperature

Hydrogenation and Cross-Coupling Reactions Catalyzed by Mn, Fe, and Co Aromatic Pincer Complexes

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Kinetic and Mechanistic Studies of the Selective Hydrogenation of (E)‐Chalcones in Biomass‐Derived γ‐Valerolactone Catalyzed by Rh−PPh₃ Complexes

Kinetic and Mechanistic Studies of the Selective Hydrogenation of (E)‐Chalcones in Biomass‐Derived γ‐Valerolactone Catalyzed by Rh−PPh₃ Complexes