A concise review on recent advances in catalytic asymmetric hydrogenation

Behera, Priyanka; Ramakrishna, D. S.; Chandrasekhar, Manchikanti M.; Kothakapu, Sridhar Reddy

doi:10.1002/chir.23559

Cited by 16 publications

(7 citation statements)

References 119 publications

(164 reference statements)

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“…Prochiral substrates for asymmetric hydrogenation include olefins, ketones, enamines and imines. It is generally performed in the presence of a homogeneous transition metal catalyst, typically a rhodium or ruthenium complex of a chiral bis(phosphine) ligand [24,25] . Hydrogenative PHIP is essentially a homogeneous catalytic hydrogenation process.…”

Section: Methodsmentioning

confidence: 99%

StereoPHIP: Stereoselective Parahydrogen‐Induced Polarization

Huynh,

Buchanan,

Chirayil

et al. 2023

Angewandte Chemie

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Parahydrogen induced polarization (PHIP) followed by polarization transfer to 13C is a rapidly developing technique for the generation of 13C hyperpolarized substrates. Chirality plays an essential role in living systems and differential metabolism of enantiomeric pairs of metabolic substrates is well documented. Inspired by asymmetric hydrogenation, here we report stereoPHIP, which involves the addition of parahydrogen to a prochiral substrate with a chiral catalyst followed by polarization transfer to 13C spins. We demonstrate that parahydrogen could be rapidly added to the prochiral precursor to both enantiomers of lactic acid (D and L), with both the (R,R) and (S,S) enantiomers of a chiral rhodium(I) catalyst to afford highly 13C‐hyperpolarized (over 20%) L‐ and D‐lactate ester derivatives, respectively, with excellent stereoselectivity. We also show that the hyperpolarized 1H signal decays obtained with the (R,R) and (S,S) catalysts were markedly different. StereoPHIP expands the scope of conventional PHIP to the production of 13C hyperpolarized chiral substrates with high stereoselectivity.

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Section: Methodsmentioning

confidence: 99%

StereoPHIP: Stereoselective Parahydrogen‐Induced Polarization

Huynh,

Buchanan,

Chirayil

et al. 2023

Angewandte Chemie

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“…Recently, some nickel catalysts , exhibited high activities and enantioselectivities in synthesizing compounds with chiral C–N bonds via reductive aminations of ketones. − However, more challenging ATH and AH reactions of ketones have been developed slowly. Despite reports of a number of hydrogenation or transfer hydrogenation reactions of ketones catalyzed by nickel complexes, most of them are not asymmetric. ,− To the best of our knowledge, , there are only three examples of nickel-catalyzed ATH reactions of ketones to date.…”

Section: Introductionmentioning

confidence: 99%

(Primary Amido)-ene(amido) Ni(II) Catalysts Containing a P-Chirogenic Substituted Ferrocene Moiety for Highly Enantioselective Asymmetric Transfer Hydrogenation of Ketones

Chen,

Zuo

2024

Organometallics

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Asymmetric transfer hydrogenation (ATH) of ketones is an efficient method for constructing chiral alcohols that are widely used in synthesizing various fine chemicals. Currently, most of the existing catalysts contain precious metals that are highly toxic and scarce, which limits industrial application and sustainability. Therefore, the development of catalysts based on earth-abundant and environmentally friendly 3d metals is an important research topic. We previously reported that amidoene(amido)diphosphine Ni(II) catalysts exhibited promising reactivities. However, the enantioselectivity of the catalytic system was not satisfactory. Here, we report (primary amido)-ene(amido)-Ni(II)diphosphine catalyst 2n containing a P-chirogenic substituted ferrocene moiety in the ligand backbone and its analogue (2m). 2n was used for ATHs of a range of ketones with improved enantioselectivity, affording secondary alcohols of the (S)configuration with up to 98% enantiomeric excess (e.e.). Computational results indicated that in the reaction system of catalyst 2n, the (S)-configuration of the phosphine kept the (S)-planar chiral ferrocene moiety far from the reacting site in the transition state that produced the (S)-configured alcohol. This created space for the aryl ring of the substrate and the ene(amido) moiety of the catalyst to approach each other and form a strong π−π interaction that enhanced the enantioselectivity.

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“…On the other hand, factors including mass transferability in the catalyst/reaction interfaces, density and accessibility of active sites on the catalyst, successful collisions and interactions of reactant molecules with active centers of catalyst, and so on, are intrinsic limitations of heterogeneous catalysts. , Moreover, another cornerstone of catalyst designing is chirality, which offers the potential for asymmetric synthesis . In other words, asymmetric catalysis is the most effective method for producing pure chiral compounds that exhibit exceptional pharmaceutical and chemical properties. , Designing and synthesizing catalysts with a chiral architecture require multistep sophisticated reactions, harsh conditions, expensive chiral ligands, and high synthetic expertise, are time-consuming, have poor efficiency, toxic organic solvents and reagents, etc …”

Section: Introductionmentioning

confidence: 99%

Chiral Pseudohomogeneous Catalyst Based on Amphiphilic Carbon Quantum Dots for the Enantioselective Kharasch–Sosnovsky Reaction

Rezaei,

Zheng,

Majidian

et al. 2023

ACS Appl. Mater. Interfaces

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The term “chiral pseudohomogeneous catalyst (PHC)” denotes a novel concept that characterizes subnanometric particles exhibiting atomic-level chirality. The PHC based on chiral amphiphilic carbon quantum dots possesses distinctive features that combine the strengths of both homogeneous and heterogeneous catalysts, thereby heralding a significant breakthrough in the fields of asymmetric synthesis and medicinal chemistry. To the best of our knowledge, this is the first and the only reported research of a chiral PHC that demonstrates exceptional performance in controlling the enantioselectivity of the Kharasch–Sosnovsky reaction, yielding the corresponding products in high conversion (95%) with a moderate enantiomeric excess (75%). Notably, the chiral information on l-tryptophan can be effectively transferred from the outer shell of the nanosized catalyst, thereby inducing enantioselectivity in C–H activation and subsequent C–O forming events. Additionally, we have investigated the impact of various factors on the allylic oxidation reaction, including the amount, diversity, and hydrophilic/hydrophobic nature of the catalyst, as well as the influence of the solvent, Cu salts, temperature, and the type of alkene and perester, in order to comprehensively explore the reaction conditions. Furthermore, the catalyst can be readily recycled from the reaction medium, making this PHC a promising innovation that can significantly impact practical applications. In summary, this breakthrough can be aptly described as a “Golden Gate” due to its unparalleled potential to open up novel avenues for research and innovation.

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A concise review on recent advances in catalytic asymmetric hydrogenation

Cited by 16 publications

References 119 publications

StereoPHIP: Stereoselective Parahydrogen‐Induced Polarization

StereoPHIP: Stereoselective Parahydrogen‐Induced Polarization

(Primary Amido)-ene(amido) Ni(II) Catalysts Containing a P-Chirogenic Substituted Ferrocene Moiety for Highly Enantioselective Asymmetric Transfer Hydrogenation of Ketones

Chiral Pseudohomogeneous Catalyst Based on Amphiphilic Carbon Quantum Dots for the Enantioselective Kharasch–Sosnovsky Reaction

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