Iridium-catalyzed chemoselective asymmetric hydrogenation of conjugated enones with ferrocene-based multidentate phosphine ligands

Ma, Jun; Li, Wendian; He, Lin; Lv, Hui

doi:10.1039/d2cc01583h

Cited by 14 publications

(1 citation statement)

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“…Chiral ferrocene moieties exhibit high chemical stabilities and a broad range of applications in asymmetric synthetic reactions. − The design of chiral ligands on the backbone of ferrocene allows for precise tuning of the asymmetric environment, resulting in high enantioselectivity. ,,,− To better tune the asymmetric environments of the nickel catalysts, we decided to introduce a planar chiral ferrocene moiety into the ligands of the nickel catalysts. The rationale for the catalyst design is similar to that of our previously reported iron catalysts that contained binaphthyl skeletons; a bifunctional ATH catalyst requires an amino ligand to cooperate with the NiH center in 2-propanol activation and carbonyl group hydrogenation.…”

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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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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Chiral P,N,N‐Ligands for Asymmetric Hydrogenation

Liang,

Hou,

et al. 2024

Adv Synth Catal

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The chiral P,N,N‐ligands represented a new type of tridentate ligand developed in recent years and displayed wide utilities in asymmetric catalysis. In the past decades, numerous chiral P,N,N‐ligands with ferrocene, phenethylamine and spiro backbones were synthesized by addition of an aminopyridine, imidazole or diamines coordinating group. These chiral tridentate P,N,N‐ligands showed excellent performance in the ruthenium, iridium, manganese, or cobalt‐catalyzed asymmetric hydrogenations. A wide range of substrates, including simple ketones, α‐halogenated ketones, α‐hydroxy ketones, α‐ or β‐amino ketones, α‐, γ‐, or δ‐keto acids, α‐ or β‐keto amides, β‐ or δ‐keto esters, α‐ or β‐enones, olefins, imines, quinolines and indoles, could be hydrogenated to afford the corresponding chiral products with high yields and enantioselectivities. In this review, progress on the asymmetric hydrogenation of C=O, C=N, C=C bonds with chiral tridentate P,N,N‐ligands was summarized.

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Copper‐Catalyzed Chemoselective Asymmetric Hydrogenation of C=O Bonds of Exocyclic α,β‐Unsaturated Pentanones

et al. 2023

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A highly chemoselective earth‐abundant transition metal copper catalyzed asymmetric hydrogenation of C=O bonds of exocyclic α,β‐unsaturated pentanones was realized using H2. The desired products were obtained with up to 99 % yield and 96 % ee (enantiomeric excess) (99 % ee, after recrystallization). The corresponding chiral exocyclic allylic pentanol products can be converted into several bioactive molecules. The hydrogenation mechanism was investigated via deuterium‐labelling experiments and control experiments, which indicate that the keto‐enol isomerization rate of the substrate is faster than that of the hydrogenation and also show that the Cu−H complex can only catalyze chemoselectively the asymmetric reduction of the carbonyl group. Computational results indicate that the multiple attractive dispersion interactions (MADI effect) between the catalyst with bulky substituents and substrate play important roles which stabilize the transition states and reduce the generation of by‐products.

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Iridium-catalyzed chemoselective asymmetric hydrogenation of conjugated enones with ferrocene-based multidentate phosphine ligands

Abstract: A series of novel and readily prepared ferrocene-based multidentate phosphine ligands (f-PNNO) have been developed and successfully used in iridium-catalyzed enantioselective 1,2-reduction of ,-unsaturated ketones, delivering chiral allylic alcohols in...

Cited by 14 publications

References 50 publications

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

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

Chiral P,N,N‐Ligands for Asymmetric Hydrogenation

Copper‐Catalyzed Chemoselective Asymmetric Hydrogenation of C=O Bonds of Exocyclic α,β‐Unsaturated Pentanones

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