A 13-million turnover-number anionic Ir-catalyst for a selective industrial route to chiral nicotine

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Июнь 22, 2023

Abstract Developing catalysts with both useful enantioselectivities and million turnover numbers (TONs) for asymmetric hydrogenation of ketones is attractive industrial production high-value bioactive chiral entities but remains a challenging. Herein , we report an ultra-efficient anionic Ir-catalyst integrated the concept multidentate ligation ketones. Biocatalysis-like efficacy up to 99% ee (enantiomeric excess), 13,425,000 TON (turnover number) 224 s −1 TOF frequency) were documented benchmark acetophenone. Up 1,000,000 achieved challenging pyridyl alkyl ketone where at most 10,000 TONs are previously reported. The showed novel preferred ONa/MH instead NNa/MH bifunctional mechanism. A selective route enantiopure nicotine has been established using this key step 500 kg batch scale, providing 40 tons scale product.

Язык: Английский

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Converting Non‐strained γ‐Valerolactone and Derivatives into Sustainable Polythioesters via Isomerization‐driven Cationic Ring‐Opening Polymerization of Thionolactone Intermediate

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(14)

Опубликована: Фев. 9, 2023

Abstract This contribution reports the efficient conversion of γ‐valerolactone and its derivatives, abundant but unexplored renewable feedstocks, into sustainable degradable polythioesters via establishment first isomerization‐driven ring‐opening polymerizations (IROPs) corresponding thionolactone intermediates. The key to this success relies on development a new simple robust [Et 3 O] + [B(C 6 F 5 ) 4 ] − cationic initiator which possesses high activity, exclusive selectivity, living nature, broad scope thionolactones. A complete inversion configuration during IROP enantiopure γ‐thionovalerolactone is also disclosed, affording isotactic semicrystalline ( T m =87.0 °C) with mechanical property compared well representative commodity polyolefins. formation highly crystalline supramolecular stereocomplex enhanced thermal =117.6 has been revealed.

Язык: Английский

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Nickel‐Catalyzed Asymmetric Hydrogenation of α‐Substituted Vinylphosphonates and Diarylvinylphosphine Oxides

Angewandte Chemie International Edition, Год журнала: 2022, Номер 62(6)

Опубликована: Дек. 12, 2022

Chiral α-substituted ethylphosphonate and ethylphosphine oxide compounds are widely used in drugs, pesticides, ligands. However, their catalytic asymmetric synthesis is still rare. Of the only hydrogenation methods available at present, all cases use rare metal catalysts. Herein, we report an efficient earth-abundant transition-metal nickel catalyzed affording corresponding chiral products with up to 99 % yield, 96 ee (enantiomeric excess) (99 ee, after recrystallization) 1000 S/C (substrate/catalyst); this also first study on of terminal olefins using a catalyst under hydrogen atmosphere. The mechanism was investigated via deuterium-labelling experiments calculations which indicate that two added atoms come from gas. Additionally, it believed reaction involves NiII rather than Ni0 cyclic process based weak attractive interactions between Ni olefin substrate.

Язык: Английский

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Nickel-Catalyzed Asymmetric Hydrogenation of γ-Keto Acids, Esters, and Amides to Chiral γ-Lactones and γ-Hydroxy Acid Derivatives

Organic Letters, Год журнала: 2022, Номер 24(14), С. 2722 - 2727

Опубликована: Апрель 1, 2022

A highly efficient asymmetric hydrogenation of a series γ-keto acid derivatives, including acids, esters, and amides, using Ni-(R,R)-QuinoxP* complex as the catalyst has been developed to afford chiral γ-hydroxy derivatives with excellent enantioselectivities, up 99.9% ee. This method provides not only an economical one-pot approach for synthesis γ-lactones but also access (S)-norfluoxetine, inhibitor neural serotonin reuptake essential intermediate pharmaceutical synthesis.

Язык: Английский

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Precise Synthesis of ChiralZ‐Allylamides by Cobalt‐Catalyzed Asymmetric Sequential Hydrogenations

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(15)

Опубликована: Фев. 8, 2023

Asymmetric sequential hydrogenations of conjugated enynes have been developed using a Ph-BPE-CoI catalyst for the precise synthesis chiral Z-allylamides in high activity (up to 1000 substrate/catalyst (S/C)) and with excellent enantioselectivity >99 % enantiomeric excess (ee)). Mechanism experiments theoretical calculations support cationic CoI /CoIII redox catalytic cycle. The difference between cobalt complexes Ph-BPE QuinoxP* was explained by process decomposition rate-determining step second hydrogenation.

Язык: Английский

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Hydrogen Bond Enhanced Enantioselectivity in the Nickel-Catalyzed Transfer Hydrogenation of α-Substituted Acrylic Acid with Formic Acid

ACS Catalysis, Год журнала: 2023, Номер 13(21), С. 14213 - 14220

Опубликована: Окт. 21, 2023

A chiral nickel complex that catalyzed asymmetric transfer hydrogenation of α-substituted acrylic acids under mild conditions and avoided the use high-pressure hydrogen gas was developed. The products included β-amino α-methyl carboxylic such as three nonsteroidal anti-inflammatory profens. Deuterium-labeling experiments DFT studies pointed to an unconventional protonation a metalacyclopropane formed by α-phenylacrylic acid which bonded with formic acid. An alternative conventional pathway hydride insertion cannot explain selective deuteration at β-position when HCO2D used.

Язык: Английский

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Chiral bisphosphine Ph-BPE ligand: a rising star in asymmetric synthesis

Chemical Society Reviews, Год журнала: 2024, Номер 53(13), С. 6735 - 6778

Опубликована: Янв. 1, 2024

The review summarizes the increasing applications of chiral bisphosphine ligand Ph-BPE in catalytic asymmetric reactions past twenty years.

Язык: Английский

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Nickel-catalyzed asymmetric hydrogenation for the preparation of α-substituted propionic acids

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Июнь 28, 2024

Abstract Transition metal-catalyzed asymmetric hydrogenation is one of the most efficient methods for preparation chiral α-substituted propionic acids. However, research on this method, employing cleaner earth-abundant metal catalysts, still insufficient in both academic and industrial contexts. Herein, we report an nickel-catalyzed acrylic acids affording corresponding with up to 99.4% ee (enantiomeric excess) 10,000 S/C (substrate/catalyst). In particular, method can be used obtain ( R )-dihydroartemisinic acid 99.8:0.2 dr (diastereomeric ratio) 5000 S/C, which essential intermediate antimalarial drug Artemisinin. The reaction mechanism has been investigated via experiments DFT (Density Functional Theory) calculations, indicate that protonolysis C-Ni bond key intramolecular proton transfer from carboxylic group substrate, rate-determining step.

Язык: Английский

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Chemoselective direct deuterodecarboxylation of free aliphatic carboxylic acids enabled by deuteron-coupled electron transfer

Chem Catalysis, Год журнала: 2024, Номер 4(3), С. 100899 - 100899

Опубликована: Янв. 24, 2024

Язык: Английский

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Ni-Catalyzed Asymmetric Hydrogenation of Aromatic Ketoacids for the Synthesis of Chiral Lactones

Organic Letters, Год журнала: 2022, Номер 24(13), С. 2494 - 2498

Опубликована: Март 29, 2022

A highly efficient Ni-catalyzed asymmetric hydrogenation of aromatic γ- and δ-ketoacids has been developed, affording a series δ-aryl lactones in high yields excellent enantioselectivities (≤98% ee). The could occur smoothly on gram scale with 0.05 mol % catalyst loading (S/C = 2000). This protocol provides an practical approach for accessing chiral important potential applications organic synthesis the pharmaceutical industry.

Язык: Английский

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