Recent Advances in the Enantioselective Synthesis of Chiral Amines via Transition Metal-Catalyzed Asymmetric Hydrogenation

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(1), P. 269 - 339

Published: Oct. 22, 2021

Chiral amines are key structural motifs present in a wide variety of natural products, drugs, and other biologically active compounds. During the past decade, significant advances have been made with respect to enantioselective synthesis chiral amines, many them based on catalytic asymmetric hydrogenation (AH). The review covers use AH bearing stereogenic center either α, β, or γ position nitrogen atom, reported from 2010 2020. Therefore, we provide an overview recent imines, enamides, enamines, allyl N-heteroaromatic

Language: Английский

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Asymmetric arene hydrogenation: towards sustainability and application

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 52(15), P. 4996 - 5012

Published: Jan. 1, 2023

This review summarises the state-of-the-art in transition-metal catalysed asymmetric hydrogenation of (hetero)arenes and highlights recent advances with a special focus on sustainability while also addressing its shortcomings.

Language: Английский

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P-Stereogenic Phosphorus Ligands in Asymmetric Catalysis

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(14), P. 8657 - 8739

Published: July 2, 2024

Chiral phosphorus ligands play a crucial role in asymmetric catalysis for the efficient synthesis of useful optically active compounds. They are largely categorized into two classes: backbone chirality and P-stereogenic ligands. Most reported belong to former class. Privileged ones such as BINAP DuPhos frequently employed wide range catalytic transformations. In contrast, latter class has remained small family many years mainly because their synthetic difficulty. The late 1990s saw emergence novel with superior enantioinduction ability Rh-catalyzed hydrogenation reactions. Since then, numerous have been synthesized used This Review summarizes thus far, including stereochemical electronic properties that afford high excellent enantioselectivities. Examples reactions use this described together applications construction key intermediates natural products therapeutic agents. literature covered dates back 1968 up until December 2023, centering on studies published later years.

Language: Английский

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Asymmetric hydrogenation of ketimines with minimally different alkyl groups

Nature, Journal Year: 2024, Volume and Issue: 631(8021), P. 556 - 562

Published: May 28, 2024

Language: Английский

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Recent advances on transition-metal-catalysed asymmetric reductive amination

Organic Chemistry Frontiers, Journal Year: 2021, Volume and Issue: 8(10), P. 2328 - 2342

Published: Jan. 1, 2021

This review focuses on the recent progress of homogeneous transition-metal-catalysed asymmetric reductive amination ketones with diverse nitrogen sources.

Language: Английский

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Continuous flow asymmetric synthesis of chiral active pharmaceutical ingredients and their advanced intermediates

Green Chemistry, Journal Year: 2021, Volume and Issue: 23(17), P. 6117 - 6138

Published: Jan. 1, 2021

Catalytic enantioselective transformations provide well-established and direct access to stereogenic synthons that are broadly distributed among active pharmaceutical ingredients (APIs). These reactions have been demonstrated benefit considerably from the merits of continuous processing microreactor technology. Over past few years, flow catalysis has grown into a mature field found diverse applications in asymmetric synthesis pharmaceutically substances. The present review therefore surveys chemistry-based approaches for chiral APIs their advanced intermediates, covering utilization biocatalysis, organometallic metal-free organocatalysis introduce asymmetry continuously operated systems. Single-step processes, interrupted multistep syntheses, combined batch/flow processes uninterrupted one-flow syntheses discussed herein.

Language: Английский

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Cobalt‐Catalyzed Chemo‐ and Enantioselective Hydrogenation of Conjugated Enynes

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(31), P. 16989 - 16993

Published: June 1, 2021

Asymmetric hydrogenation is one of the most powerful methods for preparation single enantiomer compounds. However, chemo- and enantioselective relatively inert unsaturated group in substrates possessing multiple bonds remains a challenge. We herein report protocol highly conjugated enynes while keeping alkynyl bond intact. Mechanism studies indicate that accompanying Zn2+ generated from zinc reduction CoII complex plays critical role to initiate plausible CoI /CoIII catalytic cycle. This approach allows efficient generation chiral propargylamines (up 99.9 % ee 2000 S/C) further useful chemical transformations.

Language: Английский

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Manganese‐Catalyzed Asymmetric Hydrogenation of 3H‐Indoles

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(20)

Published: March 3, 2022

The asymmetric hydrogenation (AH) of 3H-indoles represents an ideal approach to the synthesis useful chiral indoline scaffolds. However, very few catalytic systems based on precious metals have been developed realize this challenging reaction. Herein, we report a Mn-catalyzed AH with excellent yields and enantioselectivities. kinetic resolution racemic by was also achieved high s-factors construct quaternary stereocenters. Many acid-sensitive functional groups, which cannot be tolerated when using state-of-the-art ruthenium catalyst, were compatible manganese catalysis. This new process expands scope transformation highlights uniqueness earth-abundant metal reaction could proceed catalyst loadings at parts per million (ppm) level exceptional turnover number 72 350. is highest value yet reported for metal-catalyzed

Language: Английский

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

Nature Communications, Journal Year: 2023, Volume and Issue: 14(1)

Published: June 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.

Language: Английский

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Biomimetic asymmetric catalysis

Science China Chemistry, Journal Year: 2023, Volume and Issue: 66(6), P. 1553 - 1633

Published: April 25, 2023

Language: Английский

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