Molybdenum‐Catalyzed Asymmetric Amination of α‐Hydroxy Esters: Synthesis of α‐Amino Acids DOI Creative Commons
Shahida Perveen, Talat S. Rahman, Tariq Ali

и другие.

Advanced Science, Год журнала: 2025, Номер unknown

Опубликована: Март 10, 2025

Abstract Unnatural α‐amino acids are found in a wide variety of bioactive compounds ranging from proteins to pharmaceutical agents materials science. As result, the investigation efficient and simple methods for their synthesis is major purpose reaction development. In this study, it that catalyst based on molybdenum, an earth‐abundant transition metal, can facilitate amination readily accessible α‐hydroxy esters afford N ‐protected unnatural acid high yield. This process also enables enantioselective amination, which proceeds through cooperative catalysis chiral molybdenum complex with phosphoric (CPA), complements earlier procedures catalytic important class compounds. The obtained protected ester products directly useful or further utilized commercially available drugs analogs.

Язык: Английский

Enantioselective Transformations in the Synthesis of Therapeutic Agents DOI
Yang He,

Hanxiao Yu,

I. Stolarzewicz

и другие.

Chemical Reviews, Год журнала: 2023, Номер 123(15), С. 9397 - 9446

Опубликована: Июль 7, 2023

The proportion of approved chiral drugs and drug candidates under medical studies has surged dramatically over the past two decades. As a consequence, efficient synthesis enantiopure pharmaceuticals or their synthetic intermediates poses profound challenge to medicinal process chemists. significant advancement in asymmetric catalysis provided an effective reliable solution this challenge. successful application transition metal catalysis, organocatalysis, biocatalysis pharmaceutical industries promoted discovery by precise preparation enantio-enriched therapeutic agents, facilitated industrial production active ingredient economic environmentally friendly fashion. present review summarizes most recent applications (2008–2022) industry ranging from scales pilot levels. It also showcases latest achievements trends agents with state art technologies catalysis.

Язык: Английский

Процитировано

43
Multicomponent Synthesis of α-Branched Amines via a Zinc-Mediated Carbonyl Alkylative Amination Reaction DOI Creative Commons
Joseph M. Phelps, Roopender Kumar, James D. Robinson

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(13), С. 9045 - 9062

Опубликована: Март 15, 2024

Methods for the synthesis of α-branched alkylamines are important due to their ubiquity in biologically active molecules. Despite development many methods amine preparation, C(sp3)-rich nitrogen-containing compounds continue pose challenges synthesis. While carbonyl reductive amination (CRA) between ketones and is cornerstone method alkylamine synthesis, it sometimes limited by sterically demanding condensation step dialkyl amines more restricted availability compared aldehydes. We recently reported a "higher-order" variant this transformation, alkylative (CAA), which utilized halogen atom transfer (XAT)-mediated radical mechanism, enabling streamlined complex alkylamines. efficacy visible-light-driven approach, displayed scalability issues, competitive was problem certain substrate classes, limiting applicability. Here, we report change reaction regime that expands CAA platform through realization an extremely broad zinc-mediated reaction. This new strategy enabled elimination CRA, simplified purification, improved scope. Furthermore, harnessed carboxylic acid derivatives as alkyl donors facilitated α-trialkyl tertiary amines, cannot be accessed via CRA. Zn-mediated can carried out at variety scales, from 10 μmol setup microtiter plates high-throughput experimentation, gram-scale medicinally-relevant compounds. believe transformation enables robust, efficient, economical access provides viable alternative current benchmark methods.

Язык: Английский

Процитировано

20
Reductive aminations by imine reductases: from milligrams to tons DOI Creative Commons
Amelia K. Gilio, Thomas W. Thorpe, Nicholas J. Turner

и другие.

Chemical Science, Год журнала: 2022, Номер 13(17), С. 4697 - 4713

Опубликована: Янв. 1, 2022

IRED-catalyzed reductive aminations have progressed from mg to ton scale, through advances in enzyme discovery, protein engineering and process biocatalysis.

Язык: Английский

Процитировано

57
Organometallic Mn(I) Complexes in Asymmetric Catalytic (Transfer) Hydrogenation and Related Transformations DOI Creative Commons
Dexin Fu, Zheng Wang, Qingbin Liu

и другие.

ChemCatChem, Год журнала: 2024, Номер 16(14)

Опубликована: Март 7, 2024

Abstract Direct asymmetric hydrogenation (AH) and transfer (ATH) are among the most efficient approaches to produce chiral building blocks. Recently, these types of transformations have witnessed a shift towards use molecular catalysts based on earth‐abundant transition metals due their ready availability, economic advantage, novel properties. With particular regard manganese, catalyst development has seen both efficiency substrate scope in AH ATH greatly improved, with emergence large number well‐defined Mn‐complexes employed this field. The reaction includes C=O bonds, reduction C=N bonds reductive C=C bonds. Herein, our survey area focuses catalytic activity such complexes, versatility routes convert substrates target molecules. We consider collected findings article will be helpful reader by providing an insight into ligand design, thereby aiding future development. Moreover, review is aimed at highlighting remarkable progress made last seven years manganese complexes for enantioselective reduction.

Язык: Английский

Процитировано

11
Impact of aqueous micellar media on biocatalytic transformations involving transaminase (ATA); applications to chemoenzymatic catalysis DOI
Jade Dussart‐Gautheret, Tzu‐Yu Yu, Krithika Ganesh

и другие.

Green Chemistry, Год журнала: 2022, Номер 24(16), С. 6172 - 6178

Опубликована: Янв. 1, 2022

Surfactant-enabled asymmetric ATA-catalyzed reductive aminations in aqueous buffered media are described, representative of the enhanced levels conversion made possible by presence a nonionic surfactant water, thereby enabling 1-pot chemoenzymatic catalysis.

Язык: Английский

Процитировано

34
Organocatalytic Dynamic Kinetic Resolution: An Update DOI

Hélène Pellissier

European Journal of Organic Chemistry, Год журнала: 2022, Номер 2022(7)

Опубликована: Фев. 17, 2022

Abstract It is only in the two last decades that first examples of organocatalytic dynamic kinetic resolutions (DKRs) have been disclosed. These methodologies allow resolving racemic compounds with up to quantitative yield. Today, a variety chiral organocatalysts are capable providing excellent enantioselectivities many types transformations evolving through DKR. The goal this review update field DKRs since 2016. divided into six sections, according different employed these reactions, such as Brønsted acid catalysts, hydrogen‐bonding N‐heterocyclic carbene Lewis base phase‐transfer and cinchona alkaloid‐based catalysts.

Язык: Английский

Процитировано

30
Asymmetric Double Hydroxycarbonylation of Alkynes to Chiral Succinic Acids Enabled by Palladium Relay Catalysis DOI

Xiaolei Ji,

Chaoren Shen,

Xinxin Tian

и другие.

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(29)

Опубликована: Май 7, 2022

Abstract A Pd‐catalyzed asymmetric double hydroxycarbonylation of terminal alkynes was developed by using relay catalysis, providing a highly efficient route to chiral succinic acids (41 examples, 76–94 %, 94–99 % ee ). Key success the combinatorial use Pd precursor with two distinct phosphine ligands in one pot. The synthetic utilities this protocol were showcased facile synthesis key intermediates for pharmaceuticals.

Язык: Английский

Процитировано

30
Leveraging the Redox Promiscuity of Nickel To Catalyze C–N Coupling Reactions DOI
Olivia Taylor,

Paul J. Saucedo,

Ana Bahamonde

и другие.

The Journal of Organic Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Янв. 17, 2024

This perspective details advances made in the field of Ni-catalyzed C–N bond formation. The use this Earth abundant metal to decorate amines, amides, lactams, and heterocycles enables direct access a variety biologically active industrially relevant compounds sustainable manner. Herein, different strategies that leverage propensity Ni facilitate both one- two-electron processes will be surveyed. first part Perspective focuses on couplings at room temperature by accessing oxidized Ni(III) intermediates. In context, photochemical, electrochemical, chemically mediated analyzed. A special emphasis has been put providing comprehensive explanation mechanistic avenues have proposed these chemistries; either Ni(I/III) self-sustained cycles or Ni(0/II/III) photochemically pathways. second ligand designs also enable reactivity via Ni(0/II) mechanism. Finally, we discuss our thoughts possible future directions field.

Язык: Английский

Процитировано

7
Design and Application of New Pyridine-Derived Chiral Ligands in Asymmetric Catalysis DOI
Shuai Zhang,

Yizhao Ouyang,

Yuan Gao

и другие.

Accounts of Chemical Research, Год журнала: 2024, Номер 57(6), С. 957 - 970

Опубликована: Март 6, 2024

ConspectusThe innovation of chiral ligands has been crucial for the asymmetric synthesis functional molecules, as demonstrated by several types widely applied "privileged" ligands. In this context, pyridine-derived ligands, far some oldest and most utilized in catalysis, have attracted considerable research interest past half-century. However, development broadly applicable pyridine units (CPUs) plagued intertwining challenges, thus delaying advancements many reactions.This Account aims to summarize recent progress new CPU-containing focusing on a rationally designed, modular, tunable CPU developed our laboratory. A significant problem thwarting conventional designs is paradox between broad reactivity stereoselectivity; that is, while enhanced stereoselectivity may be achieved introducing elements close N atom, concomitant increase local steric hindrance often limits catalytic activity scope. Our newly features rigid [6-5-3] fused-ring framework spirocyclic ketal side wall. The well-defined three-dimensional structure minimizes (inner layer) tunes peripheral environment (outer remote substituents, securing stereoselectivity. Different chelating were readily assembled using structural module, with applications mechanistically diverse transition-metal-catalyzed reactions. Thus, series 2,2′-bipyridine successfully employed general, efficient, highly enantioselective nickel-catalyzed intermolecular reductive addition, Ullmann coupling ortho-chlorinated aryl aldehydes, carboxylation benzylic (pseudo)halides CO2. Notably, these exhibited superior reactions compared common N-based iridium-catalyzed C–H borylation was N,B-bidentate ligand. Furthermore, challenging, additive-free, broad-scope transfer hydrogenative direct amination half-sandwich iridium catalyst supported N,C-bidentate excellent performance high stereoselectivity, which, when combined experimental computational mechanistic investigations, "double-layer control" design concept.Considering described herein should inspire creation novel catalysts drive

Язык: Английский

Процитировано

6
Titanium in photocatalytic organic transformations: current applications and future developments DOI
Jia‐Lin Tu, Binbin Huang

Organic & Biomolecular Chemistry, Год журнала: 2024, Номер 22(33), С. 6650 - 6664

Опубликована: Янв. 1, 2024

Titanium, as an important transition metal, has garnered extensive attention in both industry and academia due to its excellent mechanical properties, corrosion resistance, unique reactivity organic synthesis. In the field of photocatalysis, titanium-based compounds such titanium dioxide (TiO

Язык: Английский

Процитировано

6