An Iridium Catalytic System Compatible with Inorganic and Organic Nitrogen Sources for Dual Asymmetric Reductive Amination Reactions DOI

Zhaofeng Gao,

Jingwen Liu, Haizhou Huang

et al.

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(52), P. 27307 - 27311

Published: Oct. 26, 2021

Abstract Asymmetric reductive amination (ARA) is one of the most promising methods for synthesis chiral amines. Herein we report our efforts on merging two ARA reactions into a single‐step transformation. Catalyzed by complex formed from iridium and steric hindered phosphoramidite, readily available inexpensive aromatic ketones initially undergo first with ammonium acetate to afford primary amines, which serve as amine sources second ARA, finally provide enantiopure C 2 ‐symmetric secondary products. The developed process competently enables successive coupling inorganic organic nitrogen in same reaction system. Brønsted acid additive plays multiple roles this procedure: it accelerates formation imine intermediates, minimizes inhibitory effect N‐containing species catalyst, reduces side

Language: Английский

Recent Advances in the Enantioselective Synthesis of Chiral Amines via Transition Metal-Catalyzed Asymmetric Hydrogenation DOI Creative Commons
Albert Cabré, Xavier Verdaguer, Antoni Riéra

et al.

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

Citations

286
Enantioselective Transformations in the Synthesis of Therapeutic Agents DOI
Yang He,

Hanxiao Yu,

I. Stolarzewicz

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(15), P. 9397 - 9446

Published: July 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.

Language: Английский

Citations

43
Recent Progress in Transition-Metal-Catalyzed Asymmetric Reductive Amination DOI
Noor U Din Reshi, Vitthal B. Saptal, Matthias Beller

et al.

ACS Catalysis, Journal Year: 2021, Volume and Issue: 11(22), P. 13809 - 13837

Published: Oct. 29, 2021

Asymmetric reductive amination (ARA) of a prochiral carbonyl compound with an amine using H2/hydrogen surrogate is concise and operationally simple method for the synthesis chiral amines. ARA proceeds via condensation group amine/ammonia followed by enantioselective reduction generated intermediate. The activation reductant stereoselective transfer hydrogen to intermediate imine/enamine often mediated transition metal catalyst. Considering wide applications enantiopure amines in pharmaceuticals, agrochemicals, materials, development effective catalysts has been intensively pursued last two decades. Since first report Blaser 1999, this key research area grown significantly recent years, as reflected advances catalyst design, diversifying substrate scope better mechanistic understanding. Several highly efficient general methodologies applicable challenging partners have demonstrated, providing ready access variety In Review, we present progress featuring diverse employing metal-catalysts. This Review provides organized critical discussion on engineering evolution, expanding susbstrate insights. To conclude, remaining challenges opportunities are also highlighted.

Language: Английский

Citations

100
Reductive aminations by imine reductases: from milligrams to tons DOI Creative Commons
Amelia K. Gilio, Thomas W. Thorpe, Nicholas J. Turner

et al.

Chemical Science, Journal Year: 2022, Volume and Issue: 13(17), P. 4697 - 4713

Published: Jan. 1, 2022

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

Language: Английский

Citations

57
Copper‐Catalyzed C(sp3)‐Amination of Ketone‐Derived Dihydroquinazolinones by Aromatization‐Driven C−C Bond Scission DOI Creative Commons
Xin‐Yang Lv, Roman Abrams, Rubén Martı́n

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(8)

Published: Dec. 28, 2022

Herein, we describe the development of a copper-catalyzed C(sp3 )-amination proaromatic dihydroquinazolinones derived from ketones. The reaction is enabled by intermediacy open-shell species arising homolytic C-C bond-cleavage driven aromatization. protocol characterized its operational simplicity and generality, including chemical diversification advanced intermediates.

Language: Английский

Citations

44
Biocatalytic reductive aminations with NAD(P)H-dependent enzymes: enzyme discovery, engineering and synthetic applications DOI
Bo Yuan, Dameng Yang, Ge Qu

et al.

Chemical Society Reviews, Journal Year: 2023, Volume and Issue: 53(1), P. 227 - 262

Published: Dec. 7, 2023

This review summarized NAD(P)H-dependent amine dehydrogenases and imine reductases which catalyzes asymmetric reductive amination to produce optically active amines.

Language: Английский

Citations

28
Copper-Catalyzed Enantioconvergent Radical C(sp3)–N Cross-Coupling of Activated Racemic Alkyl Halides with (Hetero)aromatic Amines under Ambient Conditions DOI
Ji‐Jun Chen, Jiayong Zhang,

Jia‐Heng Fang

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(27), P. 14686 - 14696

Published: July 1, 2023

The enantioconvergent C(sp3)-N cross-coupling of racemic alkyl halides with (hetero)aromatic amines represents an ideal means to afford enantioenriched N-alkyl yet has remained unexplored due the catalyst poisoning specifically for strong-coordinating heteroaromatic amines. Here, we demonstrate a copper-catalyzed radical activated under ambient conditions. key success is judicious selection appropriate multidentate anionic ligands through readily fine-tuning both electronic and steric properties formation stable rigid chelating Cu complex. Thus, this kind ligand could not only enhance reducing capability copper provide pathway but also avoid coordination other coordinating heteroatoms, thereby overcoming and/or chiral displacement. This protocol covers wide range coupling partners (89 examples secondary/tertiary bromides/chlorides amines) high functional group compatibility. When allied follow-up transformations, it provides highly flexible platform access synthetically useful amine building blocks.

Language: Английский

Citations

23
Organometallic Mn(I) Complexes in Asymmetric Catalytic (Transfer) Hydrogenation and Related Transformations DOI Creative Commons
Dexin Fu, Zheng Wang, Qingbin Liu

et al.

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(14)

Published: March 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.

Language: Английский

Citations

11
Transition-metal-catalyzed enantioselective C–N cross-coupling DOI
Jia Feng, Longlong Xi, Chuan‐Jun Lu

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(19), P. 9560 - 9581

Published: Jan. 1, 2024

Chiral amine scaffolds are among the most important building blocks in natural products, drug molecules, and functional materials, which have prompted chemists to focus more on their synthesis. Among accomplishments chiral synthesis, transition-metal-catalyzed enantioselective C-N cross-coupling is considered one of efficient protocols. This approach combines traditional C(sp

Language: Английский

Citations

8
Iridium-catalyzed direct asymmetric reductive amination utilizing primary alkyl amines as the N-sources DOI Creative Commons
Zitong Wu, Wenji Wang,

Haodong Guo

et al.

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: June 10, 2022

Abstract Direct asymmetric reductive amination is one of the most efficient methods for construction chiral amines, in which scope applicable amine coupling partners remains a significant challenge. In this study we describe primary alkyl amines effectively serve as N-sources direct catalyzed by iridium precursor and sterically tunable phosphoramidite ligands. The density functional theory studies reaction mechanism imply substrates ligand strengthened (N)H-O(P) hydrogen-bonding attraction, hydride addition occurs via an outer-sphere transition state, Cl-H H-bonding plays important role. Through concise procedure, cinacalcet, tecalcet, fendiline many other related have been synthesized single step with high yields excellent enantioselectivity.

Language: Английский

Citations

28