Rhodium-Catalyzed Homogeneous Asymmetric Hydrogenation of Naphthol Derivatives DOI
Shuxin Zhang, Linhong Long, Zeyu Li

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Янв. 29, 2025

Due to their strong aromaticity and difficulties in chemo-, regio-, enantioselectivity control, asymmetric hydrogenation of naphthol derivatives 1,2,3,4-tetrahydronaphthols has remained a long-standing challenge. Herein, we report the first example homogeneous catalyzed by tethered rhodium-diamine catalysts, affording wide array optically pure high yields with excellent enantioselectivities (up 98% yield >99% ee). Mechanistic studies experimental computational approaches reveal that fluorinated solvent 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) plays vital roles control reactivity selectivity, 1-naphthol is reduced via cascade reaction pathway, including dearomative tautomerization, 1,4-hydride addition, 1,2-hydride addition sequence. A novel synergistic activation mode was proposed which HFIP assists both hydrogen molecule presence base, situ-generated fleeting keto tautomer immediately trapped Rh(III)-H species before it escapes from cage. This protocol provides straightforward practical pathway for synthesis key intermediates several chiral drugs. Particularly, Nadolol, drug treatment hypertension, angina pectoris, congestive heart failure, certain arrhythmias, enantioselectively synthesized time.

Язык: Английский

Enantioconvergent Cu-catalysed N-alkylation of aliphatic amines DOI
Ji‐Jun Chen,

Jia‐Heng Fang,

Xuan‐Yi Du

и другие.

Nature, Год журнала: 2023, Номер 618(7964), С. 294 - 300

Опубликована: Март 20, 2023

Язык: Английский

Процитировано

85
Metal Stereogenicity in Asymmetric Transition Metal Catalysis DOI Creative Commons

Philipp S. Steinlandt,

Lilu Zhang,

Eric Meggers

и другие.

Chemical Reviews, Год журнала: 2023, Номер 123(8), С. 4764 - 4794

Опубликована: Март 29, 2023

Chiral transition metal catalysts represent a powerful and economic tool for implementing stereocenters in organic synthesis, with the center providing strong chemical activation upon its interaction substrates or reagents, while overall chirality of complex achieves desired stereoselectivity. Often, chiral topology implements stereogenic center, which is then involved origin asymmetric induction. This review provides comprehensive survey reported formally constitutes stereocenter. A goes along an complex, regardless whether ligands are achiral. Implications catalyst design mechanism induction discussed half-sandwich, tetracoordinated, pentacoordinated, hexacoordinated complexes containing center. The distinguishes between originating from coordination to those solely composed optically inactive (achiral rapidly interconverting enantiomers) prior complexation (dubbed “chiral-at-metal” catalysts).

Язык: Английский

Процитировано

85
Asymmetric arene hydrogenation: towards sustainability and application DOI Creative Commons

Lukas Lückemeier,

Marco Pierau,

Frank Glorius

и другие.

Chemical Society Reviews, Год журнала: 2023, Номер 52(15), С. 4996 - 5012

Опубликована: Янв. 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.

Язык: Английский

Процитировано

52
Tailoring chirality and porosity in metal-organic frameworks for efficient enantioselective recognition DOI Creative Commons
Zongsu Han, Kunyu Wang, Mengmeng Wang

и другие.

Chem, Год журнала: 2023, Номер 9(9), С. 2561 - 2572

Опубликована: Май 23, 2023

Язык: Английский

Процитировано

46
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
Ionic Liquids in Metal, Photo-, Electro-, and (Bio) Catalysis DOI
Jaı̈rton Dupont, Bárbara C. Leal, Pedro Lozano

и другие.

Chemical Reviews, Год журнала: 2024, Номер 124(9), С. 5227 - 5420

Опубликована: Апрель 25, 2024

Ionic liquids (ILs) have unique physicochemical properties that make them advantageous for catalysis, such as low vapor pressure, non-flammability, high thermal and chemical stabilities, the ability to enhance activity stability of (bio)catalysts. ILs can improve efficiency, selectivity, sustainability bio(transformations) by acting activators enzymes, selectively dissolving substrates products, reducing toxicity. They also be recycled reused multiple times without losing their effectiveness. based on imidazolium cation are preferred structural organization aspects, with a semiorganized layer surrounding catalyst. act container, providing confined space allows modulation electronic geometric effects, miscibility reactants residence time species. stabilize ionic radical species control catalytic dynamic processes. Supported IL phase (SILP) derivatives polymeric (PILs) good options molecular engineering greener The major factors governing metal, photo-, electro-, biocatalysts in discussed detail vast literature available over past two half decades. Catalytic reactions, ranging from hydrogenation cross-coupling oxidations, promoted homogeneous heterogeneous catalysts both single multiphase conditions, extensively reviewed considering knowledge accumulated until now.

Язык: Английский

Процитировано

42
P-Stereogenic Phosphorus Ligands in Asymmetric Catalysis DOI
Tsuneo Imamoto

Chemical Reviews, Год журнала: 2024, Номер 124(14), С. 8657 - 8739

Опубликована: Июль 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.

Язык: Английский

Процитировано

40
Manganese‐Catalyzed Asymmetric Hydrogenation of 3H‐Indoles DOI
Chenguang Liu, Mingyang Wang,

Yihan Xu

и другие.

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(20)

Опубликована: Март 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

Язык: Английский

Процитировано

55
Nickel-Catalyzed Regio- and Enantioselective Hydroamination of Unactivated Alkenes Using Carbonyl Directing Groups DOI
Changseok Lee, Hyung‐Joon Kang, Huiyeong Seo

и другие.

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(20), С. 9091 - 9100

Опубликована: Май 11, 2022

The asymmetric addition of an N–H bond to various alkenes via a direct catalytic method is powerful way synthesizing value-added chiral amines. Therefore, the enantio- and regioselective hydroamination unactivated remains appealing goal. Here, we report highly Ni-catalyzed readily available bearing weakly coordinating native amides or esters. This succeeds for both terminal internal has broad amine coupling partner scope. mild reaction process well suited late-stage functionalization complex molecules potential gain modular access enantioenriched β- γ-amino acid derivatives 1,2- 1,3-diamines. Mechanistic studies reveal that bisoxazoline-bound Ni specie effectively leverages carbonyl coordination achieve NiH insertion into alkenes.

Язык: Английский

Процитировано

49
Expanding chiral metamaterials for retrieving fingerprints via vibrational circular dichroism DOI Creative Commons
Cheng Xu, Zhihao Ren, Hong Zhou

и другие.

Light Science & Applications, Год журнала: 2023, Номер 12(1)

Опубликована: Июнь 25, 2023

Circular dichroism (CD) spectroscopy has been widely demonstrated for detecting chiral molecules. However, the determination of mixtures with various concentrations and enantiomeric ratios can be a challenging task. To solve this problem, we report an enhanced vibrational circular (VCD) sensing platform based on plasmonic metamaterials, which presents 6-magnitude signal enhancement selectivity Guided by coupled-mode theory, leverage both in-plane out-of-plane symmetry-breaking structures metamaterial design enabled two-step lithography process, increases near-field coupling strengths varies ratio between absorption radiation loss, resulting in improved light-matter interaction molecular VCD signals. Besides, demonstrate thin-film process BSA β-lactoglobulin proteins, contain secondary α-helix β-sheet achieve limit detection down to zeptomole level. Furthermore, also, first time, explore potential demonstrating selective mixtures, where mixing successfully differentiated our proposed metamaterials. Our findings improve molecules expand extractable information, paving way toward label-free, compact, small-volume molecule stereochemical clinical diagnosis applications.

Язык: Английский

Процитировано

28