Enantioselective Divergent Syntheses of Cephalotaxus Alkaloids: (−)-Cephalotaxine, (−)-Cephalotine B, and (−)-Fortuneicyclidins A and B DOI
Xian‐Tao An,

Xiao‐Min Ge,

Xinyu Liu

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(16), P. 9233 - 9241

Published: April 12, 2023

A new strategy focusing on the last-stage asymmetric assembly of ring D, which inherently possesses densest part stereogenic centers and functional groups in A/B/C/D system (-)-cephalotaxine, has been developed, a novel Rh-catalyzed (2 + 3) annulation tertiary enamides with enoldiazoacetates is designed explored for enantioselective construction crucial cyclopentane D bearing unique spirocyclic aza-quaternary stereocenter. Based expeditious access chiral functionalized building block tetracyclic system, concise total synthesis (-)-cephalotaxine starting from readily available homopiperonyl alcohol achieved nine steps only two column chromatography purifications. Following tactical introduction Meinwald rearrangement, divergent syntheses (-)-cephalotine B an additional C3-O-C11 oxo-bridged bond (14 steps), (-)-fortuneicyclidin unprecedented C3-C10 its 2-epimer (16 steps) have also accomplished first time.

Language: Английский

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

Jia‐Heng Fang,

Xuan‐Yi Du

et al.

Nature, Journal Year: 2023, Volume and Issue: 618(7964), P. 294 - 300

Published: March 20, 2023

Language: Английский

Citations

92
Metal Stereogenicity in Asymmetric Transition Metal Catalysis DOI Creative Commons

Philipp S. Steinlandt,

Lilu Zhang,

Eric Meggers

et al.

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(8), P. 4764 - 4794

Published: March 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).

Language: Английский

Citations

91
Asymmetric arene hydrogenation: towards sustainability and application DOI Creative Commons

Lukas Lückemeier,

Marco Pierau,

Frank Glorius

et al.

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

Citations

56
Ionic Liquids in Metal, Photo-, Electro-, and (Bio) Catalysis DOI
Jaı̈rton Dupont, Bárbara C. Leal, Pedro Lozano

et al.

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(9), P. 5227 - 5420

Published: April 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.

Language: Английский

Citations

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

et al.

Chem, Journal Year: 2023, Volume and Issue: 9(9), P. 2561 - 2572

Published: May 23, 2023

Language: Английский

Citations

49
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

45
P-Stereogenic Phosphorus Ligands in Asymmetric Catalysis DOI
Tsuneo Imamoto

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

Citations

45
Manganese‐Catalyzed Asymmetric Hydrogenation of 3H‐Indoles DOI
Chenguang Liu, Mingyang Wang,

Yihan Xu

et al.

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

Citations

56
Nickel-Catalyzed Regio- and Enantioselective Hydroamination of Unactivated Alkenes Using Carbonyl Directing Groups DOI
Changseok Lee, Hyung‐Joon Kang, Huiyeong Seo

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(20), P. 9091 - 9100

Published: May 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.

Language: Английский

Citations

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

et al.

Light Science & Applications, Journal Year: 2023, Volume and Issue: 12(1)

Published: June 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.

Language: Английский

Citations

32