
Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)
Published: April 29, 2025
Language: Английский
Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)
Published: April 29, 2025
Language: Английский
Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(10)
Published: Jan. 17, 2024
Abstract An efficient catalytic asymmetric electrophilic sulfenylation reaction for the synthesis of planar‐chiral sulfur‐containing cyclophanes has been developed first time. This was achieved by using a new Lewis base catalyst and ortho ‐trifluoromethyl‐substituted sulfenylating reagent. Using substrates with low rotational energy barrier, transformation proceeded through dynamic kinetic resolution, high barrier allowed to undergo resolution process. Meanwhile, this compatible desymmetrization process when symmetric were used. Various readily obtained in moderate excellent yields enantioselectivities (up 97 % yield 95 ee). approach used synthesize pharmaceutically relevant molecules. Density functional theory calculations showed that π‐π interactions between sulfenyl group aromatic ring substrate play crucial role enantioinduction reaction.
Language: Английский
Citations
20Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(9), P. 6283 - 6293
Published: Feb. 21, 2024
We herein introduce biarylhemiboronic esters as a new type of bridged biaryl reagent for asymmetric synthesis axially chiral structures, and the palladium-catalyzed Suzuki-Miyaura cross-coupling is developed. This dynamic kinetic atroposelective coupling reaction exhibits high enantioselectivity, good functional group tolerance, broad substrate scope. The synthetic application current method was demonstrated by transformations product programmed polyarene. Preliminary mechanistic studies suggested that proceeded via an enantio-determining transmetalation step.
Language: Английский
Citations
18ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 1147 - 1157
Published: Jan. 3, 2025
This study describes a photoredox/cobalt dual-catalyzed asymmetric Grignard-type addition reaction, enabling the synthesis of axially chiral hexatomic (six–six) N-heterobiaryls bearing extra secondary alcohol unit via an efficient dynamic kinetic transformation racemic N-heterobiaryl triflate substrates. The conversion facilitated both photoredox and classical reductive reaction conditions exhibits good functional group tolerance, broad substrate scope, satisfactory stereoselectivity. Furthermore, control experiments density theory calculations provide preliminary mechanistic insights.
Language: Английский
Citations
4Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown
Published: Feb. 14, 2025
A diverse range of Pd(II)-catalyzed enantioselective C-H activation reactions have been developed to construct point, axial, and planar chirality. Despite the importance chiral biaryl scaffolds in bioactive molecules ligands, atroposelective functionalization at meta-position remains a significant challenge. Here, we realized rare remote meta-C-H with monoprotected amino acid (MPAA) ligand racemic transient norbornene mediator. The reaction starts ortho-C-H via kinetic resolution give biaryl-palladium intermediate, which subsequently undergoes Catellani relay afford meta-functionalized products (S-factors up 458). obtained enantioenriched quinoline-based atropisomers are ubiquitous natural products, pharmaceuticals, functional materials. Moreover, unprecedented meta-alkenylation alkynylation also using this approach. wide synthetic applications 8-aryl quinolines, including synthesis novel P,N-ligand materials CPL activity, demonstrated.
Language: Английский
Citations
2Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(22)
Published: March 26, 2024
Abstract Upgrading CO 2 to value‐added chiral molecules via catalytic asymmetric C−C bond formation is a highly important yet challenging task. Although great progress on the of centrally carboxylic acids has been achieved, construction axially with never reported date. Herein, we report first synthesis , which enabled by nickel‐catalyzed dynamic kinetic reductive carboxylation racemic aza‐biaryl triflates. A variety acids, are valuable but difficult obtain catalysis, generated in an enantioconvergent version. This new methodology features good functional group tolerance, easy scale‐up, facile transformation and avoids cumbersome steps, handling organometallic reagents using stoichiometric materials. Mechanistic investigations indicate process induced nickel catalysis.
Language: Английский
Citations
15Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(6), P. 1269 - 1284
Published: Jan. 31, 2024
Abstract Axially chiral architectures exist widely in natural products, biologically relevant molecules, ligands and catalysts as well functional materials. Therefore, catalytic asymmetric synthesis of atropisomers has become one the most fast‐growing fields community chemistry rapid advances have occurred. Among different methods reported, organocatalytic atroposelective dynamic kinetic resolution (DKR) involving ring manipulations stands out a cutting‐edge technology to construct axial chirality from point atom/step economy. In this DKR strategy, configurational lability starting materials originates chirally‐labile structure cyclic substrates/intermediates or transient formation through noncovalent interactions acyclic substrates. The two material are equilibrium reaction medium, ensuring constant transformation less reactive atropisomer into more one, then single enantiopure product presence an appropriate organocatalyst. This review summarizes recent advancements on topic, including their scopes, limitations, mechanisms, applications provides some insights further developments.
Language: Английский
Citations
11ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 3700 - 3710
Published: Feb. 14, 2025
Language: Английский
Citations
1ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4017 - 4024
Published: Feb. 20, 2025
Language: Английский
Citations
1ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4051 - 4060
Published: Feb. 20, 2025
Language: Английский
Citations
1Chem Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 101329 - 101329
Published: March 1, 2025
Language: Английский
Citations
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