Reversing the Regioselectivity of Asymmetric C ̶ H and N ̶ H Bond Annulation with Bromoalkynes Under Cobalt(III)-Catalysis DOI Creative Commons

Abir Das,

Rajib Mandal,

Harihara Subramanian

и другие.

Опубликована: Март 22, 2023

Metal-catalyzed C-H bond annulation strategy offers a versatile platform, allowing the construction of complex p-chiral molecules through atom- and step-economical fashion. However, regioselective insertion -coupling partner between M-C high enantio-induction remain elusive. Using commercially available Co(II) salt chiral-salox ligands, we demonstrate an unorthodox protocol for regio-reversal, enantioselective phosphanamide with bromoalkyne asymmetric desymmetrization. This method was accomplished by sequentical activation, migratory insertion, reductive elimination, ligand exchange carboxylate, which resulted in formation novel P-stereogeneic compounds good substrate scope ee (up to 99% ee). The isolation reactive intermediates involved catalytic cycle outcomes control experiments provide support plausible mechanism.

Язык: Английский

Palladium-catalyzed cross-coupling of alcohols with olefins by positional tuning of a counteranion DOI
Sven H. Kaster, Lei Zhu, William L. Lyon

и другие.

Science, Год журнала: 2024, Номер 385(6713), С. 1067 - 1076

Опубликована: Сен. 5, 2024

Transition metal-catalyzed cross-couplings have great potential to furnish complex ethers; however, challenges in the C(sp

Язык: Английский

Процитировано

8
Controlled and Regioselective Ring-Opening Polymerization for Poly(disulfide)s by Anion-Binding Catalysis DOI

Tianyi Du,

Boming Shen,

Jieyu Dai

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(50), С. 27788 - 27799

Опубликована: Ноя. 21, 2023

Poly(disulfide)s are an emerging class of sulfur-containing polymers with applications in medicine, energy, and functional materials. However, the constituent dynamic covalent S-S bond is highly reactive presence sulfide (RS-) anion, imposing a persistent challenge to control polymerization. Here, we report anion-binding approach arrest high reactivity RS- chain end synthesis linear poly(disulfide)s, realizing rapid, living ring-opening polymerization 1,2-dithiolanes narrow dispersity regioselectivity (Mw/Mn ∼ 1.1, Ps 0.85). Mechanistic studies support formation thiourea-base-sulfide ternary complex as catalytically active species during propagation. Theoretical analyses reveal synergistic catalytic model where catalyst preorganizes protonated base anionic establish spatial confinement over bound monomer, effecting observed regioselectivity. The system amenable monomers various groups, semicrystalline also obtained from lipoic acid derivatives by enhancing

Язык: Английский

Процитировано

18
Reversal of Regioselectivity in Asymmetric C−H Bond Annulation with Bromoalkynes under Cobalt Catalysis** DOI

Abir Das,

Rajib Mandal,

Harihara Subramanian Ravi Sankar

и другие.

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(6)

Опубликована: Дек. 14, 2023

Abstract Metal‐catalyzed asymmetric C−H bond annulation strategy offers a versatile platform, allowing the construction of complex P‐chiral molecules through atom‐ and step‐economical fashion. However, regioselective insertion π‐coupling partner between M−C with high enantio‐induction remain elusive. Using commercially available Co(II) salt chiral‐Salox ligands, we demonstrate an unusual protocol for regio‐reversal, enantioselective phosphinamide bromoalkyne desymmetrization. The reaction proceeds ligand‐assisted enantiodetermining cyclocobaltation followed by Co−C, subsequent reductive elimination, halogen exchange carboxylate resulted in P‐stereogenic compounds excellent ee (up to >99 %). isolation cobaltacycle involved catalytic cycle outcome control experiments provide support plausible mechanism.

Язык: Английский

Процитировано

16
Silver(I)/Dirhodium(II) Catalytic Platform for Asymmetric N–H Insertion Reaction of Heteroaromatics DOI
Shingo Harada,

Shumpei Hirose,

Mizuki Takamura

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 146(1), С. 733 - 741

Опубликована: Дек. 27, 2023

Transition-metal-catalyzed enantioselective N–H insertion reactions of carbene species offer a powerful and straightforward strategy to produce chiral nitrogen-containing compounds. Developing highly selective using indole variants can meet synthetic demand. Herein we present an asymmetric reaction into bonds the aromatic heterocycles donor/acceptor-substituted diazo compounds based on heteronuclear catalytic platform. Although previously developed catalysis comprising silver catalyst or dirhodium(II,II) paddlewheel complexes with without phosphoric acid showed modest performance, unique combination widely available Rh2(OAc)4 silver(I) phosphate dimer [(S)-TRIP-Ag]2 enabled (up 98% ee). Moreover, Ag/Rh system facilitated regioselective C–H functionalization protic indoles. Mechanistic investigation density functional theory indicated that in situ-generated Ag–Rh trimetallic enolate is protonated environment.

Язык: Английский

Процитировано

12
Design Approaches That Utilize Ionic Interactions to Control Selectivity in Transition Metal Catalysis DOI Creative Commons
Harry Adams,

Max Kadarauch,

Nicholas J. Hodson

и другие.

Chemical Reviews, Год журнала: 2025, Номер unknown

Опубликована: Фев. 28, 2025

The attractive force between two oppositely charged ions can constitute a powerful design tool in selective catalysis. Enzymes make extensive use of ionic interactions alongside variety other noncovalent interactions; recent years have seen synthetic chemists begin to seriously explore these catalyst designs that also incorporate reactive transition metal. In isolation, single interaction exhibits low directionality, but many successful systems they exist additional which provide high degree organization at the selectivity-determining state. Even situations with key interaction, directionality is not always detrimental, and even be advantageous, conferring generality catalyst. This Review explores approaches utilize control selectivity metal It divided into halves: first, occurs outer sphere complex, using ligand or bound an anion; second, bears formal charge, associated counterion.

Язык: Английский

Процитировано

0
Charge-assisted hydrogen bonding in a bicyclic amide cage: an effective approach to anion recognition and catalysis in water DOI Creative Commons
Chengkai Xu, Quy Gia Tran, Dexin Liu

и другие.

Chemical Science, Год журнала: 2024, Номер unknown

Опубликована: Янв. 1, 2024

Hydrogen bonding is prevalent in biological systems, dictating a myriad of life-sustaining functions aqueous environments. Leveraging hydrogen for molecular recognition water encounters significant challenges synthetic receptors on account the hydration their functional groups. Herein, we introduce water-soluble cage, synthesized

Язык: Английский

Процитировано

3
Asymmetric Carbene Insertion into Se‐S Bonds by Synergistic Rh(II)/Guanidine Catalysis Involving Chalcogen‐Bond Assistance DOI
Xin He,

Yihua Fu,

Ruiying Xi

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 2, 2024

The efficient construction of chalcogen-atom-based chiral compounds remains a challenge, despite the importance organoselenium and organosulfur in life materials science. Chalcogen atoms can form net attractive interactions called chalcogen bonds, but it is an undeveloped tool to assist asymmetric catalysis. Herein, we report enantioselective insertion platform install stereogenic center bearing selenyl thiocyano functional groups. Our method operates by synergistic catalysis guanidine achiral dirhodium complex three-component or four-component reaction, through Se-S bond into carbene species, competing successfully with spontaneous racemic process showing high regioselectivity. As elucidated spectroscopic experiments computational studies, unique mechanism involving as well hydrogen bonding was established account for enantiocontrol. stereoselectivity holds broad array selenylthiocyanatopropanoates, which showed excellent anti-inflammatory toward IL-1β low cytotoxicity.

Язык: Английский

Процитировано

3
Investigating the diastereoselective synthesis of a macrocycle under Curtin–Hammett control DOI Creative Commons

Angus Yeung,

Martijn A. Zwijnenburg, Georgia R. F. Orton

и другие.

Chemical Science, Год журнала: 2024, Номер 15(15), С. 5516 - 5524

Опубликована: Янв. 1, 2024

The Curtin–Hammett principle is used to understand the diastereoselective synthesis of a heterochiral over homochiral macrocycle, both which are configurationally stable chiral macrocycles.

Язык: Английский

Процитировано

2
A chiral pentanidium and pyridinyl-sulphonamide ion pair as an enantioselective organocatalyst for Steglich rearrangement DOI Creative Commons
Ziqi Yang, Chaoran Xu,

Xianxian Zhou

и другие.

Chemical Science, Год журнала: 2023, Номер 14(45), С. 13184 - 13190

Опубликована: Янв. 1, 2023

Enantioselective ion pair catalysis has gained significant attention due to its ability exert selectivity control in various reactions. Achiral counterions have been found play crucial roles modulating reactivity and selectivity. The modular nature of an catalyst allows rapid alterations the achiral counterion achieve optimal outcomes, without need modify more onerous chiral component. In this study, we report successful development a stable pentanidium pyridinyl-sulphonamide as nucleophilic organocatalyst for asymmetric Steglich rearrangement. demonstrated excellent performance, leading enantioenriched products with up 99% ee through simple anions. We conducted extensive ROESY experiments concluded that enantioselectivity were correlated formation tight solution. Further computational analyses provided greater clarity structure Our findings reveal critical NMR design optimisation catalysts.

Язык: Английский

Процитировано

4
Enhanced Ligand Discovery through Generative AI and Latent-Space Exploration: Application to the Mizoroki-Heck Reaction DOI Creative Commons
Wenxin Lu, Haote Li, Jan Paul Menzel

и другие.

Опубликована: Март 1, 2024

The identification of catalysts that promote chemical reactions is a critical challenge in the production pharmaceuticals. One main bottlenecks this process synthesis vast libraries precatalysts, although assessing catalyst effectiveness can be rapidly conducted through high-throughput experimentation. rational design and development high-performing precatalysts circumvent lead to important advances. In study, we apply transformer-based Kernel-Elastic Autoencoder (KAE) equipped with conditioned latent space, enabling targeted generation ligands desired steric electronic properties. Our KAE model has facilitated monodentate alkynylphosphine, dubbed MachinePhos A, as an effective precatalyst for forming carbon-carbon bond. Its utility was demonstrated experimentally Mizoroki-Heck reaction, using variety nitrogen-rich arenes pertinent pharmaceutical applications.

Язык: Английский

Процитировано

1