Asymmetric synthesis of stereogenic-at-iridium(III) complexes through Pd-catalyzed kinetic resolution

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Янв. 30, 2025

Metal-centered chirality has been recognized for over one century, and stereogenic-at-metal complexes where is exclusively attributed to the metal center due specific coordination pattern of achiral ligands around ion, broadly utilized in diverse areas natural science. However, synthesis these molecules remains constrained. Notably, while asymmetric catalysis played a crucial role production optically active organic molecules, its application less straightforward. In this study, we introduce kinetic resolution strategy employing Pd-catalyzed Suzuki-Miyaura cross-coupling reaction that efficiently produces stereogenic-at-iridium from racemic mixtures with high selectivity (achieving an s-factor up 133). This method enables further relevant chiral metallodrugs photosensitizers, underscoring practical utility our approach. Mechanistic studies suggest reductive elimination likely turnover-limiting step cross-coupling.

Язык: Английский

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Enantioselective construction of inherently chiral pillar[5]arenes via palladium-catalysed Suzuki–Miyaura cross-coupling

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Март 10, 2025

Pillar[n]arenes have broad applications in biological medicine, materials science, and supramolecular gels. Notably, enantiopure pillar[5]arenes are valued for their roles enantioselective host–guest recognition, chiral sensing, asymmetric catalysis, related fields. Current methods obtaining pillar[n]arenes rely heavily on resolution agents or HPLC resolution. However, the synthesis of these compounds via catalysis remains challenging. In this study, we develop an extended side-arm Suzuki–Miyaura cross-coupling strategy to construct inherently with excellent yields high enantioselectivities using a palladium catalyst Sadphos ligand. The reaction scope extends beyond arylboronic acids encompass 2-arylvinylboronic other multi-OTf-substituted substrates, all efficiently producing desired products. Further exploration synthetic applications, along photophysical chiroptical analyses, confirm potential diverse across multiple disciplines. Enantiopure recognition but current Here, authors pillar[5]arenes.

Язык: Английский

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Bridging Homogeneous and Heterogeneous Catalysis: Phosphine‐Functionalized Metal‐Organic Frameworks

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(12)

Опубликована: Дек. 23, 2023

Abstract Phosphine‐functionalized metal‐organic frameworks (P‐MOFs) as an emerging class of coordination polymers, have provided novel opportunities for the development heterogeneous catalysts. Yet, compared with ubiquitous phosphine systems in homogeneous catalysis, heterogenization phosphines MOFs is still at its early stage. In this Minireview, we summarize synthetic strategies, characterization and catalytic reactions based on P‐MOFs reported literature. particular, various are discussed detail terms ligand structure‐function relationship, including potential obstacles future development. Finally, discuss possible solutions, new types techniques perspectives P‐MOF catalysts, highlighting challenges.

Язык: Английский

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Crossing the ortho-hurdle: Ionic stereocontrol enables atroposelective Suzuki-Miyaura coupling

Chem Catalysis, Год журнала: 2023, Номер 3(3), С. 100523 - 100523

Опубликована: Фев. 1, 2023

Язык: Английский

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Organocatalytic Atroposelective Cross‐Coupling of 1‐Azonaphthalenes and 2‐Naphthols

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(25)

Опубликована: Апрель 26, 2023

Atroposelective cross-coupling is one of the most appealing routes to construct axially chiral binaphthyl molecules due modular and succinct nature. Although transition-metal-catalyzed cross-couplings offer reliable synthetic means, alternative reaction modes that could be applied broader substrate range without their pre-functionalization highly desirable. Herein we show application Brønsted acid catalyst as organocatalyst accomplish 1-azonaphthalenes 2-naphthols with high efficiency, exclusive C4-selectivity well excellent enantioselectivity functional group compatibility. The identification acylimidazolinone auxiliary for azo activating group, effective remote control arene resonance effect synergistically play key roles in development this method. utility further demonstrated by transformations products into other compounds perfectly retained axial chirality.

Язык: Английский

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