Enantioselective Synthesis of Axially and Centrally Chiral Styrenes via Nickel-Catalyzed Desymmetric Hydrocyanation of Biaryl Dienes

Organic Letters, Год журнала: 2024, Номер 26(18), С. 3867 - 3871

Опубликована: Май 1, 2024

Herein, a highly regio-, enantio-, and diastereoselective nickel-catalyzed desymmetric hydrocyanation of biaryl dienes for the simultaneous construction axial central chiralities is presented, which offers convenient approach to variety tirenes containing union an axially chiral centrally α-chiral nitrile under mild conditions using commercially available catalyst. The synthetic utility highlighted by development novel phosphine ligand biphenyl-based diene their potential applications in field asymmetric catalytic reactions.

Язык: Английский

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Diverse Synthesis of C-Glycosides by Stereoselective Ni-Catalyzed Carboboration of Glycals

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(28), С. 18866 - 18872

Опубликована: Июль 5, 2024

C-Glycosides are important structures that common to natural products and pharmaceutical agents. Established methods for their synthesis involve the reaction of an activated anomeric carbon. In this study, we report a conceptually new approach involves stereoselective Ni-catalyzed carboboration glycals. these reactions, not only is C–C bond formed at carbon, but synthetically useful C–B also installed. Upon oxidation, differentially protected C-glycosides be formed. addition, stereospecific manipulation leads diverse C-glycosides. Finally, application method in established C-glycosides, such as C-glycosyl amino acids, well strategy make all possible diastereomers C1 C2.

Язык: Английский

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Regio- and Diastereoselective Highly Strained Alkylidenecyclobutane Isomerization/Hydroacylation: Synthesis of Multisubstituted Cyclobutanes with Consecutive Stereocenters

ACS Catalysis, Год журнала: 2024, Номер 14(3), С. 1505 - 1513

Опубликована: Янв. 16, 2024

The regio- and diastereoselective alkene isomerization hydrofunctionalization sequence enabled by transition-metal complexes allows rapid activation assembly of the C(sp3)–H bond that is either adjacent or distal to initial double bond, which has been a longstanding challenge in this field. Herein, we develop unusual rhodium-catalyzed alkylidenecyclobutanes with subsequent hydroacylation reaction provide multisubstituted cyclobutanes continuous stereocenters. Note tandem process features good diastereoselectivity profile. Isotopic labeling experiments support "exo endo" migration coordinated cyclobutene responsible for deuterium incorporation observed cyclobutane product.

Язык: Английский

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Enantioselective Synthesis of β-Aminoboronic Acids via Borylalkylation of Enamides

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(24), С. 16639 - 16647

Опубликована: Июнь 10, 2024

Aminoboronic acids represent a class of significant compounds that have attracted attention in the fields drug discovery and organic synthesis. Despite notable progress their synthesis, efficient construction chiral β-aminoboronic with alkyl side chains remains challenging endeavor. Here, we introduce an unprecedented nickel-catalyzed asymmetric borylalkylation enamides, employing simple diamine ligand, readily available B2pin2, halides as coupling partners. This reaction serves platform for assembling diverse range acid derivatives flexible chains, displaying exceptional regio-, stereo-, enantioselectivities. Moreover, this transformation exhibits broad substrate scope remarkable tolerance toward various functional groups. Theoretical calculations demonstrate benzyl group on ligand is key to high enantiocontrol transformation. Additionally, exemplify practical application strategy through concise synthesis complex bioactive molecules.

Язык: Английский

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Recent Advances in Ni‐Catalyzed 1,1‐Difunctionalization of Unactivated Olefins

Advanced Synthesis & Catalysis, Год журнала: 2023, Номер 366(4), С. 593 - 602

Опубликована: Дек. 7, 2023

Abstract Unactivated olefins rank amongst the most important feedstocks in organic synthesis. Their availability makes them particularly useful synthons for subsequent functionalization, a catalytic manner. Driven by popularity ascribed nickel catalysis as new tool to rapidly forge molecular architectures via one‐or two‐electron manifolds, recent years have witnessed significant advances Ni‐catalyzed olefin difunctionalization. While 1,2‐difunctionalization or remote functionalization “chain‐walk” become mature disciplines repurposing potential of building blocks, it was only recently that extensions this chemistry 1,1‐difunctionalization been possible. This review summarizes 1,1‐difunctionalization, holding considerable promise powerful strategy our ever‐growing synthetic repertoire.

Язык: Английский

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Mechanochemical aerobic oxidative Heck coupling by polymer-assisted grinding: cyclodextrin additive facilitating regioselectivity control

Green Chemistry, Год журнала: 2024, Номер 26(10), С. 5890 - 5899

Опубликована: Янв. 1, 2024

A novel approach utilizing the polymer-assisted grinding (POLAG) technique to facilitate regioselective oxidative Heck coupling of aryl boronic acids with electronically unbiased olefins under solvent-free conditions was presented.

Язык: Английский

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Stereoselective Construction of Multifunctional C-Glycosides Enabled by Nickel-Catalyzed Tandem Borylation/Glycosylation

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(32), С. 22413 - 22423

Опубликована: Авг. 3, 2024

Stereochemically pure saccharides have indispensable roles in fields ranging from medicinal chemistry to materials science and organic synthesis. However, the development of a simple, stereoselective, efficient glycosylation protocol access α- β-C-glycosides (particularly 2-deoxy entities) remains persistent challenge. Existing studies primarily focused on C1 modification carbohydrates transformation glycosyl radical precursors. Here, we innovate by harnessing situ generated glycosyl-Ni species achieve one-pot borylation cascade manner, which is enabled an earth-abundant nickel-catalyzed carboboration readily accessible glycals without any ligand. This work reveals potential for modular multifunctional platform facilitate simultaneous introduction C-C C-B bonds at stereogenic center saccharides, largely unexploited research area. Preliminary experimental computational indicate that endocyclic O C3 group play important stereoseclectively forging glycosidic bonds. As result, diverse range C-R (R = alkyl, aryl, alkenyl) 2-deoxygenated glycosides bearing modifiable boron groups could be rapidly made with excellent stereocontrol exhibit remarkable functional tolerance. The synthetic underscored late-stage natural products commercial drugs as well facile preparation various rare sugars, bioactive conjugates, key intermediates prorocentin, phomonol, aspergillide A.

Язык: Английский

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Enantioselective Copper-Catalyzed Three-Component Cascade Boronation–Dearomatization Reaction: Synthesis of Chiral Boron-Containing 1,4-Dihydropyridines

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Янв. 10, 2025

A three-component cascade boronation–dearomatization reaction of alkenes, a diboron compound, and pyridinium salt is diclosed, affording chiral boron-containing 1,4-dihyropyridines in high yields (≤98%) diastereoselectivity (≤10:1 dr), along with excellent enantioselectivity (typically >99% ee). The catalytic system performs efficiently at low catalyst loadings (1 mol %) was tested >50 examples, including some biologically active molecules.

Язык: Английский

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Ni-Catalyzed Regioselective and Site-divergent Reductive Arylalkylations of Allylic Amines

Chemical Science, Год журнала: 2025, Номер 16(10), С. 4442 - 4449

Опубликована: Янв. 1, 2025

Catalytic methods by switching the least parameters for regioselective and site-divergent transformations to construct different architectures from identical readily available starting materials are among most ideal catalytic protocols. However, associated challenge precisely control both regioselectivity site diversity renders this strategy appealing yet challenging. Herein, Ni-catalyzed cross-electrophile 1,2- 1,3-arylalkylations of N-acyl allylic amines have been developed. This reductive three-component protocol enables 1,2-arylalkylation 1,3-arylalkylation with aryl halides alkyl excellent chemo-, regio- site-selectivity, representing first example controlled migratory difunctionalization alkenes under conditions. A wide range terminal internal unactivated amines, precursors were tolerated, providing straightforward efficient access diverse C(sp3)-rich branched aliphatic materials.

Язык: Английский

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Ni-catalysed acceptorless dehydrogenative aromatisation of cyclohexanones enabled by concerted catalysis specific to supported nanoparticles

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

Опубликована: Фев. 7, 2025

The dehydrogenative aromatisation of cyclohexanone derivatives has had a transformative influence on the synthesis aromatic compounds because functional groups can be easily introduced at desired positions via classic organic reactions without being limited by ortho-, meta- or para-orientations. However, research is still acceptorless aromatisation, especially with regard to nonprecious-metal catalysts. Ni promising candidate catalyst as congener Pd, but thermally Ni-catalysed not been reported even in an oxidative manner difficulty β-hydride elimination and fast re-insertion Ni–H species. Here, we report CeO2-supported Ni(0) nanoparticle for derivatives. This widely applicable various such cyclohexanols, cyclohexylamines, N-heterocycles, enamines β-heteroatom-substituted ketones. Through experiments, demonstrate that present reaction was achieved concerted catalysis utilizing metal ensembles unique supported Acceptorless aromatization cyclohexanones advantageous nickel study presents method broad substrate applicability, nanoparticles.

Язык: Английский

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