Enantioselective C–C cross-coupling of unactivated alkenes

Nature Catalysis, Год журнала: 2023, Номер 6(11), С. 1087 - 1097

Опубликована: Окт. 5, 2023

Язык: Английский

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Asymmetric Total synthesis of Asperones A and B through Organocatalyzed Quinone [5 + 2] Cycloaddition

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Фев. 13, 2025

The first asymmetric total synthesis of the anti-inflammatory polyketides asperones A (1) and B (2) has been accomplished. Key synthetic steps include a Diels-Alder retro-Diels-Alder cascade to construct poly substituted phenol, an Al-Salen-catalyzed cyanosilylation form tertiary alcohol gregatin A, organocatalyzed intermolecular [5 + 2] cycloaddition p-quinone with electron-deficient alkenes build crucial [3.2.1] octane core (2).

Язык: Английский

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Enantioselective C–H annulations enabled by either nickel- or cobalt-electrocatalysed C–H activation for catalyst-controlled chemodivergence

Nature Catalysis, Год журнала: 2025, Номер unknown

Опубликована: Март 7, 2025

Язык: Английский

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Asymmetric Carbohydroxylation of Alkenes Using Photoenzymatic Catalysis

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(31), С. 17018 - 17022

Опубликована: Июль 27, 2023

Alkene difunctionalizations enable the synthesis of structurally elaborated products from simple and ubiquitous starting materials in a single chemical step. Carbohydroxylations olefins represent family reactivity that furnish complex alcohols. While examples this type three-component coupling have been reported, catalytic asymmetric remain elusive. Here, we report an enzyme-catalyzed carbohydroxylation alkenes catalyzed by flavin-dependent "ene"-reductases to produce enantioenriched tertiary Seven rounds protein engineering reshape enzyme's active site increase activity enantioselectivity. Mechanistic studies suggest C–O bond formation occurs via 5-endo-trig cyclization with pendant ketone afford α-oxy radical which is oxidized hydrolyzed form product. This work demonstrates photoenzymatic reactions involving can terminate radicals mechanisms other than hydrogen atom transfer, expanding their utility synthesis.

Язык: Английский

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Advancing Heterogeneous Organic Synthesis With Coordination Chemistry‐Empowered Single‐Atom Catalysts

Advanced Materials, Год журнала: 2024, Номер unknown

Опубликована: Сен. 18, 2024

Abstract For traditional metal complexes, intricate chemistry is required to acquire appropriate ligands for controlling the electron and steric hindrance of active centers. Comparatively, preparation single‐atom catalysts much easier with more straightforward effective accesses arrangement control The presence coordination atoms or neighboring functional on supports' surface ensures stability single‐atoms their interactions individual substantially regulate performance Therefore, collaborative interaction between surrounding environment enhances initiation reaction substrates formation transformation crucial intermediate compounds, which imparts significant catalytic efficacy, rendering them a valuable framework investigating correlation structure activity, as well mechanism in organic reactions. Herein, comprehensive overviews both homogeneous complexes reactions are provided. Additionally, reflective conjectures about advancement synthesis also proposed present reference later development.

Язык: Английский

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Copper-catalysed dynamic kinetic asymmetric C−O cross-coupling to access chiral aryl oxime ethers and diaryl ethers

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

Опубликована: Март 13, 2025

Dynamic kinetic resolution (DKR) has emerged as an elegant and powerful tool for enantioselective synthesis, enabling the transformation of racemic compounds into enantiomerically enriched products with theoretically quantitative yields. Despite its widespread success, dynamic asymmetric C−O cross-coupling presented significant challenges remains unexplored. In this study, we report a oximes phenols via copper/BOX-catalysed O-arylation diaryliodonium salts. This method efficiently produces wide range inherently chiral oxime ethers, well axially styrenes, high yields excellent regio- enantioselectivities. Through controlled experiments Density Functional Theory (DFT) studies, have elucidated process gained insights origins enantioselectivity. The Here, authors

Язык: Английский

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Dynamic kinetic asymmetric allylation, propargylation and crotylation of ketones using copper catalysis

Nature Synthesis, Год журнала: 2024, Номер 3(9), С. 1091 - 1103

Опубликована: Июнь 25, 2024

Язык: Английский

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Nickel-catalyzed acylzincation of allenes with organozincs and CO

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Окт. 31, 2023

Transition metal-catalyzed carbonylative reaction with CO gas are among the central task in organic synthesis, enabling construction of highly valuable carbonyl compound. Here, we show an earth-abundant nickel-catalyzed three-component tandem acylzincation/cyclization sequence allene and alkylzinc reagent 1 atm under mild conditions. This protocol is featured by broad functional group tolerance high selectivity, providing a rapid convenient synthetic method for diverse fully substituted benzotropone derivatives. Mechanistic studies reveal that installation cyano tethered to moiety enables regio- stereoselectivity this acylzincation allene, allowing selective formation three consecutive C-C bonds efficient manner.

Язык: Английский

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Bifunctional NHC-Promoted C2-Alkylation of Pyridine via Ni–Al Bimetallic-Catalyzed Hydroarylation of Unactivated Alkenes

ACS Catalysis, Год журнала: 2023, Номер 13(9), С. 6068 - 6075

Опубликована: Апрель 18, 2023

Achieving site-selective alkylation with pyridine under transition metal catalysis has remained a long-standing challenge, especially when using unactivated alkene as an alkylating reagent. We herein describe C2-alkylation of Ni–Al bimetallic and directing bifunctional N-heterocyclic carbene (NHC) ligand through hydroarylation alkenes. A broad range C2-alkylated pyridines various functionalities could be prepared in high efficiency (up to 99% yield) C2-selectivity, the scope heterocycles is not limited but can expanded other azines like pyrazines pyrimidines. Mechanistic studies suggest that NHC–Ni–Al–pyridine complex responsible for site selectivity control reductive elimination might rate-determining step.

Язык: Английский

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Synthesis of Enantioenriched 1,2‐cis Disubstituted Cycloalkanes by Convergent NiH Catalysis

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(36)

Опубликована: Июль 20, 2023

Enantioenriched multi-substituted cycloalkanes constitute an essential class of compounds in pharmaceuticals, natural products and agrochemicals. Here we report NiH-catalyzed asymmetric migratory hydroalkylation process for the efficient selective construction such compounds. Through a dynamic kinetic transformation (DYKAT), easily accessible racemic isomeric mixtures cycloalkenes could be directly utilized as starting materials, convergently producing thermo-dynamically disfavored chiral 1,2-cis disubstituted bearing vicinal stereocenters with high levels regio-, diastereo- enantioselectivity. In addition, prochiral cyclic alkenes can also employed, deliver through desymmetrization process.

Язык: Английский

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