Metal-organic framework boosts heterogeneous electron donor–acceptor catalysis

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

Опубликована: Ноя. 27, 2023

Abstract Metal-organic framework (MOF) is a class of porous materials providing an excellent platform for engineering heterogeneous catalysis. We herein report the design MOF Zr-PZDB consisting Zr 6 -clusters and PZDB (PZDB = 4,4’-(phenazine-5,10-diyl)dibenzoate) linkers, which served as donor catalyst enhanced electron donor–acceptor (EDA) photoactivation. The high local concentration dihydrophenazine active centers in can promote EDA interaction, therefore resulting superior catalytic performance over homogeneous counterparts. crowded environment protect center from being attacked by radical species. efficiently catalyzes Minisci-type reaction N -heterocycles with series C-H coupling partners, including ethers, alcohols, non-activated alkanes, amides, aldehydes. also enables aryl sulfonium salts heterocycles. activity extends to late-stage functionalization bioactive drug molecules, Nikethamide, Admiral, Myristyl Nicotinate. Systematical spectroscopy study analysis support interaction between pyridinium salt or salt, respectively. Photoactivation MOF-based adduct triggers intra-complex single transfer acceptor, giving open-shell species cross-coupling reactions. This research represents first example MOF-enabled

Язык: Английский

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A copper-catalyzed B–H bond insertion reaction of azide–ynamide with borane adductsviaα-imino copper carbenes

Organic Chemistry Frontiers, Год журнала: 2022, Номер 9(10), С. 2773 - 2778

Опубликована: Янв. 1, 2022

A new copper-catalyzed B–H bond insertion into α-imino copper carbenes generated from azide–ynamide cyclization has been developed, leading to a facile and practical synthesis of series α-boryl amidines.

Язык: Английский

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Synthesis of α-Boryl Ketones via Hydration or Oxidation of B(MIDA)-Decorated Alkynes

Organic Letters, Год журнала: 2023, Номер 25(7), С. 1099 - 1103

Опубликована: Фев. 15, 2023

α-Boryl ketones are traditionally challenging targets in organic synthesis. Reported herein is a mild and metal-free synthesis of α-boryl via the hydration or oxidation N-methyliminodiacetyl boronate (B(MIDA))-decorated alkynes. A new system comprised AcCl H2O HFIP allows arylethynyl B(MIDA)s at room temperature with decent functional group tolerance. An oxidative carbon deletion process propargylic also developed for aliphatic ketones. intriguing β-boron effect was observed to account unique site- chemoselectivities. The application products borylated heterocycles demonstrated.

Язык: Английский

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(1,3‐Dihydro‐1,3‐dimethyl‐2 H ‐imidazol‐2‐ylidene)trihydroboron (1)

Encyclopedia of Reagents for Organic Synthesis, Год журнала: 2024, Номер unknown, С. 1 - 8

Опубликована: Апрель 18, 2024

image [1211417‐77‐4] C 5 H 11 BN 2 (MW 109.97) InChI = 1S/C5H11BN2/c1‐7‐3‐4‐8(2)5(7)6/h3‐4H,1‐2,6H3 InChiKey WDITXRGBBBKEET‐UHFFFAOYSA‐N (hydroboration, radical reduction; hydride reduction) Alternative Name(s) : diMe‐Imdg‐BH 3 , (1,3‐Dimethyl‐1H‐imidazol‐3‐ium‐2‐yl)trihydroborate, 1,3‐Dimethylimidazoyl‐2‐ylidene borane. 1 Physical Data white solid, mp: 138–139 °C. Solubility is soluble in several organic solvents such as dimethylsulfoxide, N ‐dimethylformamide, ethyl acetate, methanol, chloroform, dichloromethane, acetonitrile, mixtures acetonitrile/water up to 0.1 M. Form Supplied commercially available the form of a solid. Analysis Reagent Purity compound air‐ and moisture‐stable at 23 °C for least 12 months, impurities derive from synthesis usually not decomposition. The purity conveniently determined via NMR (CDCl ). ) δ 6.80 (s, ), 3.74 6 1.49–0.53 (m, J 11B–H 86.5 Hz, 10B–H 29.0 Hz). 13 172.0 (q, B−C 50 Hz), 120.0, 35.9. B −37.5 B–H 86.4 Preparative Methods title prepared two‐step procedure ‐methylimidazole (eq 1), mmol scale. Step 1: Methyl iodide (1.2 equiv) added dropwise dichloromethane solution corresponding imidazole (5 M) over course 15 min an ice bath (Caution: exothermic reaction!). After addition, removed reaction mixture allowed stir h, after which concentrated dried under vacuum give 1,3‐dimethyl‐1 ‐imidazol‐3‐ium yields ranging 95% quantitative. latter can be checked H‐NMR (CD OD) typically used without any further purification. 2: suspended toluene (1 mL −1 sodium borohydride one portion. vigorously refluxed 16 h. hot solvent was decanted insoluble mixture, remaining residue extracted with (2 × volume). Toluene pressure good (usually > 90%). In case purification needed, purified flash chromatography or crystallization (vide infra). synthetic approaches rely on deprotonation strong base bis(trimethylsilyl)amide generate N‐heterocyclic carbene subsequent quenching BH (as tetrahydrofuran, dimethylsulfide, 4 amine, phosphine complex). Purification silica gel (cyclohexane:ethyl acetate 20 80). Recrystallization O (14 g gives pure fine crystals (Cryst. yield: 73%). Handling, Storage, Precautions stored room temperature (20–23 °C) air‐equilibrated conditions. sensitive ambient light. All possible precautions should taken avoid contact eyes ( H319 skin H315 inhalation H335 well. 7

Язык: Английский

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Radical borylation of vinyl azides with NHC-boranes: divergent synthesis of α-boryl ketones and borylated triazoles

Organic & Biomolecular Chemistry, Год журнала: 2022, Номер 20(17), С. 3550 - 3557

Опубликована: Янв. 1, 2022

A radical borylation of vinyl azides with NHC-boranes in the presence t BuSH is described, which enables divergent synthesis α-boryl ketones and borylated triazoles excellent functional group tolerance a broad substrate scope.

Язык: Английский

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