Heterovalent Metal Pair Sites on Metal–Organic Framework Ordered Macropores for Multimolecular Co-Activation

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(12), P. 8425 - 8434

Published: March 15, 2024

The precise design of catalytic metal centers with multiple chemical states to facilitate sophisticated reactions involving multimolecular activation is highly desirable but challenging. Herein, we report an ordered macroporous catalyst heterovalent pair (HMP) sites comprising CuII–CuI on the basis a microporous metal–organic framework (MOF) system. This HMP proximity dual copper sites, whose distance controlled ∼2.6 Å, macropore surface exhibits co-activation behavior ethanol at CuII and alkyne CuI, avoids restriction, thereby promoting additive-free hydroboration reaction. desired yield enhances dramatically compared pristine MOF both solely isovalent CuII–CuII sites. Density functional theory calculations reveal that Cu-HMP can stabilize Bpin-CuII–CuI-alkyne intermediate C–B bond formation, resulting in smooth process. work provides new perspectives catalysts for matter transformations.

Language: Английский

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Ag–NHC Complexes in the π-Activation of Alkynes

Molecules, Journal Year: 2023, Volume and Issue: 28(3), P. 950 - 950

Published: Jan. 18, 2023

Silver–NHC (NHC = N-heterocyclic carbene) complexes play a special role in the field of transition-metal due to (1) their prominent biological activity, and (2) critical as transfer reagents for synthesis metal-NHC by transmetalation. However, application silver–NHCs catalysis is underdeveloped, particularly when compared group 11 counterparts, gold–NHCs (Au–NHC) copper–NHCs (Cu–NHC). In this Special Issue on Featured Reviews Organometallic Chemistry, we present comprehensive overview silver–NHC p-activation alkynes. The functionalization alkynes one most important processes chemistry, it at bedrock organic synthesis. Recent studies show significant promise unique highly selective catalysts class reactions. review covers reactions catalyzed Ag–NHCs since 2005 (the first example Ag–NHCs) through December 2022. focuses structure NHC ligands p-functionalization methods, covering following broadly defined topics: intramolecular cyclizations; CO2 fixation; (3) hydrofunctionalization By discussing Ag–NHC alkynes, reader provided with an area research promote that are beyond other metal–NHC complexes.

Language: Английский

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ItOct (ItOctyl) – pushing the limits of ItBu: highly hindered electron-rich N-aliphatic N-heterocyclic carbenes

Chemical Science, Journal Year: 2023, Volume and Issue: 14(19), P. 5141 - 5147

Published: Jan. 1, 2023

ItBu (ItBu = 1,3-di-tert-butylimidazol-2-ylidene) represents the most important and versatile N-alkyl N-heterocyclic carbene available in organic synthesis catalysis. Herein, we report synthesis, structural characterization catalytic activity of ItOct (ItOctyl), C2-symmetric, higher homologues ItBu. The new ligand class, including saturated imidazolin-2-ylidene analogues has been commercialized collaboration with MilliporeSigma: ItOct, 929 298; SItOct, 492 to enable broad access academic industrial researchers within field inorganic synthesis. We demonstrate that replacement t-Bu side chain t-Oct results highest steric volume carbenes reported date, while retaining electronic properties inherent N-aliphatic ligands, such as extremely strong σ-donation crucial reactivity carbenes. An efficient large-scale imidazolium imidazolinium SItOct precursors is presented. Coordination chemistry Au(i), Cu(i), Ag(i) Pd(ii) well beneficial effects on catalysis using complexes are described. Considering tremendous importance catalysis, metal stabilization, anticipate class ligands will find wide application pushing boundaries existing approaches

Language: Английский

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Mechanistic Study on Copper- and Silver-Catalyzed Hydroboration of Internal Alkynes: A DFT Study

ACS Organic & Inorganic Au, Journal Year: 2025, Volume and Issue: unknown

Published: March 11, 2025

Language: Английский

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Site-Selective Copper–N-Heterocyclic Carbene-Catalyzed C(sp²)–C(sp) Cross-Coupling of Aryl Thianthrenium Salts

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 23, 2025

This work demonstrates Cu–NHC (NHC = N-heterocyclic carbene) catalyzed alkynylation of aryl thianthrenium salts via thiazol-2-ylidene ligands, achieving a Pd-free Sonogashira coupling with broad substrate compatibility and functional group tolerance. Late-stage pharmaceutical rare alkynylative C–H functionalization/ring-opening pathways are enabled. Thiazol-2-ylidenes, featuring "half-umbrella"-shaped geometry, exhibit superior catalytic performance over traditional imidazol-2-ylidenes, underscoring their unique ligand efficacy. catalysis enables the use as versatile electrophiles for diverse cross-couplings under mild conditions.

Language: Английский

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Acridine-based copper(i) PNP pincer complexes: catalysts for alkyne hydroboration and borylation of aryl halides

Dalton Transactions, Journal Year: 2024, Volume and Issue: 53(10), P. 4471 - 4478

Published: Jan. 1, 2024

Original acridine-based copper( i ) PNP pincer complexes were prepared and their catalytic viability in alkyne hydroboration the borylation of aryl iodides was examined.

Language: Английский

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Copper‐Metallized Porous N‐Heterocyclic Carbene Ligand Polymer‐Catalyzed Regio‐ and Stereoselective 1,2‐Carboboration of Alkynes

Advanced Science, Journal Year: 2023, Volume and Issue: 11(7)

Published: Dec. 8, 2023

Alkenylboronates are highly versatile building blocks and valuable reagents in the synthesis of complex molecules. Compared with that monosubstituted alkenylboronates, multisubstituted alkenylboronates is challenging. The copper-catalyzed carboboration alkynes an operationally simple straightforward method for synthesizing bis/trisubstituted alkenylboronates. In this work, a series copper-metallized N-Heterocyclic Carbene (NHC) ligand porous polymer catalysts designed synthesized accordance mechanism carboboration. By using CuCl@POL-NHC-Ph as optimal nanocatalyst, study realizes β-regio- stereoselective (syn-addition) 1,2-carboboration (regioselectivity up to >99:1) satisfactory yields wide range substrates. This work not only overcomes selectivity but also provides new strategy design nanocatalysts their application organic synthesis.

Language: Английский

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IPr*^Oxa – a new class of sterically-hindered, wingtip-flexible N,C-chelating oxazole-donor N-heterocyclic carbene ligands

Dalton Transactions, Journal Year: 2023, Volume and Issue: 52(38), P. 13608 - 13617

Published: Jan. 1, 2023

We report a new class of sterically-unsymmetrical NHC ligands. The evaluation steric, electronic properties and coordination chemistry is described. Studies catalytic activity in Ag, Pd Rh-catalyzed reactions are presented.

Language: Английский

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[Au(Np^#)Cl]: highly reactive and broadly applicable Au(i)–NHC catalysts for alkyne π-activation reactions

Catalysis Science & Technology, Journal Year: 2023, Volume and Issue: 13(17), P. 5131 - 5139

Published: Jan. 1, 2023

We report [Au(NHC)Cl] complexes featuring IPr# ligands that hinge upon modular peralkylation of aniline. Wingtip-flexible [Au(Np#)Cl] is a broadly applicable catalyst with the reactivity outperforming [Au(IPr)Cl] and [Au(IPr*)Cl] complexes.

Language: Английский

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Wingtip‐Flexible N‐Heterocyclic Carbenes: Unsymmetrical Connection between IMes and IPr

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(8)

Published: Dec. 23, 2023

IMes (IMes=1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene) and IPr (IPr=1,3- bis(2,6-diisopropylphenyl)imidazol-2-ylidene) represent by far the most frequently used N-heterocyclic carbene ligands in homogeneous catalysis, however, despite numerous advantages, these are limited lack of steric flexibility catalytic pockets. We report a new class unique unsymmetrical that characterized freely-rotatable N-aromatic wingtips imidazol-2-ylidene architecture. The combination rotatable N-CH

Language: Английский

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