Planar Core and Macrocyclic Shell Stabilized Atomically Precise Copper Nanocluster Catalyst for Efficient Hydroboration of C–C Multiple Bond

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(23), P. 16295 - 16305

Published: May 30, 2024

Atomically precise metal nanoclusters (NCs) have become an important class of catalysts due to their catalytic activity, high surface area, and tailored active sites. However, the design development bond-forming reaction based on copper NCs are still in early stages. Herein, we report synthesis atomically nanocluster with a planar core unique shell, [Cu45(TBBT)29(TPP)4(C4H11N)2H14]2+ (Cu45) (TBBT: 4-tert-butylbenzenethiol; TPP: triphenylphosphine), yield via one-pot reduction method. The resulting structurally well-defined Cu45 is highly efficient catalyst for hydroboration alkynes alkenes. Mechanistic studies show that single-electron oxidation situ-formed ate complex enables formation boryl-centered radicals under mild conditions. This work demonstrates promise as C–B heteroatom reactions. compatible wide range alkenes functional groups producing hydroborated products.

Language: Английский

---

Cu-Catalyzed Diastereo- and Enantioselective Synthesis of Borylated Cyclopropanes with Three Contiguous Stereocenters

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 17, 2025

Direct synthesis of enantioenriched scaffolds with multiple adjacent stereocenters remains an important yet challenging task. Herein, we describe a highly diastereo- and enantioselective Cu-catalyzed alkylboration cyclopropenes, less reactive alkyl iodides as electrophiles, for the efficient tetra-substituted borylated cyclopropanes bearing three consecutive stereocenters. This protocol features mild conditions, broad substrate scope, good functional group tolerance, affording array chiral in to high yields excellent enantioselectivities. Detailed mechanistic experiments kinetic studies were conducted elucidate reaction pathway rate-determining step reaction. DFT calculations revealed that π···π stacking interaction between phenyl groups on phosphorus ligand, along smaller distortion CuL-Bpin part, contributed The synthetic utility was showcased by facile some valuable centers.

Language: Английский

---

Iron-catalysed alkenylzincation of allenes via electrophilicity reversal

Nature Catalysis, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 7, 2025

Language: Английский

---

Iron-Catalyzed C(sp³)–C(sp³) Coupling to Construct Quaternary Carbon Centers

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(8), P. 5051 - 5055

Published: Feb. 19, 2024

The construction of quaternary carbon centers via C–C coupling protocols remains challenging. tertiary C(sp3) with secondary or counterparts has been hindered by pronounced steric clashes and many side reactions. Herein, we have successfully developed a type bisphosphine ligand iron complex-catalyzed reactions alkyl halides zinc reagents efficiently realized the reaction between high selectivity for initial instance, which provided an efficient method hindrance. combination catalyst directing group substrate makes great challenging transformation possible.

Language: Английский

---

Cobalt-Catalyzed Selective Hydroboration of 1,3-Enynes with HBpin toward 1,3-Dienylboronate Esters

Organic Letters, Journal Year: 2024, Volume and Issue: 26(15), P. 3258 - 3262

Published: April 3, 2024

An efficient cobalt-catalyzed selective hydroboration of 1,3-enynes with HBpin toward 1,3-dienylboronate esters is disclosed. With a commercially available catalytic system Co(acac)2 and dppf, the reactions proceeded well to afford wide range 1,3-dienylborates in moderate high yields. This protocol features cheap base-metal system, broad substrate scope, excellent selectivity, easy gram-scale preparation, good functional group tolerance provides access synthetically valuable 1,3-dienylborates.

Language: Английский

---

Cobalt-Catalyzed Regioselective 1,2-Hydroboration of N-Heteroarenes

Organic Letters, Journal Year: 2023, Volume and Issue: 25(1), P. 87 - 92

Published: Jan. 3, 2023

Regioselective hydroboration of pyridines to 1,2-dihydropyridines remains a significant challenge for the synthesis valuable nitrogenous bioactive molecules. Herein, we report base free ligand-controlled cobalt-catalyzed 1,2-hydroboration and quinolines with very low catalyst loading under neat reaction conditions. The choice sterically demanding N-heterocyclic ligands led 1,2-regioselectivity scope was demonstrated by N-heterocycles having variety functional groups. preliminary mechanistic studies corroborate that two followed distinct catalytic cycle Co(I) as an active species.

Language: Английский

---

Light-mediated sulfonyl-iodination of ynamides and internal alkynes

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(43), P. 6584 - 6587

Published: Jan. 1, 2023

We synthesized tetrasubstituted olefins regioselectively and stereoselectively from ynamides internal alkynes with sulfonyl iodides under blue LEDs in few minutes. The key features are being metal-free, easy to handle, simple, broad scope, environmentally friendly. Furthermore, a gram-scale experiment was conducted, the corresponding sulfonyl-iodinated products were smoothly altered into various other products.

Language: Английский

---

Cobalt‐Catalyzed Asymmetric Remote Borylation of Alkyl Halides

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(31)

Published: June 2, 2023

Abstract Enantioselective functionalization of racemic alkyl halides is an efficient strategy to assemble complex chiral molecules, but remains one the biggest challenges in organic chemistry. The distant and selective activation unreactive C−H bonds has received growing interest as it enables rapid generation molecular complexity from simple building blocks. Here, we reported a cobalt‐catalyzed remote borylation (pseudo)halides (alkyl−X, X=I, Br, Cl, OTs) with pinacolborane (HBpin) presented robust approach for valuable secondary organoboronates halides. This migration reaction compatible primary, secondary, tertiary bromides, offering direct access broad range alkylboronates. extension this catalytic system aryl was also demonstrated. Preliminary mechanistic studies revealed that involved radical pathway.

Language: Английский

---

Atomically precise copper clusters with dual sites for highly chemoselective and efficient hydroboration

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Nov. 5, 2024

Abstract The hydroboration of alkynes into vinylboronate esters is a vital transformation, but achieving high chemoselectivity targeted functional groups and an appreciable turnover number considerable challenge. Herein, we develop two dynamically regulating dual-catalytic-site copper clusters (Cu 4 NC Cu 8 NC) bearing N-heterocyclic thione ligands that endow catalysts with performance. In particular, the performance microcrystalline in characterized by (77786), chemoselectivity, recovery reusability under mild conditions. Mechanistic studies density theory calculations reveal that, compared catalyst, catalyst has lower activation energy for hydroboration, accounting its catalytic activity. This work reveals precisely constructed cluster dual sites may provide way to substantially improve properties fully leveraging synergistic interactions dynamic ligand effects, thus promoting development catalysts.

Language: Английский

---

Regioselective Nickel-Catalyzed Hydrotrifluoroalkylation of Alkynes to Construct Trisubstituted Allylic Trifluoromethyl Alkenes

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

Published: April 1, 2025

Introducing fluorine atoms or fluorine-containing groups into drug molecules has become a common approach in design, with the incorporation of trifluoromethyl as focal point research field organic fluorochemistry. Here, we describe nickel-catalyzed hydrotrifluoromethylation internal alkynes alkyl bromides to synthesize series highly regioselective allyl trisubstituted alkenes. This reaction is characterized by mild conditions and broad functional-group tolerance, providing an efficient practical

Language: Английский

---