Ligand-Enabled Carboamidation of Unactivated Alkenes through Enhanced Organonickel Electrophilicity DOI
Yeongyu Hwang, Steven R. Wisniewski, Keary M. Engle

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(46), С. 25293 - 25303

Опубликована: Ноя. 8, 2023

Catalytic carboamination of alkenes is a powerful synthetic tool to access valuable amine scaffolds from abundant and readily available alkenes. Although number approaches have been developed achieve the rapid buildup molecular complexity in this realm, installation diverse carbon nitrogen functionalities onto unactivated remains underdeveloped. Here we present ligand design approach enable nickel-catalyzed three-component carboamidation that applicable wide range alkenyl derivatives via tandem process involving alkyl migratory insertion inner-sphere metal-nitrenoid transfer. With method, various can be installed into both internal terminal alkenes, leading differentially substituted diamines would otherwise difficult access. Mechanistic investigations reveal tailored Ni(cod)(BQiPr) precatalyst modulates electronic properties presumed π-alkene-nickel intermediate quinone ligand, enhanced carbonickelation efficiency across C═C bond. These findings establish nickel's ability catalyze multicomponent with high exquisite selectivity.

Язык: Английский

Ni-Catalyzed Regioselective and Site-divergent Reductive Arylalkylations of Allylic Amines DOI Creative Commons
Huan Meng, Jun-Song Jia, Pengfei Yang

и другие.

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

Процитировано

0
Pyridine vs. Thiazole in Cyclometalated N^C^N Ni(II) Complexes DOI Creative Commons
Lukas Kletsch, Rose Jordan, Julian Strippel

и другие.

Inorganics, Год журнала: 2025, Номер 13(2), С. 41 - 41

Опубликована: Фев. 1, 2025

Six N^C^N cyclometalated Ni(II) complexes [Ni(N^C^N)Cl] or [Ni(N^C^N’)Br] with symmetric non-symmetric N^C^N’ ligands in which the peripheral N-groups were varied pyridine (Py), 4-thiazole (4Tz), 2-thiazole (2Tz), and 2-benzothiazole (2Btz) complementing previously reported di(2-pyridyl)phenide [Ni(Py(Ph)Py)X] X = Cl Br. The synthesized from NiBr2 N^CH^N’ protoligands through base-assisted nickelation, while received N^C(Cl)^N [Ni(COD)2] (COD 1,5-cyclooctadiene). Introduction of 4Tz on both sides shifted electrochemical gap ΔEexp Eox–Ered long wavelength UV-vis absorption maxima to higher energies, 2Tz leads a shift lower energies. When introducing only one as groups, remaining PhPy moiety dominates electronic properties electrochemistry photophysics are very similar Py(Ph)Py derivatives. In contrast this, introduction 2Btz shifts values regardless two groups character frontier molecular orbitals complexes, DFT calculations show. Long-wavelength absorptions vary 416 443 nm, their energies correlate well first reduction potentials. Negishi-type C–C cross-coupling reactions gave total yields ranging 1 60% 44%. reactivities roughly Facilitated (E around –2 higher) goes generally along improved performance, making thiazole-containing interesting candidates for such catalysis.

Язык: Английский

Процитировано

0
Recent Update on Catalytic Activity of N-Heterocyclic Carbene Supported on Graphene Nanosheets: A Mini Review DOI

Raed Muslim Mhaibes,

Abdul Amir H. Kadhum, H Al-Salman

и другие.

Journal of Organometallic Chemistry, Год журнала: 2025, Номер unknown, С. 123660 - 123660

Опубликована: Апрель 1, 2025

Язык: Английский

Процитировано

0
Facile synthesis of half-sandwich (NHC)Ni(Cp)X complexes from labile NHC proligands DOI

Oleg V. Khazipov,

Anastasia S. Pyatachenko,

Olga V Khazipova

и другие.

Mendeleev Communications, Год журнала: 2025, Номер 35(4), С. 427 - 429

Опубликована: Янв. 1, 2025

Язык: Английский

Процитировано

0
Ligand-Enabled Carboamidation of Unactivated Alkenes through Enhanced Organonickel Electrophilicity DOI
Yeongyu Hwang, Steven R. Wisniewski, Keary M. Engle

и другие.

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(46), С. 25293 - 25303

Опубликована: Ноя. 8, 2023

Catalytic carboamination of alkenes is a powerful synthetic tool to access valuable amine scaffolds from abundant and readily available alkenes. Although number approaches have been developed achieve the rapid buildup molecular complexity in this realm, installation diverse carbon nitrogen functionalities onto unactivated remains underdeveloped. Here we present ligand design approach enable nickel-catalyzed three-component carboamidation that applicable wide range alkenyl derivatives via tandem process involving alkyl migratory insertion inner-sphere metal-nitrenoid transfer. With method, various can be installed into both internal terminal alkenes, leading differentially substituted diamines would otherwise difficult access. Mechanistic investigations reveal tailored Ni(cod)(BQiPr) precatalyst modulates electronic properties presumed π-alkene-nickel intermediate quinone ligand, enhanced carbonickelation efficiency across C═C bond. These findings establish nickel's ability catalyze multicomponent with high exquisite selectivity.

Язык: Английский

Процитировано

9