Nickel-Catalyzed Remote C(sp³)–N/O Bond Formation of Alkenes with Unactivated Amines and Alcohols

ACS Catalysis, Год журнала: 2023, Номер 13(7), С. 4409 - 4420

Опубликована: Март 17, 2023

Transition metal-catalyzed remote hydrofunctionalization of alkenes is an efficient method to realize C(sp3)–H functionalization. However, with unactivated amines and alcohols has not been successfully developed date. Herein, we report nickel-catalyzed hydroamination hydroetherification alcohols, accessing a series gem-diamine N,O-acetal derivatives in good high yields (up 93%) exclusive regioselectivities. The mechanistic investigations DFT computations indicated that the use 2-iodo-2-methylpropane (tBuI) as both mild hydride source radical precursor was essential afford functionalized products. This research work provides install amino or alkoxyl group at position far from double bond alkenes.

Язык: Английский

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Functionalization of Olefinic C−H Bonds by an Aryl‐to‐Vinyl 1,4‐Nickel Migration/Reductive Coupling Sequence

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(28)

Опубликована: Май 6, 2023

An attractive approach to selective functionalization of remote C-H bonds is a metal/hydride shift/cross-coupling reaction sequence. Complimentary the heavily exploited 1,2-nickel/hydride shift along an sp3 chain, chain-walking process, 1,4-nickel/hydride sp2 chain more complex. Here we report unprecedented aryl-to-vinyl reaction, in which migratory alkenylnickel species generated situ selectively trapped by one various coupling partners, such as isocyanates, alkyl bromides, aryl chlorides or alkynyl allowing regio- and stereoselective access trisubstituted alkenes. In contrast well-reported ipso-aryl reactions, this strategy provides alkenyl functionalized products with good yield excellent chemo-, E/Z-selectivity.

Язык: Английский

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Stereospecific Acylative Suzuki–Miyaura Cross-Coupling: General Access to Optically Active α-Aryl Carbonyl Compounds

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(13), С. 7075 - 7083

Опубликована: Март 2, 2023

A novel strategy for the stereospecific Pd-catalyzed acylative cross-coupling of enantiomerically enriched alkylboron compounds has been developed. The protocol features an extremely high level enantiospecificity to allow facile access synthetically challenging and valuable chiral ketones carboxylic acid derivatives. use a sterically encumbered electron-rich phosphine ligand proved be crucial success reaction. Furthermore, on basis experimental computational studies, unique mechanism transmetalation, assisted by noncovalent interactions C(sp3)-based organoboron reagent, identified.

Язык: Английский

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Nickel-Catalyzed Reductive Cross-Coupling of Alkyl Bromides and Chlorosilanes

Organic Letters, Год журнала: 2021, Номер 23(19), С. 7645 - 7649

Опубликована: Сен. 22, 2021

A novel nickel-catalyzed highly selective reductive cross-coupling of alkyl bromides and chlorosilanes to construct the C–Si bond has been developed. Under benign reaction conditions, a series structurally interesting organosilanes can be accessed without Ni-catalyzed isomerization. The utility this chemistry is illustrated by further transformations product. Moreover, radical mechanism control experiments.

Язык: Английский

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Three-Component Ni-Catalyzed Silylacylation of Alkenes

ACS Catalysis, Год журнала: 2021, Номер 11(3), С. 1858 - 1862

Опубликована: Янв. 26, 2021

A Ni-catalyzed silylacylation of alkenes is presented. The reaction combines alkenes, ClZnSiR3, and acid chlorides to provide rapid access β-silyl ketones. Importantly, the method involves a [Ni]-SiR3 complex as catalytic intermediate, which rarely described for three-component alkene functionalization. Finally, synthetic utility products demonstrated, mechanistic details are described.

Язык: Английский

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