Cobalt‐Catalyzed Hydroarylation of 2,3‐Dihydrofuran to Access α‐Arylated Tetrahydrofurans DOI

Hao-Kai Sun,

Xi Lu, Yao Fu

и другие.

ChemCatChem, Год журнала: 2024, Номер unknown

Опубликована: Ноя. 11, 2024

Abstract The α ‐arylated tetrahydrofurans, commonly found in biologically active molecules, exhibit diverse biological activities and pharmacological effects. functionalization of 2,3‐dihydrofuran offers a potential route for the synthesis substituted tetrahydrofurans. Nevertheless, development earth‐abundant metal‐catalyzed regioselective hydrofunctionalization tetrahydrofurans remains to be pursued. Herein, we report cobalt‐catalyzed hydroarylation 2,3‐dihydrofuran, which serves as first example cobalt hydride‐catalyzed alkene hydroarylation. This reaction provides an efficient method with high efficiency, exclusive ‐arylation selectivity, remarkable functional group compatibility.

Язык: Английский

Enantioselective synthesis of chiral α,α-dialkyl indoles and related azoles by cobalt-catalyzed hydroalkylation and regioselectivity switch DOI Creative Commons
Jiangtao Ren,

Sun Zheng,

Shuang Zhao

и другие.

Nature Communications, Год журнала: 2024, Номер 15(1)

Опубликована: Май 6, 2024

Abstract General, catalytic and enantioselective construction of chiral α,α -dialkyl indoles represents an important yet challenging objective to be developed. Herein we describe a cobalt catalyzed anti- Markovnikov alkene hydroalkylation via the remote stereocontrol for synthesis other N -heterocycles. This asymmetric C(sp 3 )−C(sp ) coupling features high flexibility in introducing diverse set alkyl groups at α -position The utility this methodology has been demonstrated by late-stage functionalization drug molecules, bioactive natural products functional materials, identification class molecules exhibiting anti-apoptosis activities UVB-irradiated HaCaT cells. Ligands play vital role controlling reaction regioselectivity. Changing ligand from bi-dentate L6 tridentate L12 enables CoH-catalyzed hydroalkylation. Mechanistic studies disclose that involves migratory insertion process while MHAT process.

Язык: Английский

Процитировано

10

Parametrization of κ2-N,O-Oxazoline Preligands for Enantioselective Cobaltaelectro-Catalyzed C–H Activations DOI Creative Commons
Suman Dana, Neeraj Kumar Pandit, Philipp Boos

и другие.

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 4450 - 4459

Опубликована: Фев. 28, 2025

Enantioselective electrocatalyzed C–H activations have emerged as a transformative platform for the assembly of value-added chiral organic molecules. Despite recent progress, construction multiple C(sp3)-stereogenic centers via C(sp3)–C(sp3) bond formation has thus far proven to be elusive. In contrast, we herein report an annulative activation strategy, generating Fsp3-rich molecules with high levels diastereo- and enantioselectivity. κ2-N,O-oxazoline preligands were effectively employed in enantioselective cobalt(III)-catalyzed reactions. Using DFT-derived descriptors regression statistical modeling, performed parametrization study on modularity preligands. The resulted model describing ligands' selectivity characterized by key steric, electronic, interaction behaviors.

Язык: Английский

Процитировано

1

Palladium-Catalyzed Enantioselective Multicomponent Cross-Coupling of Trisubstituted Olefins DOI

Wenyi Huang,

Yang Xi, Deng Pan

и другие.

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(24), С. 16892 - 16901

Опубликована: Июнь 6, 2024

The development of a catalytic method for stereogenic carbon center formation holds immense significance in organic synthesis. Transition-metal-catalyzed cross-coupling reaction has been regarded as straightforward and efficient tool stereoselectively forging C–C bond. Nevertheless, the creation acyclic all-carbon quaternary-containing vicinal stereocenters remains notoriously challenging within domain chemistry despite their prominence various bioactive small molecules. Herein, we describe palladium-catalyzed asymmetric multicomponent trisubstituted alkene with aryl diazonium salts arylboronic acids to realize tertiary-quaternary centers high regio-, distereo-, enantioselectivity. Specifically, precise manipulation stereoconfiguration alkenes enables divergent stereoselective reaction, thus allowing facile construction all four enantiomers. Harnessing ligand-swap strategy involving chiral bisoxazoline an achiral fumarate individually accelerates enantioselective migratory insertion reductive elimination step process, supported by density functional theory (DFT) calculations, obviating requirement neighboring directing group internal olefin skeleton.

Язык: Английский

Процитировано

9

Hydrodeuteroalkylation of Unactivated Olefins Using Thianthrenium Salts DOI
Jie Zhang,

Mengjie Jiao,

Zheng Lu

и другие.

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(36)

Опубликована: Июнь 13, 2024

Isotopically labeled alkanes play a crucial role in organic and pharmaceutical chemistry. While some deuterated methylating agents are readily available, the limited accessibility of other deuteroalkyl reagents has hindered synthesis corresponding products. In this study, we introduce nickel-catalyzed system that facilitates various deuterium-labeled through hydrodeuteroalkylation d2-labeled alkyl TT salts with unactivated alkenes. Diverging from traditional reagents, thianthrenium (TT) can effectively selectively deuterium at α position chains using D

Язык: Английский

Процитировано

8

Enantioselective alkene hydroalkylation overcoming heteroatom constraints via cobalt catalysis DOI
Yan Li, Deguang Liu, Xiao Hu

и другие.

Nature Synthesis, Год журнала: 2024, Номер 3(9), С. 1134 - 1144

Опубликована: Июль 10, 2024

Язык: Английский

Процитировано

8

Regiodivergent Hydroamidation of Alkenes via Cobalt-Hydride Catalysis DOI

Bingxue Liu,

Qianqian Lü, Xiao Hu

и другие.

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Апрель 10, 2025

Regiodivergent hydroamin(d)ation of alkenes presents a valuable strategy for the synthesis diverse amines or amides from common set starting materials, yet achieving controlled regioselectivity remains significant challenge. In this work, we present cobalt-catalyzed regiodivergent hydroamidation alkenes, enabling enantioselective ipso- and migratory heterocyclic alkenes. The ability to finely tune various reaction parameters allows seamless switch in regioselectivity. Notably, selectivity are governed by choice cobalt catalyst anions. Mechanistic studies reveal neutral Co-H species mediating ipso-hydroamidation cationic intermediate promoting hydroamidation. This protocol exhibits broad substrate scope, high functional group tolerance, provides an efficient pathway synthetizing structurally amides.

Язык: Английский

Процитировано

1

CoH-catalyzed asymmetric remote hydroalkylation of heterocyclic alkenes: a rapid approach to chiral five-membered S- and O-heterocycles DOI Creative Commons
Lingzi Zhao,

Feipeng Liu,

Yan Zhuang

и другие.

Chemical Science, Год журнала: 2024, Номер 15(23), С. 8888 - 8895

Опубликована: Янв. 1, 2024

A highly efficient method achieves precise construction of alkyl chiral centers at remote C3-positions in five-membered S/O-heterocycles via cobalt-catalyzed asymmetric hydroalkylation heterocyclic alkenes.

Язык: Английский

Процитировано

4

Enantio- and Diastereoselective Synthesis of P-Stereogenic Phospholane Oxides via Cobalt-Catalyzed Hydroalkylation DOI
Dao‐Yong Zhu, Yating Zhang,

Fu Cheng

и другие.

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Апрель 10, 2025

Chiral phospholane ligands and catalysts have been widely applied in asymmetric catalysis synthesis. However, the construction of chiral skeleton remains challenging primarily relies on use auxiliaries or resolution. In this work, a highly enantioselective diastereoselective synthesis P-stereogenic oxides has achieved through cobalt-catalyzed desymmetric hydroalkylation strategy. This method enables two discrete stereocenters with excellent yields enantiomeric excesses.

Язык: Английский

Процитировано

0

Regio- and Enantioselective Hydromethylation of 3-Pyrrolines and Glycals Enabled by Cobalt Catalysis DOI Creative Commons

Mengyang Shen,

C. NIU,

Xuchao Wang

и другие.

JACS Au, Год журнала: 2024, Номер 4(6), С. 2312 - 2322

Опубликована: Июнь 11, 2024

Enantioenriched 3-methylpyrrolidine, with its unique chiral nitrogen-containing core skeleton, exists widely in various functional molecules, including natural products, bioactive compounds, and pharmaceuticals. Traditional methods for synthesizing these valuable methyl-substituted heterocycles often involve enzymatic processes or complex procedures auxiliaries, limiting the substrate scope efficiency. Efficient catalytic methylation, especially an enantioselective manner, has been a long-standing challenge chemical synthesis. Herein, we present novel approach remote stereoselective installation of methyl group onto N-heterocycles, leveraging CoH-catalyzed asymmetric hydromethylation strategy. By effectively combining commercial cobalt precursor modified bisoxazoline (BOX) ligand, variety easily accessible 3-pyrrolines can be converted to enantiopure 3-(isotopic labeling)methylpyrrolidine compounds outstanding enantioselectivity. This efficient protocol streamlines two-step synthesis enantioenriched which previously required up five six steps under harsh conditions expensive starting materials.

Язык: Английский

Процитировано

3

Photoinduced Co/Ni-cocatalyzed Markovnikov hydroarylation of unactivated olefins with aryl bromides DOI Creative Commons
Hongchao Liu, Xinyu Xu, Siyuan Tang

и другие.

Chemical Science, Год журнала: 2024, Номер 15(36), С. 14865 - 14871

Опубликована: Янв. 1, 2024

A novel photoinduced Co/Ni-cocatalyzed Markovnikov hydroarylation of unactivated alkenes with aryl bromides by using proton as a hydrogen source has been developed for the first time.

Язык: Английский

Процитировано

3