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

Hao-Kai Sun,

Xi Lu, Yao Fu

et al.

ChemCatChem, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 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.

Language: 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

et al.

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

Published: May 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.

Language: Английский

Citations

8
Enantioselective alkene hydroalkylation overcoming heteroatom constraints via cobalt catalysis DOI
Yan Li, Deguang Liu, Xiao Hu

et al.

Nature Synthesis, Journal Year: 2024, Volume and Issue: 3(9), P. 1134 - 1144

Published: July 10, 2024

Language: Английский

Citations

8
Parametrization of κ2-N,O-Oxazoline Preligands for Enantioselective Cobaltaelectro-Catalyzed C–H Activations DOI Creative Commons
Suman Dana, Neeraj Kumar Pandit, Philipp Boos

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4450 - 4459

Published: Feb. 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.

Language: Английский

Citations

1
Palladium-Catalyzed Enantioselective Multicomponent Cross-Coupling of Trisubstituted Olefins DOI

Wenyi Huang,

Yang Xi,

Deng Pan

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(24), P. 16892 - 16901

Published: June 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.

Language: Английский

Citations

7
Hydrodeuteroalkylation of Unactivated Olefins Using Thianthrenium Salts DOI
Jie Zhang,

Mengjie Jiao,

Zheng Lu

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(36)

Published: June 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

Language: Английский

Citations

6
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

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(23), P. 8888 - 8895

Published: Jan. 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.

Language: Английский

Citations

4
Enantioselective Cobalt-Catalyzed Remote Hydroboration of Alkenylboronates DOI
Wenke Dong,

Zheming Liu,

Aoxuan Bai

et al.

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

Published: Feb. 14, 2025

Heteroatomic groups in alkenes typically direct thermodynamically favored chain walking of C═C bonds toward themselves, thereby facilitating C-H bond functionalization near the heteroatoms. We present herein an efficient cobalt-catalyzed contra-thermodynamic remote hydroboration alkenylboronates with pinacolborane to synthesize chiral 1,n-diboronates. This protocol features a broad substrate scope, high functional group tolerance, and excellent enantioselectivity. Mechanistic studies indicate involvement chain-walking process. Gram-scale reactions various product derivatizations further highlight its practicality.

Language: Английский

Citations

0
Regiodivergent Hydroamidation of Alkenes via Cobalt-Hydride Catalysis DOI

Bingxue Liu,

Qianqian Lü, Xiao Hu

et al.

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

Published: April 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.

Language: Английский

Citations

0
Enantio- and Diastereoselective Synthesis of P-Stereogenic Phospholane Oxides via Cobalt-Catalyzed Hydroalkylation DOI
Dao‐Yong Zhu, Yating Zhang,

Fu Cheng

et al.

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

Published: April 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.

Language: Английский

Citations

0
Regio- and Enantioselective Hydromethylation of 3-Pyrrolines and Glycals Enabled by Cobalt Catalysis DOI Creative Commons

Mengyang Shen,

C. NIU,

Xuchao Wang

et al.

JACS Au, Journal Year: 2024, Volume and Issue: 4(6), P. 2312 - 2322

Published: June 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.

Language: Английский

Citations

3