Hydroalkylation of unactivated olefins with C(sp 3 )─H compounds enabled by NiH-catalyzed radical relay DOI Creative Commons

Jiang‐Ling Shi,

Youcheng Wang,

Yufeng Han

et al.

Science Advances, Journal Year: 2024, Volume and Issue: 10(51)

Published: Dec. 18, 2024

The hydroalkylation reaction of olefins with alkanes is a highly desirable synthetic transformation toward the construction C(sp 3 )─C(sp ) bonds. However, such has proven to be challenging for unactivated olefins, particularly when substrates lack directing groups or acidic )─H Here, we address this challenge by merging NiH-catalyzed radical relay strategy HAT (hydrogen atom transfer) process. In catalytic system, nucleophilic alkyl generated from compound in presence promotor, which couples an metallic intermediate olefin substrate NiH catalyst form bond. Starting easily available materials, not only demonstrates wide functional group compatibility but also provides products regiodivergence and excellent enantioselectivity through effective control under mild conditions.

Language: Английский

Ligand-Controlled Cobalt-Catalyzed Regio-, Enantio-, and Diastereoselective Oxyheterocyclic Alkene Hydroalkylation DOI
Zhen Li,

Bingxue Liu,

Cheng-Yu Yao

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(5), P. 3405 - 3415

Published: Jan. 29, 2024

Metal-hydride-catalyzed alkene hydroalkylation has been developed as an efficient method for C(sp

Language: Английский

Citations

19
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
Regio- and Enantioselective Nickel-Catalyzed Ipso- and Remote Hydroamination Utilizing Organic Azides as Amino Sources for the Synthesis of Primary Amines DOI

Shi‐Chao Wang,

Lin Liu,

Mei Duan

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 23, 2024

Primary amines serve as key synthetic precursors to most other

Language: Английский

Citations

6
NiH-catalyzed C–N bond formation: insights and advancements in hydroamination of unsaturated hydrocarbons DOI Creative Commons
Changseok Lee, Hyung‐Joon Kang, Sungwoo Hong

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 15(2), P. 442 - 457

Published: Dec. 6, 2023

The formation of C-N bonds is a fundamental aspect organic synthesis, and hydroamination has emerged as pivotal strategy for the synthesis essential amine derivatives. In recent years, there been surge interest in metal hydride-catalyzed reactions common alkenes alkynes. This method avoids need stoichiometric organometallic reagents overcomes problems associated with specific compounds that may impact functional group compatibility. Notably, developments have brought to forefront olefinic hydroamidation facilitated by nickel hydride (NiH) catalysis. inclusion suitable chiral ligands paved way realization asymmetric realm olefins. review aims provide an in-depth exploration latest achievements bond through intermolecular catalyzed hydrides. Leveraging this innovative approach, diverse range alkene alkyne substrates can be efficiently transformed into value-added enriched bonds. intricacies are succinctly elucidated, offering concise overview underlying reaction mechanisms. It our aspiration comprehensive will stimulate further progress NiH-catalytic techniques, fine-tune systems, drive innovation catalyst design, foster deeper understanding

Language: Английский

Citations

14
Regiodivergent and Enantioselective Synthesis of Cyclic Sulfones via Ligand‐Controlled Nickel‐Catalyzed Hydroalkylation DOI Creative Commons
Chao Fan, Uttam Dhawa, Deyun Qian

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(29)

Published: April 29, 2024

Abstract Cyclic sulfones have demonstrated important applications in drug discovery. However, the catalytic and enantioselective synthesis of chiral cyclic remains challenging. Herein, we develop nickel‐catalyzed regiodivergent hydroalkylation sulfolenes to streamline alkyl sulfones. The method has broad scope high functional group tolerance. regioselectivity can be controlled by ligands only. A neutral PYROX ligand favors C3‐alkylation whereas an anionic BOX C2‐alkylation. This control is kinetic origin as C2‐bound Ni intermediates are always thermodynamically more stable. Reactivity study a wide range relevant reveal I /Ni III cycle with II −H species resting state. regio‐ enantio‐determining step insertion this into 2‐sulfolene. work provides efficient for class organic compounds enhances mechanistic understanding Ni‐catalyzed stereoselective hydroalkylation.

Language: Английский

Citations

5
Asymmetric Intramolecular Amination Catalyzed with Cp*Ir-SPDO via Nitrene Transfer for Synthesis of Spiro-Quaternary Indolinone DOI
Shiqiang Wei, Zihao Li, Shuanghu Wang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(28), P. 18841 - 18847

Published: July 8, 2024

An asymmetric intramolecular spiro-amination to high steric hindering

Language: Английский

Citations

5
Chiral Magnesium(II)-Catalyzed Asymmetric Hydroalkylation of Imine-Containing Vinylazaarenes through Conjugate Addition DOI
Dong Ye, Mingyi Jiang, Lichao Ning

et al.

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

Published: March 29, 2025

The synthesis of chiral azaarenes is great importance for pharmaceutical development. A direct and versatile approach to obtaining such compounds the functionalization imine-containing 2-vinylazaarenes. We have developed a N,N'-dioxide/Mg(II) Lewis acid catalytic system control nucleophilic β-cyclic or acyclic ketone amides/esters overcome strong background reaction, enabling highly efficient enantioselective hydroalkylation 2-vinylazaarenes via conjugate addition. As result, library bearing an all-carbon quaternary stereocenter can be obtained in high yields with good excellent ee values. DFT calculations indicate assistances hydrogen transfer, CH-π interaction between substrate ligand's amide group differentiation.

Language: Английский

Citations

0
Synergistic Photoenzymatic Anti-Markovnikov Hydroarylation of Olefins via Heteroaryl Radical Intermediates DOI
Prasun Mukherjee,

Zayed Alassad,

Todd K. Hyster

et al.

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

Published: April 16, 2025

Heteroaromatic alkylations are indispensable reactions for synthesizing biologically active molecules. The anti-Markovnikov hydroarylation of olefins using heteroaryl halides furnishes the product as a single regioisomer; however, catalytic variants ineffective at controlling stereochemical outcome these reactions. Here, we report synergistic photoenzymatic flavin-dependent "ene"-reductases with ruthenium photoredox catalysts. Enzyme homologues were identified, which provide access to both enantiomers in greater than 80% yield up 99:1 er. This method is effective styrenyl- and unactivated alkenes, highlighting generality this approach. highest yielding system involves carboxylated photocatalyst increased affinity enzyme. work expands types radical intermediates that enzymes can use stereoselective intermolecular coupling

Language: Английский

Citations

0
Ligand Relay Catalysis Enables Asymmetric Migratory Hydroarylation for the Concise Synthesis of Chiral α‐(Hetero)Aryl‐Substituted Amines DOI Creative Commons

Junqian Zhou,

Yuli He, Zihao Liu

et al.

Advanced Science, Journal Year: 2024, Volume and Issue: 11(16)

Published: Feb. 28, 2024

Abstract Complementary to the design of a single structurally complex chiral ligand promote each step in transition‐metal catalysis, multiligand relay catalysis through dynamic exchange with catalytic cycle promoted by its best provides an attractive approach enhance whole reaction reactivity and selectivity. Herein, regio‐ enantioselective NiH‐catalyzed migratory hydroarylation process simple combination chain‐walking asymmetric arylation ligand, producing high‐value α ‐(hetero)aryl‐substituted amines their derivatives under mild conditions, is reported. The potential synthetic applications this transformation are demonstrated concise synthesis ( S )‐nicotine CDK8 inhibitor.

Language: Английский

Citations

3