Efficient Construction of β-Arylethylamines via Selective C(sp3)-H Arylation of Aliphatic Amines DOI Creative Commons
Tu Hua,

Xi Deng,

Hongyi Li

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 17535 - 17546

Published: Nov. 13, 2024

The synthetic innovations in generating β-arylethylamines have the potential to propel advancements drug discovery, as are common structural motifs various bioactive compounds and drugs. Here, we report an efficient Pd (II)-catalyzed method for selective β-C(sp3)-H arylation of aliphatic amines construct β-arylethylamine frameworks. With easy installation removal nitroso directing group on amine nitrogen, this Pd-catalyzed enables (hetero)arylation bonds scaffolds produce tolerates a variety functional groups both coupling partners. It offers approach direct syntheses drugs from native amines, thereby overcoming inherent limitations previously known methods. This identified Pd-catalyst-system features low catalyst loading C–H functionalization high reaction rate, originating pyridone-amide-ester ligand that increases activity while protecting all active species forming inactive complexes. Experimental computational studies disclose valuable effect partially results pendant ester participates several steps C(sp3)-H activation process favors Pd-catalytic cycle.

Language: Английский

Ir-Catalyzed, Nitrogen-Directed C(sp3)–H and C(sp2)–H Borylation with a Spiro-Fluorene-Indenoindenyl Ligand DOI Creative Commons

Tomonori Inoue,

Yu Sato, Yuki Nagashima

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 4061 - 4068

Published: Feb. 21, 2025

Language: Английский

Citations

1
Selective Borylation of C(sp3)−H Bond of Methyl Ethers Catalyzed by Iron Complexes Bearing Anionic Benzene‐Based PCP‐Pincer Ligands DOI Creative Commons
Shogo Kuriyama,

Yuto Suga,

Ken Sakata

et al.

ChemistryEurope, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 28, 2025

Abstract Highly selective catalytic C(sp 3 )−H borylation of methoxy groups has been achieved using newly synthesized iron complexes bearing benzene‐based PCP‐type pincer ligands as catalysts. Reactions various aryl and alkyl methyl ethers substrates with bis(pinacolato)diboron under mild reaction conditions proceeded to afford the corresponding borylated products in good high yields. A successful example iron‐catalyzed a methylene group tetrahydrofuran (THF) was also presented. plausible pathway is proposed based on experimental result some stoichiometric reactions DFT calculations model reaction, where iron‐boryl ‐alkyl may work key intermediates.

Language: Английский

Citations

0
Bis-CF3-bipyridine Ligands for the Iridium-Catalyzed Borylation of N-Methylamides DOI
Daniel Marcos‐Atanes, Gonzalo Jiménez‐Osés, José L. Mascareñas

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 7112 - 7120

Published: April 16, 2025

Language: Английский

Citations

0
Do we really need ligands in Ir-catalyzed C–H borylation? DOI Creative Commons
Janis M. Zakis,

Simone L. Kuhn,

Joanna Wencel‐Delord

et al.

Published: May 29, 2024

Direct borylation of C–H bonds is a privileged strategy to access versatile building blocks and valuable derivatives complex molecules (late-stage functionalization, metabolite synthesis). This perspective aims provide an overview classification the catalytic systems developed in this fast-growing area research. Unexpected selectivity differences between two established directed-borylation have been discovered using high-throughput experimentation highlighting importance classical control experiments catalysis

Language: Английский

Citations

1
Boronyl-Group-Assisted Decatungstate-Catalyzed Benzylic C(sp3)–H Alkylation DOI

Hui Jiang,

Takeru Torigoe, Yoichiro Kuninobu

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(23), P. 4853 - 4856

Published: June 5, 2024

Boronic acid synthesis primarily involves the introduction of boronyl groups. However, an alternative route that functionalization boronic acids has not received much attention. This study describes catalytic C(sp3)–H alkylation ortho-tolylboronic utilizing interaction between a free group [−B(OH)2] and decatungstate photocatalyst [W10O32]4–. The groups alkylated products could be converted without isolation product.

Language: Английский

Citations

1
Do we really need ligands in Ir-catalyzed C–H borylation? DOI Creative Commons
Janis M. Zakis,

Simone L. Kuhn,

Joanna Wencel‐Delord

et al.

CHIMIA International Journal for Chemistry, Journal Year: 2024, Volume and Issue: 78(7-8), P. 513 - 517

Published: Aug. 21, 2024

Direct borylation of C–H bonds is a privileged strategy to access versatile building blocks and valuable derivatives complex molecules (late-stage functionalization, metabolite synthesis). This perspective aims provide an overview classification the catalytic systems developed in this fast-growing area research. Unexpected selectivity differences between two established directed-borylation have been discovered using high-throughput experimentation highlighting importance classical control experiments catalysis

Language: Английский

Citations

1
The Difference in Ir-Catalyzed C(sp2)–H and C(sp3)–H Bond Activation Assisted by a Directing Group: Cyclometalation via Cis- or Trans-Chelation? DOI

Ling-Qi Meng,

Jian-Sen Wang,

Xiao-Xia You

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(38), P. 17626 - 17638

Published: Sept. 5, 2024

Iridium-catalyzed C-H borylation of aromatic and aliphatic hydrocarbons assisted by a directing group was theoretically investigated. Density functional theory (DFT) calculations revealed both Ir-catalyzed C(sp

Language: Английский

Citations

1
Merging Ring-Opening 1,2-Metallate Shift with Asymmetric C(sp3)–H Borylation of Aziridines DOI
Bailin Wang,

Hongliang Zhao,

Xing‐Wang Wang

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(28), P. 18879 - 18885

Published: July 5, 2024

Chiral secondary alkyl amines with a vicinal quaternary stereocenter are undoubtedly important and ubiquitous subunits in natural products pharmaceuticals. However, their asymmetric synthesis remains formidable challenge. Herein, we merge the ring-opening 1,2-metallate shift iridium-catalyzed enantioselective C(

Language: Английский

Citations

0
Metal-free C–H borylation of heterocycles by merging photoredox and hydrogen atom transfer catalysis DOI

Changfu Wu,

Shuang Luo,

Xiaozu Liu

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(17), P. 4785 - 4793

Published: Jan. 1, 2024

Reported herein is a method that merges organophotoredox and hydrogen atom transfer catalysis to enable the C–H borylation of heterocycles using O 2 as an environmentally friendly oxidant.

Language: Английский

Citations

0
Efficient Construction of β-Arylethylamines via Selective C(sp3)-H Arylation of Aliphatic Amines DOI Creative Commons
Tu Hua,

Xi Deng,

Hongyi Li

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 17535 - 17546

Published: Nov. 13, 2024

The synthetic innovations in generating β-arylethylamines have the potential to propel advancements drug discovery, as are common structural motifs various bioactive compounds and drugs. Here, we report an efficient Pd (II)-catalyzed method for selective β-C(sp3)-H arylation of aliphatic amines construct β-arylethylamine frameworks. With easy installation removal nitroso directing group on amine nitrogen, this Pd-catalyzed enables (hetero)arylation bonds scaffolds produce tolerates a variety functional groups both coupling partners. It offers approach direct syntheses drugs from native amines, thereby overcoming inherent limitations previously known methods. This identified Pd-catalyst-system features low catalyst loading C–H functionalization high reaction rate, originating pyridone-amide-ester ligand that increases activity while protecting all active species forming inactive complexes. Experimental computational studies disclose valuable effect partially results pendant ester participates several steps C(sp3)-H activation process favors Pd-catalytic cycle.

Language: Английский

Citations

0