Selectivity Switch in Non‐Directed Palladium‐Catalyzed C−H Olefination of Chlorobenzene Derivatives DOI
Jeanne Fichez, Maria I. Lapuh,

Lina Truong

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(12), P. 2811 - 2822

Published: April 25, 2024

Abstract A palladium(II)‐catalyzed oxidative C−H olefination of chlorobenzene derivatives, which favored the functionalization at ortho ‐to‐chlorine position, was reported. The catalytic system employed a commercially available quinoline ligand to access wide panel olefinated aryl chlorides in moderate high yields from feedstock chemicals (42 examples, 28 93% yields). synthetic utility method further demonstrated by coupling various bio‐relevant acrylate partners offering straightforward structurally diverse complex molecules. computational study reaction allowed us confirm that activation step, occurring through Concerted Metalation‐Deprotonation mechanism, determined site‐selectivity transformation. regioselectivity controlled p K bond (more acidic position) and lower distortion key transition structure.

Language: Английский

TFA‐Prompted/Rh(III)‐Catalysed Chemoselective C3− or C2−H Functionalization of Indoles with Methylenecyclopropanes DOI
Min Wu, Shengdong Wang, Yi Wang

et al.

European Journal of Organic Chemistry, Journal Year: 2021, Volume and Issue: 2021(40), P. 5507 - 5517

Published: Sept. 25, 2021

Abstract The TFA‐prompted/Rh(III)‐catalysed chemoselective C 3 −H alkylation, 2 dienylation and cyclopropylation of indoles have been realized by virtue methylenecyclopropanes as the versatile coupling partners. This protocol features broad substrate/functional group compatibility tunable regio‐/chemoselectivity. Diversified derivatization obtained products has also successfully demonstrated, which further strengthened potential for synthetic utility developed protocols.

Language: Английский

Citations

5
Iridium catalysed C2 site-selective methylation of indoles using a pivaloyl directing group through weak chelation-assistance DOI Creative Commons

Subban Kathiravan,

Tianshu Zhang, Ian A. Nicholls

et al.

RSC Advances, Journal Year: 2023, Volume and Issue: 13(17), P. 11291 - 11295

Published: Jan. 1, 2023

Here we present an iridium catalysed C2-selective methylation of indoles using methyltrifluoroborate as a source methyl group. The catalyst selectively discriminates the indole C2 and C4 C-H bonds by coordination with pivaloyl directing

Language: Английский

Citations

1
DBU-catalyzed substitution-controlled synthesis of oxa[3.3.1] bridged ring and naphthylamine derivatives DOI

Shiyu Xu,

Zhihui Sun,

Pengyutian Liu

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(10), P. 2845 - 2850

Published: Jan. 1, 2024

A switchable cascade cyclization reaction of ortho -alkynyl arylketones with amines has been developed, where the different pathways are controlled by substituent on α-carbon in-situ -generated arylaldimines.

Language: Английский

Citations

0
Assessing the Cooperating Ability of 6‐Hydroxypicolinic Acid and Pyridyl‐Amide Ligands in Palladium‐Mediated C–H Activation DOI Creative Commons
Cintya Pinilla, Ana C. Albéniz

European Journal of Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 27(17)

Published: May 23, 2024

Abstract The behavior of 6‐hydroxypicolinic acid (pic‐6‐OH) and pyridyl‐amides as cooperating ligands in the C−H activation arenes has been studied experimentally. When deprotonated, both compounds are chelating bear either a pyridone moiety or an N ‐acyl substituent that can assist cleavage same way successful bipyridone MPAAs do. In addition, they easily available, commercially via straightforward syntheses. Palladium complexes formula (NBu 4 )[Pd(κ 2 ‐ O , ‐pic‐6‐O)(C 6 F 5 )py] ( ) [Pd(κ py‐CH N(COCF 3 )(C have synthesized their decomposition presence arene gives C ‐arene coupling product, showing enable (arene=pyridine, toluene, ethyl benzoate). amount products observed leads to following trend ability: pic‐6‐OH > pyridyl‐amide. DFT calculations on pyridine consistent with experimental findings. does not occur for isomeric complex ‐pic‐4‐O)(C oxygen far from metal, involvement this cleavage. performance these direct arylation evaluated.

Language: Английский

Citations

0
Selectivity Switch in Non‐Directed Palladium‐Catalyzed C−H Olefination of Chlorobenzene Derivatives DOI
Jeanne Fichez, Maria I. Lapuh,

Lina Truong

et al.

Advanced Synthesis & Catalysis, Journal Year: 2024, Volume and Issue: 366(12), P. 2811 - 2822

Published: April 25, 2024

Abstract A palladium(II)‐catalyzed oxidative C−H olefination of chlorobenzene derivatives, which favored the functionalization at ortho ‐to‐chlorine position, was reported. The catalytic system employed a commercially available quinoline ligand to access wide panel olefinated aryl chlorides in moderate high yields from feedstock chemicals (42 examples, 28 93% yields). synthetic utility method further demonstrated by coupling various bio‐relevant acrylate partners offering straightforward structurally diverse complex molecules. computational study reaction allowed us confirm that activation step, occurring through Concerted Metalation‐Deprotonation mechanism, determined site‐selectivity transformation. regioselectivity controlled p K bond (more acidic position) and lower distortion key transition structure.

Language: Английский

Citations

0