Advances in Chiral Pincer Complexes: Insights and Applications in Catalytic Asymmetric Reactions DOI Open Access
Sanaa Musa,

Yuval Peretz,

Gil Dinnar

et al.

International Journal of Molecular Sciences, Journal Year: 2024, Volume and Issue: 25(19), P. 10344 - 10344

Published: Sept. 26, 2024

Chiral pincer complexes, characterized by their rigid tridentate coordination framework, have emerged as powerful catalysts in asymmetric synthesis. This review provides a comprehensive overview of recent advancements the development chiral pincer-type ligands and corresponding transition metal complexes. We highlight latest progress application across range catalytic reactions, including (transfer) hydrogenation polar non-polar bonds, hydrophosphination, alkynylation, Friedel-Crafts enantioselective reductive cyclization alkynyl-tethered cyclohexadienones, hydrosilylation, well Aza–Morita–Baylis–Hillman reactions. The structural rigidity tunability complexes enable precise control over stereoselectivity, resulting high enantioselectivity efficiency complex molecular transformations. As field advances, innovations ligand design exploration new centers are expected to expand scope utility these catalysts, bearing significant implications for synthesis enantioenriched compounds pharmaceuticals, materials science, beyond.

Language: Английский

Rhodium-Catalyzed Homogeneous Asymmetric Hydrogenation of Naphthol Derivatives DOI
Shuxin Zhang, Linhong Long, Zeyu Li

et al.

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

Published: Jan. 29, 2025

Due to their strong aromaticity and difficulties in chemo-, regio-, enantioselectivity control, asymmetric hydrogenation of naphthol derivatives 1,2,3,4-tetrahydronaphthols has remained a long-standing challenge. Herein, we report the first example homogeneous catalyzed by tethered rhodium-diamine catalysts, affording wide array optically pure high yields with excellent enantioselectivities (up 98% yield >99% ee). Mechanistic studies experimental computational approaches reveal that fluorinated solvent 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) plays vital roles control reactivity selectivity, 1-naphthol is reduced via cascade reaction pathway, including dearomative tautomerization, 1,4-hydride addition, 1,2-hydride addition sequence. A novel synergistic activation mode was proposed which HFIP assists both hydrogen molecule presence base, situ-generated fleeting keto tautomer immediately trapped Rh(III)-H species before it escapes from cage. This protocol provides straightforward practical pathway for synthesis key intermediates several chiral drugs. Particularly, Nadolol, drug treatment hypertension, angina pectoris, congestive heart failure, certain arrhythmias, enantioselectively synthesized time.

Language: Английский

Citations

1
Unlocking the Phosphoric Acid Catalyzed Asymmetric Transfer Hydrogenation of 2-Alkenyl Quinolines for Efficient Flow Synthesis of Hancock Alkaloids DOI Creative Commons
Bence S. Nagy, Aitor Maestro, Miquel À. Pericàs

et al.

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

Published: March 21, 2025

Chiral tetrahydroquinolines are present in several bioactive molecules, such as the Hancock alkaloids. Although organocatalytic asymmetric transfer hydrogenation of 2-aryl quinolines has emerged a safer alternative to using hydrogen gas, analogous reactions with 2-alkenyl remain unexplored. Here we protocol synthesize key enantioenriched intermediates alkaloids, providing constant outcome for, at least, 24 h continuous flow operation.

Language: Английский

Citations

0
Dynamic Kinetic Resolution of β-Cyano α-Ketoesters via Asymmetric Transfer Hydrogenation DOI

Ruiyu Hu,

Fangyuan Wang,

Fan Pan

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(35), P. 7457 - 7462

Published: Aug. 26, 2024

An efficient rhodium-catalyzed asymmetric transfer hydrogenation of β-cyano α-ketoesters via dynamic kinetic resolution has been developed. Despite the challenge posed by multiple functional groups, reaction proceeded smoothly under mild conditions, generating versatile synthons with two adjacent stereocenters in high yields excellent enantio- and diastereoselectivities. Furthermore, power this strategy is highlighted scale-up follow-up synthesis cytoxazone paclitaxel intermediates.

Language: Английский

Citations

1
Catalytic Asymmetric Transfer Hydrogenation of β,γ-Unsaturated α-Diketones DOI

Zhifei Zhao,

Wennan Dong,

Jinggong Liu

et al.

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

Published: Nov. 27, 2024

Asymmetric transfer hydrogenation (ATH) has been recognized as a highly valuable strategy that allows access to enantioenriched substances and widely applied in the industrial production of drug molecules. However, despite great success ATH ketones, efficient, regio- stereoselective on enones remains underdeveloped. Moreover, optically pure acyloins 1,2-diols are both extremely useful building blocks organic synthesis, medicinal chemistry, materials science, but concise asymmetric approaches allowing different types have scarcely discovered. We report this paper first efficient readily accessible β,γ-unsaturated α-diketones. The protocol affords four fashion. synthetic value work showcased by divergent synthesis related natural products. systematic mechanistic studies density functional theory (DFT) calculations illustrated origin reactivity divergence, revealed roles aromatic aliphatic substituents substrates, provided range unique rationales not disclosed ATH-related studies.

Language: Английский

Citations

1
Enantioselective α-C(sp3)–H Borylation of Masked Primary Alcohols Enabled by Iridium Catalysis DOI
Qian Gao, Yinwu Li, Lili Chen

et al.

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

Published: Dec. 18, 2024

Functional group-directed site- and enantioselective C(sp3)–H functionalization of alcohols or masked represents a formidable challenge. We herein report the first example iridium-catalyzed asymmetric α-C(sp3)–H borylation primary alcohol-derived carbamates by judicious choice directing groups. A variety chiral borylated were obtained with good to high enantioselectivities. also demonstrated synthetic utility taking advantage highly transformable feature C–B bonds leaving ability carbamates.

Language: Английский

Citations

1
Advances in Chiral Pincer Complexes: Insights and Applications in Catalytic Asymmetric Reactions DOI Open Access
Sanaa Musa,

Yuval Peretz,

Gil Dinnar

et al.

International Journal of Molecular Sciences, Journal Year: 2024, Volume and Issue: 25(19), P. 10344 - 10344

Published: Sept. 26, 2024

Chiral pincer complexes, characterized by their rigid tridentate coordination framework, have emerged as powerful catalysts in asymmetric synthesis. This review provides a comprehensive overview of recent advancements the development chiral pincer-type ligands and corresponding transition metal complexes. We highlight latest progress application across range catalytic reactions, including (transfer) hydrogenation polar non-polar bonds, hydrophosphination, alkynylation, Friedel-Crafts enantioselective reductive cyclization alkynyl-tethered cyclohexadienones, hydrosilylation, well Aza–Morita–Baylis–Hillman reactions. The structural rigidity tunability complexes enable precise control over stereoselectivity, resulting high enantioselectivity efficiency complex molecular transformations. As field advances, innovations ligand design exploration new centers are expected to expand scope utility these catalysts, bearing significant implications for synthesis enantioenriched compounds pharmaceuticals, materials science, beyond.

Language: Английский

Citations

0