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http://hdl.handle.net/1843/61104
Type: | Artigo de Periódico |
Title: | Asymmetric Transfer Hydrogenation of Aryl Heteroaryl Ketones and o-Hydroxyphenyl Ketones Using Noyori-Ikariya Catalysts |
Authors: | Ye Zheng Jaime A. Martinez-Acosta Mohammed Khimji Luiz Cláudio de Almeida Barbosa Guy J. Clarkson Martin Wills |
Abstract: | In 1995, Noyori and co-workers made a breakthrough with their design of practical ruthenium-based catalysts, which combined the homochiral TsDPEN ligand with a Ru(II) arene [1,2]. Using (R,R)-1 at a loading of 0.5 mol% in either KOH-iPrOH or the azeotropic mixture of formic acid–triethylamine (FA:TEA, 5:2 molar ratio), the reduction of acetophenone was achieved in up to 98% ee (Figure 1).The mechanism for the asymmetric transfer hydrogenation (ATH) with Noyori–Ikariya catalysts is now well-established (Figure 2) [3,4,5,6,7,8,9]. The precatalyst can be activated by elimination of HCl to form a 16-electron neutral Ru(II) complex. Then, the 16-electron complex abstracts two hydrogen atoms from the hydrogen donor, such as isopropanol, a formic acid/triethylamine (FA/TEA) mixture or sodium formate, to form a hydride that contains an 18-electron Ru(II) centre. Finally, the two hydrogen atoms are transferred to the C=O group and reduce ketone substrates into chiral alcohol products. Meanwhile, the 16-electron neutral Ru(II) complex is regenerated and can restart the catalytic cycle. The six-membered transition state can be stabilized by the combination of electrostatic interactions and steric effects. Edge/face (or CH/π) electrostatic interaction makes the electron-rich aryl group of a substrate favour the position adjacent to the η6-arene ring of the catalyst (Figure 3), whereas the large group and electron group favour the position distal to η6-arene ring (Figure 4). |
Subject: | Química Catálise Redução (Química) Hidrogenação |
language: | eng |
metadata.dc.publisher.country: | Brasil |
Publisher: | Universidade Federal de Minas Gerais |
Publisher Initials: | UFMG |
metadata.dc.publisher.department: | ICEX - INSTITUTO DE CIÊNCIAS EXATAS ICX - DEPARTAMENTO DE QUÍMICA |
Rights: | Acesso Aberto |
metadata.dc.identifier.doi: | https://doi.org/10.3390/ecsoc-25-11774 |
URI: | http://hdl.handle.net/1843/61104 |
Issue Date: | 14-Nov-2022 |
metadata.dc.url.externa: | http://https://doi.org/10.3390/ecsoc-25-11774 |
metadata.dc.relation.ispartof: | Chemistry Proceedings |
Appears in Collections: | Artigo de Periódico |
Files in This Item:
File | Description | Size | Format | |
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Asymmetric Transfer Hydrogenation of Aryl Heteroaryl Ketones and o-Hydroxyphenyl Ketones Using Noyori-Ikariya Catalysts.pdf | 1.59 MB | Adobe PDF | View/Open |
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