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      Easy To Synthesize, Robust Organo‐osmium Asymmetric Transfer Hydrogenation Catalysts

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          Abstract

          Asymmetric transfer hydrogenation (ATH) is an important process in organic synthesis for which the Noyori‐type Ru II catalysts [(arene)Ru(Tsdiamine)] are now well established and widely used. We now demonstrate for the first time the catalytic activity of the osmium analogues. X‐ray crystal structures of the 16‐electron Os II catalysts are almost identical to those of Ru II. Intriguingly the precursor complex was isolated as a dichlorido complex with a monodentate amine ligand. The Os II catalysts are readily synthesised (within 1 h) and exhibit excellent enantioselectivity in ATH reactions of ketones.

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          Bifunctional transition metal-based molecular catalysts for asymmetric syntheses.

          Takao Ikariya, Kunihiko Murata, Ryoji Noyori (2006)
          The discovery and development of conceptually new chiral bifunctional transition metal-based catalysts for asymmetric reactions is described. The chiral bifunctional Ru catalyst was originally developed for asymmetric transfer hydrogenation of ketones and imines and is now successfully applicable to enantioselective C-C bond formation reaction with a wide scope and high practicability. The deprotonation of 1,3-dicarbonyl compounds with the chiral amido Ru complexes leading to the amine Ru complexes bearing C- or O-bonded enolates, followed by further reactions with electrophlies gives C-C bond formation products. The present bifunctional Ru catalyst offers a great opportunity to open up new fundamentals for stereoselective molecular transformation including enantioselective C-H and C-C as well as C-O, C-N bond formation.
          Article 0 comments Cited 96 times – based on 0 reviews     Review now
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            Broader, greener, and more efficient: recent advances in asymmetric transfer hydrogenation.

            Jianliang Xiao, Chao Hsun Wang, Xiaofeng Wu (2008)
            Asymmetric transfer hydrogenation has become a practically useful tool in reduction chemistry in the last decade or so. This was largely triggered by the seminal work of Noyori and co-workers in the mid-1990s and is driven by its complementing chemistry to hydrogenation employing H(2). This Focus Review attempts to present a "holistic" overview on the advances in the area, focusing on the achievements recorded around the last three years. These include more-efficient and "greener" metal catalysts, catalysts that enable hydrogenation as well as transfer hydrogenation, biomimetic and organocatalysts, and their applications in the reduction of C==O, C==N, and C==C bonds. Also highlighted are efforts in the development of environmentally benign and reusable catalytic systems.
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              Reaction development and mechanistic study of a ruthenium catalyzed intramolecular asymmetric reductive amination en route to the dual Orexin inhibitor Suvorexant (MK-4305).

              Neil Strotman, Carl A Baxter, Karel M J Brands … (2011)
              The first example of an intramolecular asymmetric reductive amination of a dialkyl ketone with an aliphatic amine has been developed for the synthesis of Suvorexant (MK-4305), a potent dual Orexin antagonist under development for the treatment of sleep disorders. This challenging transformation is mediated by a novel Ru-based transfer hydrogenation catalyst that provides the desired diazepane ring in 97% yield and 94.5% ee. Mechanistic studies have revealed that CO(2), produced as a necessary byproduct of this transfer hydrogenation reaction, has pronounced effects on the efficiency of the Ru catalyst, the form of the amine product, and the kinetics of the transformation. A simple kinetic model explains how product inhibition by CO(2) leads to overall first-order kinetics, but yields an apparent zero-order dependence on initial substrate concentration. The deleterious effects of CO(2) on reaction rates and product isolation can be overcome by purging CO(2) from the system. Moreover, the rate of ketone hydrogenation can be greatly accelerated by purging of CO(2) or trapping with nucleophilic secondary amines.
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                Author and article information

                Contributors
                Prof. Dr. Martin Wills: m.wills@warwick.ac.uk
                Prof. Dr. Peter J. Sadler: p.j.sadler@warwick.ac.uk
                Journal
                Journal ID (nlm-ta): Chemistry
                Journal ID (iso-abbrev): Chemistry
                Journal ID (doi): 10.1002/(ISSN)1521-3765
                Journal ID (publisher-id): CHEM
                Title: Chemistry (Weinheim an Der Bergstrasse, Germany)
                Publisher: WILEY‐VCH Verlag (Weinheim )
                ISSN (Print): 0947-6539
                ISSN (Electronic): 1521-3765
                Publication date (Electronic): 08 April 2015
                Publication date (Print): 26 May 2015
                Volume: 21
                Issue: 22 ( doiID: 10.1002/chem.v21.22 )
                Pages: 8043-8046
                Affiliations
                [ 1 ]Department of Chemistry, University of Warwick, Coventry, CV4 7AL (UK)
                Author notes
                [*] [* ]Department of Chemistry, University of Warwick, Coventry, CV4 7AL (UK)
                Article
                Publisher ID: CHEM201500534
                DOI: 10.1002/chem.201500534
                PMC ID: 4832837
                PubMed ID: 25853228
                SO-VID: b73e597b-5a64-4e06-9ad1-e36cc2aa36e5
                Copyright © © 2015 The Authors. Published by Wiley‐VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited.
                License:

                Open access.

                History
                Date received : 09 February 2015
                Page count
                Figures: 6, Tables: 2, References: 70, Pages: 4
                Funding
                Funded by: Funded Access
                Funded by: ERC
                Award ID: 247450
                Funded by: EPSRC
                Award ID: EP/F034210/1
                Funded by: WCPRS and Bruker Daltonics
                Funded by: Leverhulme Trust
                Award ID: RGP 374
                Categories
                Subject: Communication
                Subject: Communications
                Subject: Asymmetric Catalysis
                Custom metadata
                source-schema-version-number 2.0
                cover-date May 26, 2015
                details-of-publishers-convertor Converter:WILEY_ML3GV2_TO_NLMPMC version:4.8.6 mode:remove_FC converted:15.04.2016

                ScienceOpen disciplines: Chemistry
                Keywords: asymmetric catalysis,hydrogen transfer,ketone reduction,organometallic complexes,osmium
                Data availability:
                ScienceOpen disciplines: Chemistry
                Keywords: asymmetric catalysis, hydrogen transfer, ketone reduction, organometallic complexes, osmium

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