E-Mail Alert

Add your e-mail address to receive forthcoming issues of this journal:

Journal Browser

Journal Browser

Special Issue "Catalytic Asymmetric Synthesis"

Quicklinks

A special issue of Molecules (ISSN 1420-3049).

Deadline for manuscript submissions: closed (31 May 2011)

Special Issue Editor

Guest Editor
Prof. Dr. Michael North (Website)

School of Chemistry, Bedson Building, University of Newcastle upon Tyne, Newcastle upon Tyne, UK
Phone: 44 191 2227128
Interests: catalytic asymmetric synthesis; carbon-carbon bonds formation

Special Issue Information

Dear Colleagues,

Asymmetric catalysis has a long a distinguished history (well over 100 years), yet it remains at the forefront of chemical research. Not only do chemists constantly seek to improve catalysts activity and enantioselectivity and to broaden their substrate scope, but catalysts for new reactions are constantly being developed and progress is being made in unconventional use of asymmetric catalysts, for example in cascade sequences and under unconventional reaction conditions (flow reactors, green solvents etc). The application of asymmetric catalysts under these conditions often requires their structural modification and/or immobilization. Thus, asymmetric catalysis encompasses both homogeneous and heterogeneous catalysis and aspects of chemical engineering are becoming increasingly relevant to the large scale application of asymmetric catalysts. Our depth of understanding of mechanisms in asymmetric catalysis is also rapidly increasing aided by the introduction of powerful new experimental and computational tools. Especially notable over the last ten years has been the renaissance of asymmetric organocatalysis.

Asymmetric catalysis also plays a central role in many other areas of chemistry. The pharmaceutical industry is steadily making increasing use of asymmetric catalysis as an attractive alternative to other more wasteful methods for the preparation of enantiomerically pure pharmaceuticals. Catalysis in general and asymmetric catalysis in particular is central to Green chemistry and the whole of biological chemistry is essentially the chemistry of Nature’s own asymmetric catalysts – enzymes. Indeed one of the currently unsolved major questions in science – how was life able to exploit enantiomerically pure building blocks? Is at least partly a question for asymmetric catalysis to answer through non-linear effects and autocatalytic asymmetric induction.

The aim of this special issue of Molecules is to bring together new research in the development and application of asymmetric catalysis to illustrate the state of the art. Work in all areas of asymmetric catalysis is welcome including, but not limited too:

  • Development of metal based catalysts
  • Development of organocatalysts and organocatalysed reactions
  • Asymmetric Lewis base catalysis
  • Enzyme catalysis
  • Mechanistic studies on the mode of action of asymmetric catalysts
  • Theoretical studies on asymmetric catalysis
  • Application of asymmetric catalysis in synthesis
  • Use of asymmetric catalysts in non-conventional solvents and reactors

I strongly encourage authors to submit their work to this special issue of Molecules and look forward to reading their contributions.

Prof. Dr. Michael North
Guest Editor

Keywords

  • asymmetric
  • catalysis
  • metal
  • organocatalyst
  • chiral-ligand

Published Papers (8 papers)

View options order results:
result details:
Displaying articles 1-8
Export citation of selected articles as:

Research

Jump to: Review

Open AccessArticle Enantioselective Addition of Allyltin Reagents to Amino Aldehydes Catalyzed with Bis(oxazolinyl)phenylrhodium(III) Aqua Complexes
Molecules 2011, 16(7), 5387-5401; doi:10.3390/molecules16075387
Received: 30 May 2011 / Revised: 20 June 2011 / Accepted: 23 June 2011 / Published: 27 June 2011
Cited by 3 | PDF Full-text (222 KB)
Abstract
Bis(oxazolinyl)phenylrhodium(III) aqua complexes, (Phebox)RhX2(H2O) [X = Cl, Br], were found to be efficient Lewis acid catalysts for the enantioselective addition of allyl- and methallyltributyltin reagents to amino aldehydes. The reactions proceed smoothly in the presence of 5–10 mol [...] Read more.
Bis(oxazolinyl)phenylrhodium(III) aqua complexes, (Phebox)RhX2(H2O) [X = Cl, Br], were found to be efficient Lewis acid catalysts for the enantioselective addition of allyl- and methallyltributyltin reagents to amino aldehydes. The reactions proceed smoothly in the presence of 5–10 mol % of (Phebox)RhX2(H2O) complex at ambient temperature to give the corresponding amino alcohols with modest to good enantioselectivity (up to 94% ee). Full article
(This article belongs to the Special Issue Catalytic Asymmetric Synthesis)
Open AccessArticle Enantio and Diastereoselective Addition of Phenylacetylene to Racemic α-chloroketones
Molecules 2011, 16(6), 5298-5314; doi:10.3390/molecules16065298
Received: 26 May 2011 / Revised: 17 June 2011 / Accepted: 22 June 2011 / Published: 23 June 2011
Cited by 4 | PDF Full-text (235 KB)
Abstract
In this report, we have presented the first diastereoselective addition of phenylacetylene to chiral racemic chloroketones. The addition is controlled by the reactivity of the chloroketones that allowed the stereoselective reaction to be performed at –20 °C. Chiral racemic chloroketones are used [...] Read more.
In this report, we have presented the first diastereoselective addition of phenylacetylene to chiral racemic chloroketones. The addition is controlled by the reactivity of the chloroketones that allowed the stereoselective reaction to be performed at –20 °C. Chiral racemic chloroketones are used in the reaction. By carefully controlling the temperature and the reaction time we were able to isolate the corresponding products in moderate yields and with good, simple and predictable facial stereoselection. Our reaction is a rare example of the use of chiral ketones in an enantioselective alkynylation reaction and opens new perspectives for the formation of chiral quaternary stereocenters. Full article
(This article belongs to the Special Issue Catalytic Asymmetric Synthesis)
Figures

Open AccessArticle Enantioselective Evans-Tishchenko Reduction of b-Hydroxyketone Catalyzed by Lithium Binaphtholate
Molecules 2011, 16(6), 5008-5019; doi:10.3390/molecules16065008
Received: 1 June 2011 / Revised: 10 June 2011 / Accepted: 15 June 2011 / Published: 17 June 2011
Cited by 4 | PDF Full-text (211 KB)
Abstract Lithium diphenylbinaphtholate catalyzed the enantioselective Evans-Tishchenko reduction of achiral b-hydroxyketones to afford monoacyl-protected 1,3-diols with high stereoselectivities. In the reaction of racemic b-hydroxyketones, kinetic optical resolution occurred in a highly stereoselective manner. Full article
(This article belongs to the Special Issue Catalytic Asymmetric Synthesis)
Open AccessArticle Ru/Me-BIPAM-Catalyzed Asymmetric Addition of Arylboronic Acids to Aliphatic Aldehydes and α-Ketoesters
Molecules 2011, 16(6), 5020-5034; doi:10.3390/molecules16065020
Received: 31 May 2011 / Revised: 13 June 2011 / Accepted: 15 June 2011 / Published: 17 June 2011
Cited by 34 | PDF Full-text (266 KB)
Abstract A ruthenium-catalyzed asymmetric arylation of aliphatic aldehydes and α-ketoesters with arylboronic acids has been developed, giving chiral alkyl(aryl)methanols and α-hydroxy esters in good yields. The use of a chiral bidentate phosphoramidite ligand (Me-BIPAM) achieved excellent enantioselectivities. Full article
(This article belongs to the Special Issue Catalytic Asymmetric Synthesis)
Figures

Open AccessArticle Proline-Catalysed Amination Reactions in Cyclic Carbonate Solvents
Molecules 2011, 16(4), 3420-3432; doi:10.3390/molecules16043420
Received: 6 April 2011 / Revised: 19 April 2011 / Accepted: 20 April 2011 / Published: 21 April 2011
Cited by 27 | PDF Full-text (214 KB)
Abstract
Propylene carbonate is shown to be an environmentally friendly and sustainable replacement for dichloromethane and acetonitrile in proline-catalysed a-hydrazinations of aldehydes and ketones. Enantioselectivities comparable to those obtained in conventional solvents or ionic liquids can be obtained, even when using a lower [...] Read more.
Propylene carbonate is shown to be an environmentally friendly and sustainable replacement for dichloromethane and acetonitrile in proline-catalysed a-hydrazinations of aldehydes and ketones. Enantioselectivities comparable to those obtained in conventional solvents or ionic liquids can be obtained, even when using a lower catalyst loading. Full article
(This article belongs to the Special Issue Catalytic Asymmetric Synthesis)
Figures

Open AccessArticle Catalytic Enantioselective Aryl Transfer to Aldehydes Using Chiral 2,2’-Bispyrrolidine-Based Salan Ligands
Molecules 2011, 16(4), 2971-2981; doi:10.3390/molecules16042971
Received: 24 December 2010 / Revised: 15 March 2011 / Accepted: 16 March 2011 / Published: 6 April 2011
Cited by 3 | PDF Full-text (238 KB)
Abstract
Chiral C2-symmetric diamines have emerged as versatile auxiliaries or ligands in numerous asymmetric transformations. Chiral 2,2’-bispyrrolidine-based salan ligands were prepared and applied to the asymmetric aryl transfer to aldehydes with arylboronic acids as the source of transferable aryl groups. The [...] Read more.
Chiral C2-symmetric diamines have emerged as versatile auxiliaries or ligands in numerous asymmetric transformations. Chiral 2,2’-bispyrrolidine-based salan ligands were prepared and applied to the asymmetric aryl transfer to aldehydes with arylboronic acids as the source of transferable aryl groups. The corresponding diarylmethanols were obtained in high yields with moderate to good enantioselectivitives of up to 83% ee. Full article
(This article belongs to the Special Issue Catalytic Asymmetric Synthesis)

Review

Jump to: Research

Open AccessReview In Mesopore Protein Digestion: A New Forthcoming Strategy in Proteomics
Molecules 2011, 16(7), 5938-5962; doi:10.3390/molecules16075938
Received: 2 June 2011 / Revised: 7 July 2011 / Accepted: 13 July 2011 / Published: 15 July 2011
Cited by 14 | PDF Full-text (756 KB)
Abstract
The conventional protocols for in solution or in gel protein digestion require many steps and long reaction times. The use of trypsin immobilized onto solid supports has recently captured the attention of many research groups, because these systems can speed-up protein digestion [...] Read more.
The conventional protocols for in solution or in gel protein digestion require many steps and long reaction times. The use of trypsin immobilized onto solid supports has recently captured the attention of many research groups, because these systems can speed-up protein digestion significantly. The utilization of new materials such as mesoporous silica as supports, in which enzyme and substrate are dramatically concentrated and confined in the nanospace, offers new opportunities to reduce the complexity of proteomics workflows. An overview of the procedures for in situ proteolysis of single proteins or complex protein mixtures is reported, with a special focus on porous materials used as catalysts. The challenging efforts for designing such systems aimed at mimicking the biochemistry of living cells are reviewed. Potentials, limitations and challenges of this branch of enzyme catalysis, which we indicate as in mesopore digestion, are discussed, in relation to its suitability for high-speed and high-throughput proteomics. Full article
(This article belongs to the Special Issue Catalytic Asymmetric Synthesis)
Open AccessReview Opportunities Offered by Chiral η6-Arene/N-Arylsulfonyl-diamine-RuII Catalysts in the Asymmetric Transfer Hydrogenation of Ketones and Imines
Molecules 2011, 16(7), 5460-5495; doi:10.3390/molecules16075460
Received: 25 May 2011 / Revised: 14 June 2011 / Accepted: 17 June 2011 / Published: 28 June 2011
Cited by 38 | PDF Full-text (821 KB)
Abstract
Methods for the asymmetric transfer hydrogenation (ATH) of ketones and imines are still being intensively studied and developed. Of foremost interest is the use of Noyori’s [RuCl(η6-arene)(N-TsDPEN)] complexes in the presence of a hydrogen donor (i-PrOH, [...] Read more.
Methods for the asymmetric transfer hydrogenation (ATH) of ketones and imines are still being intensively studied and developed. Of foremost interest is the use of Noyori’s [RuCl(η6-arene)(N-TsDPEN)] complexes in the presence of a hydrogen donor (i-PrOH, formic acid). These complexes have found numerous practical applications and have been extensively modified. The resulting derivatives have been heterogenized, used in ATH in water or ionic liquids and even some attempts have been made to approach the properties of biocatalysts. Therefore, an appropriate modification of the catalyst that suits the specific requirements for the reaction conditions is very often readily available. The mechanism of the reaction has also been explored to a great extent. Model substrates, acetophenone (a ketone) and 6,7-dimethoxy-1-methyl-3,4-dihydroisoquinoline (an imine), are both reduced by this Ru catalytic system with almost perfect selectivity. However, in each case the major product is a different enantiomer (S- for an alcohol, R- for an amine when the S,S-catalyst is used), which demanded an in-depth mechanistic investigation. Full-scale molecular modelling of this system enabled us to visualize the plausible 3D structures of the transition states, allowing the proposition of a viable explanation of previous experimental findings. Full article
(This article belongs to the Special Issue Catalytic Asymmetric Synthesis)

Journal Contact

MDPI AG
Molecules Editorial Office
St. Alban-Anlage 66, 4052 Basel, Switzerland
molecules@mdpi.com
Tel. +41 61 683 77 34
Fax: +41 61 302 89 18
Editorial Board
Contact Details Submit to Molecules
Back to Top