E-Mail Alert

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

Journal Browser

Journal Browser

Special Issue "Bifunctional Catalysis"

Quicklinks

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

Deadline for manuscript submissions: closed (15 October 2010)

Special Issue Editor

Guest Editor
Prof. Dr. Takao Ikariya

Department of Applied Chemistry, Graduate School of Science and Engineering, Tokyo Institute of Technology, Japan
E-Mail
Fax: +81 3 5734 2637

Special Issue Information

Dear Colleagues,

Recent advances in green and sustainable science and technology strongly demand powerful and sophisticated catalysts with a tunable multifunction. The design and development of molecular catalysts with a bifunction based on the combination of Lewis acid and Lewis base working in concert is of ongoing interest in organic synthetic chemistry. Since the bifunctional catalysts contain two or more active sites for activation of the electrophiles and nucleophiles, they can efficiently effect a wide range of molecular transformation including C–H, C–C, C–O, or C–N bond formation by dual activation and effective accumulation of reacting substrates on the neighboring active centers in the same molecules. Thus, the rational design of the cooperating ligand that also adjust the balance of the electronic factors in the bifunctional catalysts is crucially important to exploit unprecedented catalyst performance.

Prof. Dr. Takao Ikariya
Guest Editor

Keywords

  • bifunctional catalyst
  • acid-base synergy effect
  • cooperating lignad
  • multi-metallic center catalyst
  • non-innocent ligand
  • dual activation
  • asymmetric catalysis
  • concerto molecular catalysis
  • environmental benign synthetic process

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 Catalytic Asymmetric Synthesis of Both Enantiomers of 4‑Substituted 1,4-Dihydropyridines with the Use of Bifunctional Thiourea-Ammonium Salts Bearing Different Counterions
Molecules 2010, 15(11), 8305-8326; doi:10.3390/molecules15118305
Received: 13 October 2010 / Revised: 8 November 2010 / Accepted: 12 November 2010 / Published: 15 November 2010
Cited by 12 | PDF Full-text (318 KB)
Abstract
Organoammonium salts composed of a Brønsted acid and an anilinothiourea promoted the Michael addition of β-keto esters and α,β-unsaturated aldehydes in the presence of primary amines to give functionalized 1,4-dihydropyridines enantioselectively. With the use of the different Brønsted acids such as DFA and
[...] Read more.
Organoammonium salts composed of a Brønsted acid and an anilinothiourea promoted the Michael addition of β-keto esters and α,β-unsaturated aldehydes in the presence of primary amines to give functionalized 1,4-dihydropyridines enantioselectively. With the use of the different Brønsted acids such as DFA and HBF4 with the same bifunctional thiourea, both enantiomers of 4-substituted 1,4-dihydropyridine were synthesized from the same starting materials. Full article
(This article belongs to the Special Issue Bifunctional Catalysis)
Figures

Open AccessArticle Synthesis and Properties of Chiral Thioureas Bearing an Additional Function at a Remote Position Tethered by a 1,5-Disubstituted Triazole
Molecules 2010, 15(11), 8327-8348; doi:10.3390/molecules15118327
Received: 20 October 2010 / Revised: 8 November 2010 / Accepted: 10 November 2010 / Published: 15 November 2010
Cited by 4 | PDF Full-text (250 KB)
Abstract
The synthesis and properties of multifunctional thioureas bearing a variety of functional groups at a position remote from the thiourea moiety are described. A 1,5-disubstituted triazole tether connected with a thiourea and another functional group was synthesized via ruthenium catalyzed Huisgen cycloaddition. We
[...] Read more.
The synthesis and properties of multifunctional thioureas bearing a variety of functional groups at a position remote from the thiourea moiety are described. A 1,5-disubstituted triazole tether connected with a thiourea and another functional group was synthesized via ruthenium catalyzed Huisgen cycloaddition. We demonstrate the utility of the synthetic thioureas as asymmetric catalysts and probes for the mechanistic elucidation of the course of the Michael reaction of an α,β-unsaturated imide Full article
(This article belongs to the Special Issue Bifunctional Catalysis)
Open AccessCommunication Application of Phosphine-Phosphite Ligands in the Iridium Catalyzed Enantioselective Hydrogenation of 2-Methylquinoline
Molecules 2010, 15(11), 7732-7741; doi:10.3390/molecules15117732
Received: 6 October 2010 / Revised: 26 October 2010 / Accepted: 28 October 2010 / Published: 29 October 2010
Cited by 14 | PDF Full-text (121 KB)
Abstract
The hydrogenation of 2-methylquinoline with Ir catalysts based on chiral phosphine-phosphites has been investigated. It has been observed that the reaction is very sensitive to the nature of the ligand. Optimization of the catalyst, allowed by the highly modular structure of these phosphine-phosphites,
[...] Read more.
The hydrogenation of 2-methylquinoline with Ir catalysts based on chiral phosphine-phosphites has been investigated. It has been observed that the reaction is very sensitive to the nature of the ligand. Optimization of the catalyst, allowed by the highly modular structure of these phosphine-phosphites, has improved the enantioselectivity of the reaction up to 73% ee. The influence of additives in this reaction has also been investigated. Contrary to the beneficial influence observed in related catalytic systems, iodine has a deleterious effect in the present case. Otherwise, aryl phosphoric acids produce a positive impact on catalyst activity without a decrease on enantioselectivity. Full article
(This article belongs to the Special Issue Bifunctional Catalysis)
Open AccessArticle Bifunctional Catalysis: Direct Reductive Amination of Aliphatic Ketones with an Iridium-Phosphate Catalyst
Molecules 2010, 15(4), 2453-2472; doi:10.3390/molecules15042453
Received: 9 March 2010 / Revised: 29 March 2010 / Accepted: 2 April 2010 / Published: 8 April 2010
Cited by 31 | PDF Full-text (316 KB)
Abstract
Chiral amines are one of the ubiquitous functional groups in fine chemical, pharmaceutical and agrochemical products, and the most convenient, economical, and eco-benign synthetic pathway to these amines is direct asymmetric reductive amination (DARA) of prochiral ketones. This paper shows that a wide
[...] Read more.
Chiral amines are one of the ubiquitous functional groups in fine chemical, pharmaceutical and agrochemical products, and the most convenient, economical, and eco-benign synthetic pathway to these amines is direct asymmetric reductive amination (DARA) of prochiral ketones. This paper shows that a wide range of aliphatic ketones can be directly aminated under hydrogenation conditions, affording chiral amines with good to excellent yields and with enantioselectivities up to 96% ee. The catalysis is effected by the cooperative action of a cationic Cp*Ir(III) complex and its phosphate counteranion. Full article
(This article belongs to the Special Issue Bifunctional Catalysis)
Figures

Open AccessArticle Catalytic Asymmetric Nitro-Mannich Reactions with a Yb/K Heterobimetallic Catalyst
Molecules 2010, 15(3), 1280-1290; doi:10.3390/molecules15031280
Received: 1 February 2010 / Revised: 10 February 2010 / Accepted: 2 March 2010 / Published: 4 March 2010
Cited by 14 | PDF Full-text (158 KB)
Abstract
A catalytic asymmetric nitro-Mannich (aza-Henry) reaction with rare earth metal/alkali metal heterobimetallic catalysts is described. A Yb/K heterobimetallic catalyst assembled by an amide-based ligand promoted the asymmetric nitro-Mannich reaction to afford enantioenriched anti-b-nitroamines in up to 86% ee. Facile reduction of the
[...] Read more.
A catalytic asymmetric nitro-Mannich (aza-Henry) reaction with rare earth metal/alkali metal heterobimetallic catalysts is described. A Yb/K heterobimetallic catalyst assembled by an amide-based ligand promoted the asymmetric nitro-Mannich reaction to afford enantioenriched anti-b-nitroamines in up to 86% ee. Facile reduction of the nitro functionality allowed for efficient access to optically active 1,2-diamines. Full article
(This article belongs to the Special Issue Bifunctional Catalysis)
Figures

Open AccessArticle Catalytic Asymmetric 1,4-Additions of β-Keto Esters to Nitroalkenes Promoted by a Bifunctional Homobimetallic Co2-Schiff Base Complex
Molecules 2010, 15(1), 532-544; doi:10.3390/molecules15010532
Received: 24 December 2009 / Revised: 18 January 2010 / Accepted: 21 January 2010 / Published: 22 January 2010
Cited by 15 | PDF Full-text (212 KB)
Abstract
Catalytic asymmetric 1,4-addition of β-keto esters to nitroalkenes is described. 2.5 mol % of a homobimetallic Lewis acid/Brønsted base bifunctional Co2-Schiff base complex smoothly promoted the reaction in excellent yield (up to 99%), diastereoselectivity, and enantioselectivity (up to >30:1 dr and
[...] Read more.
Catalytic asymmetric 1,4-addition of β-keto esters to nitroalkenes is described. 2.5 mol % of a homobimetallic Lewis acid/Brønsted base bifunctional Co2-Schiff base complex smoothly promoted the reaction in excellent yield (up to 99%), diastereoselectivity, and enantioselectivity (up to >30:1 dr and 98% ee). Catalyst loading was successfully reduced to 0.1 mol %. Mechanistic studies suggested that intramolecular cooperative functions of the two Co-metal centers are important for high catalytic activity and stereoselectivity. Full article
(This article belongs to the Special Issue Bifunctional Catalysis)

Review

Jump to: Research

Open AccessReview Development of Heterogeneous Olympic Medal Metal Nanoparticle Catalysts for Environmentally Benign Molecular Transformations Based on the Surface Properties of Hydrotalcite
Molecules 2010, 15(12), 8988-9007; doi:10.3390/molecules15128988
Received: 15 November 2010 / Revised: 29 November 2010 / Accepted: 7 December 2010 / Published: 8 December 2010
Cited by 27 | PDF Full-text (447 KB)
Abstract
In this review, we describe the development by our research group of highly functionalized heterogeneous Olympic medal metal (gold, silver, and copper) nanoparticle catalysts using hydrotalcite as a support, aimed towards Green and Sustainable Chemistry. Olympic medal metal nanoparticles can cooperate with the
[...] Read more.
In this review, we describe the development by our research group of highly functionalized heterogeneous Olympic medal metal (gold, silver, and copper) nanoparticle catalysts using hydrotalcite as a support, aimed towards Green and Sustainable Chemistry. Olympic medal metal nanoparticles can cooperate with the basic sites on the hydrotalcite surface, providing unique and high performance catalysis in environmentally-benign organic transformations such as aerobic oxidation of alcohols, lactonization of diols and selective deoxygenation of epoxides and nitro aromatic compounds. Full article
(This article belongs to the Special Issue Bifunctional Catalysis)
Open AccessReview Norcoclaurine Synthase: Mechanism of an Enantioselective Pictet-Spengler Catalyzing Enzyme
Molecules 2010, 15(4), 2070-2078; doi:10.3390/molecules15042070
Received: 2 March 2010 / Revised: 18 March 2010 / Accepted: 22 March 2010 / Published: 24 March 2010
Cited by 19 | PDF Full-text (135 KB)
Abstract
The use of bifunctional catalysts in organic synthesis finds inspiration in the selectivity of enzymatic catalysis which arises from the specific interactions between basic and acidic amino acid residues and the substrate itself in order to stabilize developing charges in the transition state.
[...] Read more.
The use of bifunctional catalysts in organic synthesis finds inspiration in the selectivity of enzymatic catalysis which arises from the specific interactions between basic and acidic amino acid residues and the substrate itself in order to stabilize developing charges in the transition state. Many enzymes act as bifunctional catalysts using amino acid residues at the active site as Lewis acids and Lewis bases to modify the substrate as required for the given transformation. They bear a clear advantage over non-biological methods for their ability to tackle problems related to the synthesis of enantiopure compounds as chiral building blocks for drugs and agrochemicals. Moreover, enzymatic synthesis may offer the advantage of a clean and green synthetic process in the absence of organic solvents and metal catalysts. In this work the reaction mechanism of norcoclaurine synthase is described. This enzyme catalyzes the Pictet-Spengler condensation of dopamine with 4-hydroxyphenylacetaldehyde (4-HPAA) to yield the benzylisoquinoline alkaloids central precursor, (S)-norcoclaurine. Kinetic and crystallographic data suggest that the reaction mechanism occurs according to a typical bifunctional catalytic process. Full article
(This article belongs to the Special Issue Bifunctional Catalysis)

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