Catalytic activities of Schiff base transition metal complexes

Laboratory for Advanced Materials and New Catalysis, School of Chemistry and Materials Science, Hubei University, Wuhan 430062, China,Laboratory of Natural Gas Utilization and Applied Catalysis, Dalian Institute of Chemical Physics of Chinese Academy of Sciences, Dalian 116023,China, and Jingmen Technological College, Jingmen 448000, ChinaReceived June 30, 2004

Advances in Homogeneous and Heterogeneous Catalytic Asymmetric Epoxidation

The first salen ligand and Cu complex were discovered in 1889, and gradually the potential catalytic activity of subsequent salen species has been recognised, particularly in the case of achiral salen complexes in oxidation reactions. The development of chiral salen metal complexes and catalysts in the last decade has however stimulated a very rapid growth in the chemistry and application of these species. The variety of asymmetric reactions in which particular chiral metal salen complexes are proving useful grows steadily, and there is no evidence of this growth slowing. This review summarises the key work and references on soluble chiral metal salen complex catalysts categorised according to the metal centre. It also describes the work to date on producing supported heterogeneous chiral analogues of some of these.

Utilisation of homogeneous and supported chiral metal(salen) complexes in asymmetric catalysis

Chiral Salen Complexes: An Overview to Recoverable and Reusable Homogeneous and Heterogeneous Catalysts

Asymmetric catalysis is a challenge for chemists: How can we design catalysts to achieve the goal of forming optically active compounds? This review provides the reader with an overview of the development of catalytic asymmetric hetero-Diels–Alder reactions of carbonyl compounds and imines. Since its discovery, the Diels–Alder reaction has undergone intensive development and is of fundamental importance for synthetic, physical, and theoretical chemists. The Diels–Alder reaction has been through different stages of development, and at the beginning of the 21st century catalytic Diels–Alder reactions are one of the main areas of focus. The preparation of numerous compounds of importance for our society is based on cycloaddition reactions to carbonyl compounds and imines. There are several parallels between the reactions of carbonyl compounds and those of imines, which, however, begin to vanish on entering the field of catalytic reactions. Why? From a mechanistic point of view some similarities can be drawn, but the synthetic development of catalytic enantioselective hetero-Diels–Alder reactions of imines are several years behind those of the carbonyl compounds. For hetero-Diels–Alder reactions of carbonyl compounds there a number of different chiral catalysts, and great progress has been achieved in developing enantioselective reactions for unactivated and activated carbonyl compounds. In contrast the development of catalytic enantioselective hetero-Diels–Alder reactions of imines is in its infancy and only few catalytic reactions have been published. This review will focus on the most important developments, and discuss the synthetic and mechanistic aspects of enantioselective hetero-Diels–Alder reactions of carbonyl compounds catalyzed by chiral Lewis acids. For the hetero-Diels–Alder reactions of imines, the diastereoselective reactions of optically substrates catalyzed by Lewis acids will be presented first, followed by the catalytic enantioselective reactions.

Catalytic Asymmetric Hetero‐Diels–Alder Reactions of Carbonyl Compounds and Imines

Asymmetric Hetero-Diels−Alder Reactions Catalyzed by Chiral (Salen)Chromium(III) Complexes

It is axiomatic in medicinal chemistry that optimization of the potency of a small molecule at a macromolecular target requires complementarity between the ligand and target. In order to minimize the conformational penalty on binding, both enthalpically and entropically, it is therefore preferred to have the ligand preorganized in the bound conformation. In this Perspective, we highlight the role of allylic strain in controlling conformational preferences. Allylic strain was originally described for carbon-based allylic systems, but the same principles apply to other types of structure with sp2 or pseudo-sp2 arrangements. These systems include benzylic (including heteroaryl methyl) positions, amides, N-aryl groups, aryl ethers, and nucleotides. We have derived torsion profiles from small molecule X-ray structures for these systems. Through multiple examples, we show how these effects have been applied in drug discovery and how they can be used prospectively to influence conformation in the design process.

Jonas Brånalt

Papers

Asymmetric Hetero-Diels−Alder Reactions Catalyzed by Chiral (Salen)Chromium(III) Complexes

The Role of Allylic Strain for Conformational Control in Medicinal Chemistry.