Combinatorial Methods for the Discovery and Optimisation of Homogeneous Catalysts

Abstract

The use of combinatorial methods to discover new catalysts is one of the youngest fields of combinatorial chemistry. The main focus of this review is the application of combinatorial liquid- and solid-phase methods for the discovery and optimisation of homogeneous catalysts. In addition, high-throughput screening techniques for fast detection of activity and selectivity in catalytic reactions are discussed. The literature from 1995 to December 2000 is covered.

• 1 Introduction

• 2 Methods in Combinatorial Catalysis

• 3 Combinatorial Liquid-Phase Methods

• 3.1 Reaction Examples

• 3.1.1 Carbene Insertion

• 3.1.2 Reductive Aldol Reaction

• 3.1.3 Michael Addition

• 3.1.4 Diethyl Zinc Addition to Aldehydes

• 3.1.5 Aza-Diels-Alder Reaction

• 3.2 Modular Ligand Systems for Homogeneous Metal Catalysis

• 4 Combinatorial Solid-Phase Methods

• 4.1 Screening for Metal Binders

• 4.2 Catalysts in C-C Bond Formation

• 4.2.1 Diethyl Zinc Addition to Aldehydes

• 4.2.2 Addition of Trimethylsilylcyanide to meso-Epoxides

• 4.2.3 Asymmetric Strecker Reaction

• 4.2.4 Allylic Substitution Reactions

• 4.3 Catalytic Oxidation and Reduction Reactions

• 4.3.1 Alkene Epoxidation

• 4.3.2 Catalytic Hydrogenation

• 4.4 Catalytic Phosphate Hydrolysis

• 5 High-Throughput Screening in Catalysis

• 5.1 IR-Thermography

• 5.2 Isotope Labelling/Pseudo Enantiomers

• 5.3 Fluorescence Assays

• 5.4 Reactive Dyes

• 5.5 One-pot Multi Substrate Screening

• 5.6 Screening of Mixtures of Catalysts

• 5.7 Miscellaneous Chromatographic Methods

• 6 Conclusion

Key words

combinatorial catalysis - catalysis - combinatorial chemistry - asymmetric catalysis - high-throughput screening

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5

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21

(CuOTf)C₆H₆ and sparteine in THF were used.

22

[Rh(nbd)]BPh₄ and sparteine in toluene were used.

24

Abbrevations: i-Pr-pybox = 2,6-bis(4-isopropyl-2-oxazolin-2-yl)pyridine, t-Bu-box = 2,2"-isopropylidenebis(4-tert-butyl-2-oxazoline), Ph-semicorrin = 4-phenyl-α-[4-phenyloxazolidin-2-ylidene]-2-oxazoline-2-acetonitrile, MOP = 2-(diphenylphosphino-2"-methoxy)-1,1"-binaphthyl, BINAP = 2,2"-bis(diphenylphosphino)-1,1"-binaphthyl, DuPhos = 1,2-bis(2,5-dimethylphospholano)benzene, quinap = 1-(2-diphenylphosphino-1-naphtyl)isoquinoline, cod = cyclooctadiene.

71

The relationship between the two phosphine-containing amino acids is determined by their relative position in the peptide sequence. If the first is placed in the position i of the peptide sequence, the second is e.g. in the i+4 position. In this case three other amino acids are positioned between them.

94

MegaBASE is commercially available from Amersham Pharmacia Biotech (Freiburg, Germany).