The increasing demand to produce enantiomerically pure pharmaceuticals, agrochemicals, flavors, and other fine chemicals has advanced the field of asymmetric catalytic technologies.1,2 Among all asymmetric catalytic methods, asymmetric hydrogenation utilizing molecular hydrogen to reduce prochiral olefins, ketones, and imines, have become one of the most efficient methods for constructing chiral compounds.3 The development of homogeneous asymmetric hydrogenation was initiated by Knowles4a and Horner4b in the late 1960s, after the discovery of Wilkinson’s homogeneous hydrogenation catalyst [RhCl(PPh3)3]. By replacing triphenylphosphine of the Wilkinson’s catalystwithresolvedchiralmonophosphines,6Knowles and Horner reported the earliest examples of enantioselective hydrogenation, albeit with poor enantioselectivity. Further exploration by Knowles with an improved monophosphine CAMP provided 88% ee in hydrogenation of dehydroamino acids.7 Later, two breakthroughs were made in asymmetric hydrogenation by Kagan and Knowles, respectively. Kagan reported the first bisphosphine ligand, DIOP, for Rhcatalyzed asymmetric hydrogenation.8 The successful application of DIOP resulted in several significant directions for ligand design in asymmetric hydrogenation. Chelating bisphosphorus ligands could lead to superior enantioselectivity compared to monodentate phosphines. Additionally, P-chiral phosphorus ligands were not necessary for achieving high enantioselectivity, and ligands with backbone chirality could also provide excellent ee’s in asymmetric hydrogenation. Furthermore, C2 symmetry was an important structural feature for developing new efficient chiral ligands. Kagan’s seminal work immediately led to the rapid development of chiral bisphosphorus ligands. Knowles made his significant discovery of a C2-symmetric chelating bisphosphine ligand, DIPAMP.9 Due to its high catalytic efficiency in Rh-catalyzed asymmetric hydrogenation of dehydroamino acids, DIPAMP was quickly employed in the industrial production of L-DOPA.10 The success of practical synthesis of L-DOPA via asymmetric hydrogenation constituted a milestone work and for this work Knowles was awarded the Nobel Prize in 2001.3k This work has enlightened chemists to realize * Corresponding author. 3029 Chem. Rev. 2003, 103, 3029−3069

New Chiral Phosphorus Ligands for Enantioselective Hydrogenation

Preparation of polymer-supported ligands and metal complexes for use in catalysis.

Recoverable Catalysts for Asymmetric Organic Synthesis

1 Review 1.1 Overview 1.2 Solid-phase organic synthesis (SPOS) 1.3 Beyond conventional solid-phase organic synthesis 1.4 The review 1.5 Some definitions 1.6 Solid-supported reagents and scavengers 1.7 Multi-step use of solid-supported reagents and scavenging reagents 1.8 Conclusions and future perspective 2 Introduction to the tables 2.1 Organisation of tables (reagent and catalyst section) 2.2 Representative data entry (reagent and catalyst section) 2.3 Organisation of tables (scavenging agents section) 2.4 Representative data entry (scavenging agents section) 3 Tables of reagents and catalysts 4 Tables of scavengers 5 Other relevant reviews 5.1 Insoluble polymers 5.1.1 Structure and physical properties (insoluble polymers) 5.1.2 General (insoluble polymers) 5.1.3 Reactions (insoluble polymers) 5.1.4 Miscellaneous (insoluble polymers) 5.2 Soluble polymers 5.2.1 General (soluble polymers) 5.2.2 Reactions (soluble polymers) 5.3 Inorganic solids 5.3.1 Structure and physical properties (inorganic solids) 5.3.2 General (inorganic solids) 5.3.3 Reactions (inorganic solids) 5.3.4 Miscellaneous (inorganic solids) 5.4 Miscellaneous supports 5.4.1 Structure and physical properties (miscellaneous supports) 5.4.2 General (miscellaneous supports) 5.4.3 Reactions (miscellaneous supports) 5.4.4 Miscellaneous (miscellaneous supports) 5.5 Purification strategies 5.5.1 Various supports (purification strategies) 5.5.2 Insoluble polymers (purification strategies) 6 Acknowledgements 7 Abbreviations 8 References 1 Review

Multi-step organic synthesis using solid-supported reagents and scavengers: a new paradigm in chemical library generation

Contents 1.0Introduction
1.1 Polystyrene Supports as Carriers for Reagents and Catalysts
1.2 Catalyst and Reagent Attachment to Polymer Supports
2.0C-C Bond Formation Using Recyclable Resin-Based Reagents and Catalysts
2.1 Palladium-Catalyzed Coupling Reactions
2.2 Other Transition Metal Catalyzed Reactions
2.3 Resin-Supported Olefin Metathesis
2.4 Resin-Mediated Cycloaddition Reactions
2.4.1 Diels-Alder Cycloadditions
2.4.2 Resin-Based Catalysts for 1,3-Dipolar Cycloadditions
2.5 Immobilized Chiral Ligands for Diethylzinc Additions to Aldehydes
2.6 Miscellaneous: Other C-C Bond Forming Reactions
3.0Immobilized Oxidants
3.1Oxidation with Immobilized Transition Metal Complexes
3.2 Alcohol Oxidation
3.3 Alkene Oxidation
3.3.1 Dihydroxylation
3.3.2 Epoxidation
3.3.3 Asymmetric Epoxidation
3.3.4 Other Alkene Oxidation Reactions
3.4 Potpourri: Other Immobilized Oxidants
4.0Immobilized Resin-Based Reductants
4.1 General Reduction Processes
4.2 Asymmetric Reduction of Ketones
4.3 Alkene Reduction
4.4 Resin-Based Tin and Germanium Reductants
5.0Conclusions
6.0Abbreviations
7.0Acknowledgments
8.0References

Recoverable Catalysts and Reagents Using Recyclable Polystyrene-Based Supports

Preparation and Use of a Polymer Supported BINAP Hydrogenation Catalyst

The intramolecular silyl modified Sakurai (ISMS) reaction is a powerful tool for the construction of tetrahydropyrans, spiroethers, and spiroketals. The ISMS methodology was applied to a short and stereocontrolled synthesis of a minor component of the rectal gland secretion of the female Dacus olea fruit fly

Daniel J. Bayston

Papers

Preparation and Use of a Polymer Supported BINAP Hydrogenation Catalyst

The intramolecular silyl-modified Sakurai (ISMS) reaction. A simple and versatile synthesis of tetrahydropyrans, spiro ethers, and spiro ketals

The Intramolecular Silyl-Modified Sakurai (ISMS) reaction. Synthetic studies towards ambruticine

The Intramolecular Silyl-Modified Sakurai (ISMS) reaction. Stereoselective preparation of tri-and tetra-substituted tetrahydropyrans.

Concise and stereocontrolled assembly of substituted dihydropyrans. Synthetic studies towards the trans-dioxadecalin subunit of okadaic acid