1st Edition

CRC Handbook of Optical Resolutions via Diastereomeric Salt Formation

Edited By

David Kozma




ISBN 9780849300196
Published October 18, 2001 by CRC Press
704 Pages

USD $290.00

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Book Description

Optically active compounds are gaining ever-increasing importance in organic chemistry, both in the academic and the industrial arenas. The rational synthesis of the growing number of chiral chemicals, drugs, and natural products demands efficient methods for producing these compounds in an enantiomerically, highly pure form. Despite the available alternative techniques, optical resolution via Diastereomeric salt formation remains the most widely used method of preparing pure enantiomers.

The CRC Handbook of Optical Resolutions Via Diastereomeric Salt Formation is the first book to exclusively address this important organic chemical process. It provides fast, one-stop access to a wealth of information, including all of the available data on 100 resolving agents, a list of 500 optically active compounds available in bulk along with their suppliers, data on more than 3,500 resolutions, and 4,200 citations.

This handbook helps answer virtually any question that may arise during the development of a new resolution process.

Which resolving agent and solvent should I use under these conditions?

How can I separate the diastereoisomers?

How can I optimize a resolution process?

How do I determine enantiomeric purity?

Which supplier has the resolving agent I need?

For a racemate already resolved, what were the resolving agent, solvent, and relevant citation?

This is the first book to deal exclusively with all aspects of this important organic chemical process, both theoretical and practical. With an abundance of analyzed examples, this single, authoritative reference provides all of the information you need to perform, develop, and optimize optical resolutions via Diastereomeric salt formation

Table of Contents

INTRODUCTION
BASIC CONCEPTS AND NOMENCLATURE OF STEREOCHEMISTRY
Chirality, Enantiomers and Diastereomers
Stereochemical Nomenclature
Principles of Separation of Diastereomers and Enantiomers
RESOLUTION BY FORMATION AND FRACTIONAL CRYSTALLISATION OF DIASTEREOMERIC SALTS
The Concept of Resolvability
Stoichiometry of Resolution
Resolution with One Equivalent of Resolving Agent
Resolution with Half Equivalent of Resolving Agent in Combination with an Achiral Additive
Use of Half Molar Equivalent of Resolving Agent without an Achiral Additive
Salt-Salt Resolution
Resolution with the Enantiomer of the Resolving Agent
Reciprocal Resolution
Mutual Resolution
Resolution with Difunctional Resolving Agents
Resolution of Amphoteric Racemates
Resolution by Salt Formation of Compounds Lacking Acidic or Basic Groups
Asymmetric Transformations during Resolution by Salt Formation
RESOLVING AGENTS
Basic Resolving Agents
Acidic Resolving Agents (Including Amino Acids)
RESEARCH ON RESOLVING AGENTS
Attempts to Devise A Generally Applicable Resolving Agent
Correlation of the Efficiency of Resolution with the Structure of Racemate and Resolving Agent.
Resolutions with a Derivative of the Racemate
Resolutions with a Mixture of Structurally Similar Resolving Agents
SELECTION OF THE RESOLVING AGENT
SELECTION OF THE RESOLVING AGENT BY EXPERIMENTATION
Selection of the Resolving Agent by Small-Scale Preliminary Preparative Experiments
Selection of the Resolving Agent by Combined Application of Several Resolving Agents
Selection of the Resolving Agent by Distillation Tests
Selection of the Resolving Agent Based on the Principle of Maximum Similarity
Selection of the Resolving Agent by Statistical Evaluation
SELECTION OF A RESOLVING AGENT BASED ON THE DETERMINATION OF PHYSICO-CHEMICAL PARAMETERS
Solubility
Selection of a Resolving Agent Based on Melting Point Phase Diagrams of Diastereomeric Salt Pairs
Calculation of Resolvability by DSC of a Mixture of Diastereomeric Salts Formed from the Racemate
Determination of the Optical Rotation of Diastereomeric salts
SELECTION OF THE RESOLVING AGENT BASED ON THEORETICAL CONSIDERATIONS
RESOLUTION IN PRACTICE, SELECTION OF THE OPTIMAL PARAMETERS
Reacting the Components
Initiation of Crystallisation
Role of Temperature in Resolution
Further Purification of Diastereomeric Salts with the Aid of a Chiral
Additive
Recovery of the Components from the Diastereomeric Salts
Upgrading of Optical Purity without a Chiral Additive (Enantiomeric Enrichment)
ALTERNATIVE METHODS OF RESOLUTION BY DIASTEREOMERIC SALT FORMATION
Classification of Alternative Resolution Processes by Type of Phase Transition
Resolution by Distillation
Resolution by Extraction
Resolution by Supercritical Extraction
Resolution by Sublimation
Mechanical Separation of Diastereomeric Salt Mixtures
DETAILED DESCRIPTIONS OF SELECTED RESOLUTIONS

APPENDIX 1: Resolutions Ordered According to the Resolving Agent
APPENDIX 2: Commercially Produced Resolving Agents and Optically Active Industrial Products which may be Eligible as Resolving Agents
APPENDIX 3. Chiral Selective Chromatographic Analysis

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Reviews

"…a comprehensive survey of the most widely used methods of obtaining pure enantiomers…a wealth of information on all aspects of the optical resolution of racemates by diastereomeric salt formation, including priniciples of resolvability, mechanisms, and kinetics, very valuable lists of commonly used resolving agents, and of optically active commercially produced agents…and summaries of 4000 resolutions by diastereomeric salt formation, which are invaluable in resolving an unknown racemate…well organized to facilitate fast access to the information and data…The handbook will be useful for researchers, engineers, and graduates…affordable for many research libraries, laboratories, and personal collections."
- Svetlana Korlev, University of Wisconsin, Golda Meir Library, USA in E-Streams, vol. 5 no. 8