Organolithiums: Selectivity for Synthesis.

This volume, number 23 in the "Tetrahedron Organic Chemistry" series, presents organolithium chemistry from the perspective of a synthetic organic chemist, drawing from the synthetic literature to present a unified overview of how organolithiums can be used to make molecules. The development of methods for the regioselective synthesis of organolithiums has replaced their image of indiscriminate high reactivity with one of controllable and subtle selectivity. Organolithium chemistry has a central role in the selective construction of C-C bonds in both simple and complex molecules, and for example has arguably overtaken aromatic electrophilic substitution as the most powerful method for regioselective functionalisation of aromatic rings. The twin themes of reactivity and selectivity run through the book, which reviews the ways by which organolithiums may be formed and the ways in which they react. Topics include advances in directed metallation, reductive lithiation and organolithium cyclisation reactions, along with a discussion of organolithium stereochemistry and the role played by ligands such as (-)-sparteine.

This volume is the first dedicated to a comprehensive coverage of this rapidly developing transdisciplinary field. It provides a rich source of essential information on synthesizing molecules in an enantioselective manner using organolithiums, and serves as an inspiration for future developments.

The Chemistry of Organolithium Compounds is a comprehensive review of the status of organolithium compound chemistry. This book is composed of four parts and nineteen chapters that particularly describe the reactions involving these compounds The first part highlights the constitution of organolithium compounds, specifically in the absence and presence of electron donors, as well as the configurational stability of these compounds. The second part deals with their preparation from organic halides and lithium metal involving metallation and metal-halogen exchange, while the third part focuses on their organic synthesis. The fourth part considers the synthesis of organometallic compound derivatives from main group and transition metals. This book will prove useful to organic chemists and organic chemistry researchers.

Selectivity is an increasingly important part of organic synthesis. The whole basis of organic chemistry, and especially organic synthesis, depends upon the selectivity which can be achieved in organic reactions. This concise textbook describes the strategies which can be adopted to improve selectivity, and the reactions which have been specially designed to afford high selectivity. The aim is to illustrate the range of processes to which these principles can be applied and the high degree of selectivity which can be achieved. Selectivity in Organic Synthesis aims to provide a solid introduction to this subject, focusing on the key areas and applications.

Topics in Stereochemistry, previously edited by "the father of stereochemistry" Ernest L. Eliel, is a longstanding, successful series covering the most important advances in the field. The much-anticipated Volume 26 on stereochemical aspects of organolithium compounds includes chapters on the following topics: * Asymmetric Deprotonations Using Chiral Lithium Amide Bases * Self-Regeneration of Stereocenters (SRS) via Stereolabile Axially Chiral Intermediates * Overview of Carbanion Dynamics and Electrophilic Substitutions in Chiral Organolithium Compounds * Oxiranyllithiums as Chiral Synthons for Asymmetric Synthesis * Test on the Configurational Stability/Lability of Organolithium Compounds * Mechanism and Stereochemical Features in Asymmetric Deprotonation Using RLi/(-)-Sparteine Bases * Dynamic Resolutions of Chiral Organolithiums Volume 26 of Topics in Stereochemistry marks the end of an era, while developing a bridge to the next generation. A new generation in publishing, parallel to a new generation in Stereochemistry mandated a new venue and modus operandi for Topics. Zurich, the home of Werner and Wislicenus, has a unique heritage in Stereochemistry. Fortunately, the Wiley family's publishing partnerships include Verlag Helvetica Chimica Acta, a house with a reputation for superior quality in publishing. Indeed, within the pages of its namesake periodical, Helvetica Chimica Acta, one finds many of the seminal research works of stereochemistry's giants. As such, a transfer of editorial operations to Zurich and a collaboration bringing Topics as a series closer to periodical status provides a growth platform for the future.

Bringing together examples that until now were often hidden and widely spread throughout the original literature, this textbook shows how to use the correct reagents, conditions or reaction sequences to have access to all possible stereoisomers when beginning synthesis with only a single starting material. Adopting a didactic approach, the authors have chosen general and simple examples throughout the book so that these reactions can be transferred easily to other reaction types. While of major interest to master and PhD students alike, this book is also a source of valuable information for organic chemists in both academia and industry. Additional material for lectures at www.wiley-vch.de/textbooks

This volume presents an account of the applications of organolithium compounds in synthesis. General considerations, such as solvents, inert atmospheres, apparatus and safety, are discussed as well as detailed specific methods.

The world is chiral. Most of the molecules in it are chiral, and asymmetric synthesis is an important means by which enantiopure chiral molecules may be obtained for study and sale. Using examples from the literature of asymmetric synthesis (more than 1300 references), the aim of this book is to present a detailed analysis of the factors that govern stereoselectivity in organic reactions. It is important to note that the references were each individually checked by the authors to verify relevance to the topics under discussion. The study of stereoselectivity has evolved from issues of diastereoselectivity, through auxiliary-based methods for the synthesis of enantiomerically pure compounds (diastereoselectivity followed by separation and auxiliary cleavage), to asymmetric catalysis. In the latter instance, enantiomers (not diastereomers) are the products, and highly selective reactions and modern purification techniques allow preparation - in a single step - of chiral substances in 99% ee for many reaction types. After an explanation of the basic physical-organic principles of stereoselectivity, the authors provide a detailed, annotated glossary of stereochemical terms. A chapter on "Analytical Methods" provides a critical overview of the most common methods for analysis of stereoisomers. The authors then follow the 'tried-and-true' format of grouping the material by reaction type. Thus, there are four chapters on carbon-carbon bond forming reactions (enolate alkylations, organometal additions to carbonyls, aldol and Michael reactions, and cycloadditions and rearrangements), one chapter on reductions and hydroborations (carbon-hydrogen bond forming reactions), and one on oxidations (carbon-oxygen and carbon-nitrogen bond forming reactions). Leading references are provided to natural product synthesis that have been accomplished using a given reaction as a key step. In addition to tables of examples that show high selectivity, a transition state analysis is presented to explain - to the current level of understanding - the stereoselectivity of each reaction. In one case (Cram's rule) the evolution of the current theory is detailed from its first tentative (1952) postulate to the current Felkin-Anh-Heathcock formalism. For other reactions, only the currently accepted rationale is presented. Examination of these rationales also exposes the weaknesses of current theories, in that they cannot always explain the experimental observations. These shortcomings provide a challenge for future mechanistic investigations.