Science of Synthesis

Science of Synthesis is the authoritative and comprehensive reference work for the entire field of organic and organometallic synthesis.

Science of Synthesis presents the important synthetic methods for all classes of compounds and includes: – Methods critically evaluated by leading scientists – Background information and detailed experimental procedures – Schemes and tables which illustrate the reaction scope Science of Synthesis Houben–Weyl Methods of Molecular Transformations

Editorial Board D. Bellus P. J. Reider E. N. Jacobsen E. Schaumann S. V. Ley I. Shinkai R. Noyori E. J. Thomas M. Regitz B. M. Trost

Managing Director G. F. Herrmann

Managing Editor M. F. Shortt de Hernandez

Scientific Editors C. A. Carter M. Sainsbury C. J. Drayton E. Smeaton K. E. du Plooy M. H. Smith R. M. Owen C. Twomey

Assistant M. J. White Scientific Editor

b Georg Thieme Verlag Stuttgart · New York Science of Synthesis Houben–Weyl Methods of Molecular Transformations

Category 1 Organometallics Volume 8a Compounds of Group 1 (Li…Cs) Volume Editors M. Majewski and V. Snieckus

Responsible Member B. M. Trost of the Editorial Board

Authors L. Brandsma G. W. Gribble N. Ono D. Caine M. Khodaei J. N. Reed R. K. Dieter R. Klein V. Snieckus T. Durst S. MacNeil C. F. Sturino J. Eames M. Majewski U. Wietelmann R. W. Friesen C. Metallinos M. Yus R. E. Gawley C. Njera J. W. Zwikker J. R. Green S. OConnor

2006 b Georg Thieme Verlag Stuttgart · New York IV

2006 Georg Thieme Verlag KG Date of publication: November 9, 2005 Rdigerstrasse 14 D-70469 Stuttgart Copyright and all related rights reserved, especially the right of copying and distribution, multiplication Printed in Germany and reproduction, as well as of translation. No part of Typesetting: Ziegler + Mller, Kirchentellinsfurt this publication may be reproduced by any process, Printing: Gulde Druck, Tbingen whether by photostat or microfilm or any other proce- Binding: Lachenmaier, Reutlingen dure, without previous written consent by the pub- lisher. This also includes the use of electronic media of data processing or reproduction of any kind.

This reference work mentions numerous commercial and proprietary trade names, registered trademarks and the like (not necessarily marked as such), patents, production and manufacturing procedures, registered designs, and designations. The editors and publishers Bibliographic Information published by wish to point out very clearly that the present legal sit- Die Deutsche Bibliothek uation in respect of these names or designations or trademarks must be carefully examined before mak- Die Deutsche Bibliothek lists this publication in the ing any commercial use of the same. Industrially pro- Deutsche Nationalbibliografie; detailed bibliographic duced apparatus and equipment are included to a nec- data is available on the internet at essarily restricted extent only and any exclusion of products not mentioned in this reference work does not imply that any such selection of exclusion has Library of Congress Cataloging in Publication Data been based on quality criteria or quality considera- Science of synthesis : Houben–Weyl methods of tions. molecular transformations. p. cm. Warning! Read carefully the following: Although Includes bibliographical references and index. this reference work has been written by experts, the Contents: category 1. Organometallics. v. 8a. Com- user must be advised that the handling of chemicals, pounds of Group 1 (Li…Cs) / volume editors, M. Ma- microorganisms, and chemical apparatus carries po- jewski and V. Snieckus tentially life-threatening risks. For example, serious ISBN 3-13-112221-8 – ISBN 0-86577-947-3 (v. 8a) dangers could occur through quantities being incor- 1. Organic compounds–Synthesis. I. Title: Houben– rectly given. The authors took the utmost care that Weyl methods of molecular transformations. the quantities and experimental details described QD262 .S35 2000 herein reflected the current state of the art of science 547'.2–dc21 when the work was published. However, the authors, 00-061560 editors, and publishers take no responsibility as to the correctness of the content. Further, scientific know- (Houben–Weyl methods of organic chemistry) ledge is constantly changing. As new information be- comes available, the user must consult it. Although the authors, publishers, and editors took great care in British Library Cataloguing in Publication Data publishing this work, it is possible that typographical Science of Synthesis : Houben–Weyl methods errors exist, including errors in the formulas given of molecular transformations. herein. Therefore, it is imperative that and the re- Category 1: Organometallics: Vol. 8a: Compounds of sponsibility of every user to carefully check Group 1 (Li… Cs). – (Houben–Weyl methods whether quantities, experimental details, or oth- of organic chemistry) er information given herein are correct based on 1. Organometallic compounds – Synthesis the users own understanding as a scientist. Scale- I. Majewski, M., II. Brandsma, L. up of experimental procedures published in Science 547.2 of Synthesis carries additional risks. In cases of doubt, the user is strongly advised to seek the opinion of an expert in the field, the publishers, the editors, or the authors. When using the information described here- ISBN 3-13-112221-8 in, the user is ultimately responsible for his or her (Georg Thieme Verlag, Stuttgart) own actions, as well as the actions of subordinates ISBN 0-86577-947-3 and assistants, and the consequences arising there- (Thieme New York) from. V

Preface

As our understanding of the natural world increases, we begin to understand complex phenomena at molecular levels. This level of understanding allows for the design of mo- lecular entities for functions ranging from material science to biology. Such design re- quires synthesis and, as the structures increase in complexity as a necessity for specifici- ty, puts increasing demands on the level of sophistication of the synthetic methods. Such needs stimulate the improvement of existing methods and, more importantly, the devel- opment of new methods. As scientists confront the synthetic problems posed by the mo- lecular targets, they require access to a source of reliable synthetic information. Thus, the need for a new, comprehensive, and critical treatment of synthetic chemistry has become apparent. To meet this challenge, an entirely new edition of the esteemed reference work Houben–Weyl Methods of Organic Chemistry will be published starting in the year 2000. To reflect the new broader need and focus, this new edition has a new title, Science of Synthesis, Houben–Weyl Methods of Molecular Transformations. Science of Syn- thesis will benefit from more than 90 years of experience and will continue the tradition of excellence in publishing synthetic chemistry reference works. Science of Synthesis will be a balanced and critical reference work produced by the collaborative efforts of chemists, from both industry and academia, selected by the editorial board. All published results from journals, books, and patent literature from the early 1800s until the year of publication will be considered by our authors, who are among the leading experts in their field. The 48 volumes of Science of Synthesis will provide chemists with the most relia- ble methods to solve their synthesis problems. Science of Synthesis will be updated pe- riodically and will become a prime source of information for chemists in the 21st century. Science of Synthesis will be organized in a logical hierarchical system based on the target molecule to be synthesized. The critical coverage of methods will be supported by information intended to help the user choose the most suitable method for their applica- tion, thus providing a strong foundation from which to develop a successful synthetic route. Within each category of product, illuminating background information such as history, nomenclature, structure, stability, reactivity, properties, safety, and environmen- tal aspects will be discussed along with a detailed selection of reliable methods. Each method and variation will be accompanied by reaction schemes, tables of examples, ex- perimental procedures, and a background discussion of the scope and limitations of the reaction described. The policy of the editorial board is to make Science of Synthesis the ultimate tool for the synthetic chemist in the 21st century.

We would like to thank all of our authors for submitting contributions of such out- standing quality, and, also for the dedication and commitment they have shown through- out the entire editorial process.

The Editorial Board October 2000 D. Bellus (Basel, Switzerland) P. J. Reider (New Jersey, USA) E. N. Jacobsen (Cambridge, USA) E. Schaumann (Clausthal-Zellerfeld, Germany) S. V. Ley (Cambridge, UK) I. Shinkai (Tsukuba, Japan) R. Noyori (Nagoya, Japan) E. J. Thomas (Manchester, UK) M. Regitz (Kaiserslautern, Germany) B. M. Trost (Stanford, USA)

Dedicated To: All chemists mesmerized by the utter beauty of methyllithium sparks. All those who nurture perseverance and collaboration of minds. Our parents, our children, and theirs. All students, past, present, and future. And to the indomitable Krista Voigt.

IX

Volume 8: Compounds of Group 1 (Li…Cs)

Volume 8a

8.1 Lithium Compounds

Keyword Index

Author Index

Abbreviations

Volume 8b

8.2 Sodium Compounds

8.3 Potassium Compounds

8.4 Rubidium and Cesium Compounds

Keyword Index

Author Index

Abbreviations

XI

Volume 8a: Compounds of Group 1 (Li…Cs)

Preface ...... V

Table of Contents ...... XV

Introduction M. Majewski and V. Snieckus ...... 1

8.1 Product Class 1: Lithium Compounds M. Majewski and V. Snieckus ...... 5

8.1.1 Product Subclass 1: Lithium Metal R. K. Dieter ...... 43

8.1.2 Product Subclass 2: Lithium Hydride U. Wietelmann ...... 133

8.1.3 Product Subclass 3: Lithium Halides, Lithium Cyanide, and Related Salts U. Wietelmann ...... 139

8.1.4 Product Subclass 4: Lithium–Oxygen Compounds U. Wietelmann ...... 165

8.1.5 Product Subclass 5: Lithium–Sulfur, –Selenium, and –Tellurium Compounds U. Wietelmann ...... 171

8.1.6 Product Subclass 6: Lithium Amides J. Eames ...... 173

8.1.7 Product Subclass 7: Alkyllithium and Cycloalkyllithium Compounds L. Brandsma and J. W. Zwikker ...... 243

8.1.8 Product Subclass 8: Alkenyllithium Compounds L. Brandsma and J. W. Zwikker ...... 253

8.1.9 Product Subclass 9: Allenyllithium Compounds L. Brandsma and J. W. Zwikker ...... 271

8.1.10 Product Subclass 10: Lithium Acetylides L. Brandsma and J. W. Zwikker ...... 285 XII Overview

8.1.11 Product Subclass 11: Lithium Alkynolates, Alkynethiolates, and Alkyneselenolates L. Brandsma and J. W. Zwikker ...... 305

8.1.12 Product Subclass 12: Allyllithium Compounds L. Brandsma and J. W. Zwikker ...... 313

8.1.13 Product Subclass 13: Benzyllithium Compounds and (Lithiomethyl)hetarenes J. N. Reed ...... 329

8.1.14 Product Subclass 14: Aryllithium and Hetaryllithium Compounds G. W. Gribble ...... 357

8.1.15 Product Subclass 15: Æ-Lithiocarboxylic Acids and Related Lithium Compounds (Including Enolates) J. R. Green ...... 427

8.1.16 Product Subclass 16: -Lithiocarboxylic Acids and Related Lithium Compounds D. Caine ...... 487

8.1.17 Product Subclass 17: Æ-Lithio Aldehydes, Æ-Lithio Ketones, and Related Compounds D. Caine ...... 499

8.1.18 Product Subclass 18: -Lithio Aldehydes, -Lithio Ketones, and Related Compounds D. Caine ...... 619

8.1.19 Product Subclass 19: sp3-Hybridized Æ-Lithio Ethers and O-Carbamates S. MacNeil ...... 637

8.1.20 Product Subclass 20: Æ-Lithio Sulfoxides T. Durst and M. Khodaei ...... 661

8.1.21 Product Subclass 21: Æ-Lithioamines R. E. Gawley, S. OConnor, and R. Klein ...... 677

8.1.22 Product Subclass 22: Lithium Nitronates N. Ono ...... 759

8.1.23 Product Subclass 23: ª-Lithio Ethers and Related Compounds D. Caine ...... 775

8.1.24 Product Subclass 24: Carbamoyllithium and Trihalomethyllithium Compounds C. Metallinos ...... 795 Overview XIII

8.1.25 Product Subclass 25: Tris(organosulfanyl)- and Tris(organoselanyl)methyllithium Compounds C. Njera and M. Yus ...... 805

8.1.26 Product Subclass 26: Bis(organosulfanyl)- and Bis(organoselanyl)methyllithium Compounds C. Njera and M. Yus ...... 813

8.1.27 Product Subclass 27: Æ-Lithio Vinyl Ethers R. W. Friesen and C. F. Sturino ...... 841

Keyword Index ...... i

Author Index ...... xxxiii

Abbreviations ...... lxxxv