METHOD SUBCLASS PRODUCT Vol /3 C X bonds C X bonds. (Vols ) (Vols ) Synthesis. of Organic.

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2 rganizational Structure of Science of Synthesis* CATEGRY 1 rganometallics (Vols 1 8 ) 2 Hetarenes (Vols 9 17 ) Products of rganic Synthesis /3 C X bonds (Vols ) C X bonds (Vols ) C X bond (Vols ) 6 All C bonds (Vols 43 8 ) 4 Classification is based on the product, with all products belonging to one of six broad-ranging categories. All products occupy a strict hierarchical position in Science of Synthesis, defined according to the classification principles*. Products in Categories 3 6 are organized according to oxidation state, with products containing the greatest number of carbon heteroatom (C X) or C C -bonds to a single carbon occupying the highest positions (e.g., carboxylates, enolates, and alcoholates are covered in Categories 3, 4, and 5, respectively). * A complete description of the full classification principles can be found in the Science of Synthesis Guidebook. VLUME Vol. 9 PRDUCT CLASS Vol. 10 etc PRDUCT SUBCLASS METHD etc etc etc. VARIATIN etc. Selected Products and Reactions Each category is subdivided into volumes (see opposing page), each of which is devoted to discrete groupings of compounds called product classes (e.g., Thiophenes is Product Class 10 of Volume 9). Product classes may be further subdivided into, (e.g., Thiophene 1,1-Dioxides is Product product subclasses Subclass 3 of Product Class 10 of Volume 9). Consequently, the relationship between heading name and heading number varies below product class level within individual volumes. For each product class or subclass, a number of methods are described for synthesizing the general product type. ften there are variations on a method given. Both methods and variations contain experimental procedures with relevant background information and literature references. Selected display the scope and limitations of products and reactions the methods.

3 CATEGRY UPDATED VLUMES rganometallics a 8b (Vols 1 8 ) Hetarenes (Vols 9 17 ) 4/3 C X bonds 3 (Vols ) a 20b C X bonds a 31b (Vols ) 1 C X bond a 40b (Vols ) All C bonds a 45b 46 47a 47b 48 (Vols ) 5 Compounds of Group 14 (Ge, Sn, Pb) 7 Compounds of Groups 13 and 2 (Al, Ga, In, Tl, Be Ba) 9 Fully Unsaturated Small-Ring Heterocycles and Monocyclic Five-Membered Hetarenes with ne Heteroatom 16 Six-Membered Hetarenes with Two Identical Heteroatoms * Detailed listings of product classes and subclasses, methods, and variations can be found in the Table of Contents sections of every volume.

4 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

5 Science of Synthesis Editorial Board E. M. Carreira C. P. Decicco A. Fuerstner G. A. Molander P. J. Reider E. Schaumann M. Shibasaki E. J. Thomas B. M. Trost Managing Director G. F. Herrmann Managing Editor Senior Scientific Editor Scientific Editors M. F. Shortt de Hernandez M. H. Smith T. B. Reeve I. M. Thomas M. Weston F. Wuggenig Georg Thieme Verlag KG Stuttgart New York

6 Science of Synthesis Knowledge Updates 2013/1 Volume Editors A. Fuerstner (Vol. 9) K. Ishihara (Vol. 7) J. J. Li (Vol. 16) M. G. Moloney (Vol. 5) Responsible Members of the Editorial Board A. Fuerstner (Vols. 7 and 9) G. A. Molander (Vol. 16) E. J. Thomas (Vol. 5) Authors N. Boutard A. Dçrr J. Dufour-Gallant M. Hatano R. Hopewell T. Kassem R. Krishnamoorthy J. W. Lippert, III W. D. Lubell Z. Song D. J. St-Cyr T. Takahashi K. Tchabanenko R. Zelli 2013 Georg Thieme Verlag KG Stuttgart New York

7 IV 2013 Georg Thieme Verlag KG Rüdigerstrasse 14 D Stuttgart Printed in Germany Typesetting: Konrad Triltsch GmbH, chsenfurt-hohestadt Printing and Binding: AZ Druck und Datentechnik GmbH, Kempten Bibliographic Information published by Die Deutsche Bibliothek Die Deutsche Bibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data is available on the internet at < Library of Congress Cataloging in Publication Data Science of synthesis : Houben Weyl methods of molecular transformations. p. cm. Includes bibliographical references. Contents: Science of Synthesis Knowledge Updates 2013/1 / volume editors, A. Fuerstner, K. Ishihara, J. J. Li, M. G. Moloney ISBN rganic compounds Synthesis. I. Title: Houben Weyl methods of molecular transformations. QD262.S '.2 dc (Houben Weyl methods of organic chemistry) British Library Cataloguing in Publication Data A catalogue record for this book is available from the British Library ISBN Date of publication: April 24, 2013 Copyright and all related rights reserved, especially the right of copying and distribution, multiplication and reproduction, as well as of translation. No part of this publication may be reproduced by any process, whether by photostat or microfilm or any other procedure, without previous written consent by the publisher. 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 wish to point out very clearly that the present legal situation in respect of these names or designations or trademarks must be carefully examined before making any commercial use of the same. Industrially produced apparatus and equipment are included to a necessarily restricted extent only and any exclusion of products not mentioned in this reference work does not imply that any such selection of exclusion has been based on quality criteria or quality considerations. Warning! Read carefully the following: Although this reference work has been written by experts, the user must be advised that the handling of chemicals, microorganisms, and chemical apparatus carries potentially life-threatening risks. For example, serious dangers could occur through quantities being incorrectly given. The authors took the utmost care that the quantities and experimental details described herein reflected the current state of the art of science when the work was published. However, the authors, editors, and publishers take no responsibility as to the correctness of the content. Further, scientific knowledge is constantly changing. As new information becomes available, the user must consult it. Although the authors, publishers, and editors took great care in publishing this work, it is possible that typographical errors exist, including errors in the formulas given herein. Therefore, it is imperative that and the responsibility of every user to carefully check whether quantities, experimental details, or other information given herein are correct based on the users own understanding as a scientist. Scaleup of experimental procedures published in Science 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 herein, the user is ultimately responsible for his or her own actions, as well as the actions of subordinates and assistants, and the consequences arising therefrom.

8 V Preface As the pace and breadth of research intensifies, organic synthesis is playing an increasingly central role in the discovery process within all imaginable areas of science: from pharmaceuticals, agrochemicals, and materials science to areas of biology and physics, the most impactful investigations are becoming more and more molecular. As an enabling science, synthetic organic chemistry is uniquely poised to provide access to compounds with exciting and valuable new properties. rganic molecules of extreme complexity can, given expert knowledge, be prepared with exquisite efficiency and selectivity, allowing virtually any phenomenon to be probed at levels never before imagined. With ready access to materials of remarkable structural diversity, critical studies can be conducted that reveal the intimate workings of chemical, biological, or physical processes with stunning detail. The sheer variety of chemical structural space required for these investigations and the design elements necessary to assemble molecular targets of increasing intricacy place extraordinary demands on the individual synthetic methods used. They must be robust and provide reliably high yields on both small and large scales, have broad applicability, and exhibit high selectivity. Increasingly, synthetic approaches to organic molecules must take into account environmental sustainability. Thus, atom economy and the overall environmental impact of the transformations are taking on increased importance. The need to provide a dependable source of information on evaluated synthetic methods in organic chemistry embracing these characteristics was first acknowledged over 100 years ago, when the highly regarded reference source Houben Weyl Methoden der rganischen Chemie was first introduced. Recognizing the necessity to provide a modernized, comprehensive, and critical assessment of synthetic organic chemistry, in 2000 Thieme launched Science of Synthesis, Houben Weyl Methods of Molecular Transformations. This effort, assembled by almost 1000 leading experts from both industry and academia, provides a balanced and critical analysis of the entire literature from the early 1800s until the year of publication. The accompanying online version of Science of Synthesis provides text, structure, substructure, and reaction searching capabilities by a powerful, yet easy-to-use, intuitive interface. From 2010 onward, Science of Synthesis is being updated quarterly with high-quality content via Science of Synthesis Knowledge Updates. The goal of the Science of Synthesis Knowledge Updates is to provide a continuous review of the field of synthetic organic chemistry, with an eye toward evaluating and analyzing significant new developments in synthetic methods. A list of stringent criteria for inclusion of each synthetic transformation ensures that only the best and most reliable synthetic methods are incorporated. These efforts guarantee that Science of Synthesis will continue to be the most up-to-date electronic database available for the documentation of validated synthetic methods. Also from 2010, Science of Synthesis includes the Science of Synthesis Reference Library, comprising volumes covering special topics of organic chemistry in a modular fashion, with six main classifications: (1) Classical, (2) Advances, (3) Transformations, (4) Applications, (5) Structures, and (6) Techniques. Titles will include Stereoselective Synthesis, Water in rganic Synthesis, and Asymmetric rganocatalysis, among others. With expertevaluated content focusing on subjects of particular current interest, the Science of Synthesis Reference Library complements the Science of Synthesis Knowledge Updates, to make Science of Synthesis the complete information source for the modern synthetic chemist.

9 VI Preface The overarching goal of the Science of Synthesis Editorial Board is to make the suite of Science of Synthesis resources the first and foremost focal point for critically evaluated information on chemical transformations for those individuals involved in the design and construction of organic molecules. Throughout the years, the chemical community has benefited tremendously from the outstanding contribution of hundreds of highly dedicated expert authors who have devoted their energies and intellectual capital to these projects. We thank all of these individuals for the heroic efforts they have made throughout the entire publication process to make Science of Synthesis a reference work of the highest integrity and quality. The Editorial Board July 2010 E. M. Carreira (Zurich, Switzerland) E. Schaumann (Clausthal-Zellerfeld, Germany) C. P. Decicco (Princeton, USA) M. Shibasaki (Tokyo, Japan) A. Fuerstner (Muelheim, Germany) E. J. Thomas (Manchester, UK) G. A. Molander (Philadelphia, USA) B. M. Trost (Stanford, USA) P. J. Reider (Princeton, USA)

10 VII Abstracts 2013 p Product Subclass 1: Tin Hydrides K. Tchabanenko This chapter is a revision of an earlier Science of Synthesis contribution describing methods for the synthesis and synthetic applications of tin hydrides. Synthetic methods based on free-radical chain reactions promoted by tin hydrides are discussed, including cascade reactions that proceed with rearrangement of radical intermediates. Free-radical and transition-metal-catalyzed hydrostannylations of multiple carbon-carbon bonds are also discussed in the chapter. Bu 3 SnH AIBN benzene reflux H + 50% H SePh H Pr Bu 3 SnH Mo(C) 3 (CNt-Bu) 3 (cat.) hydroquinone (cat.) THF, 55 o C 80% Pr SnBu 3 Keywords: stannanes radical reactions cyclizations rearrangements C-C bond formation C-Sn bond formation transition-metal catalysis cascade reactions 2013 p Grignard Reagents with Transition Metals Z. Song and T. Takahashi This chapter is an update to Science of Synthesis Section , which describes the reactions of Grignard reagents in conjunction with transition metals. This update briefly summarizes the related publications that appeared from 2004 onwards. MgX 1 R 2 X 2 transition metal + R 2 Keywords: Grignard reagents C-C coupling enantioselectivity transition metals transmetalation 2013 Updated Section 2013 Completely Revised Contributions New New Contributions

11 VIII Science of Synthesis Abstracts 2013 p Product Class 7: Calcium Compounds M. Hatano This chapter is a revision of the earlier Science of Synthesis contribution describing methods for the synthesis of calcium compounds. Recent interest in this area has in part been generated by the observation that complexes of calcium with chiral diols, diamines, or phosphoric acids possess potent activity in asymmetric catalysis. P H Ca(iPr) 2 P Ca P Keywords: alkylation amination arylation 1,1 -binaphthalene-2,2 -diols bis(oxazolines) C-C bond formation cyclization diamines diols oxidation phosphoric acids pybox ligands 2013 p H-Pyrroles W. D. Lubell, D. J. St-Cyr, J. Dufour-Gallant, R. Hopewell, N. Boutard, T. Kassem, A. Dçrr, and R. Zelli This chapter updates the previous Science of Synthesis contribution on 1H-pyrroles, which covers the literature up to This update includes the literature to 2011, with coverage of >900 references. Modern advances in pyrrole synthesis, reactivity, and functionalgroup modification, are described, including syntheses of nitrogen-, oxygen-, and sulfursubstituted pyrroles, multicomponent and annulation reactions, selective modifications at the 1-, 2-, and 3-positions of the pyrrole ring, and enantioselective additions of chiral side chains. Various annulation, ring-contraction, and ring-expansion approaches to the heterocycle, as well as modifications of pyrrole by carbon-hydrogen, carbon-halogen, carbon-heteroatom, and carbon-carboxylate transformations, and substituent migration strategies, all are covered in detail, along with many other recent synthetic developments. In addition, examples of various applications of pyrrole chemistry are presented to illustrate the growing importance of this heterocycle in fields such as medicinal chemistry, materials science, and natural product synthesis. R 3 R 4 modifications syntheses R 2 N R 5 applications Keywords: pyrrole Paal Knorr condensation Knorr-type reactions tosylmethyl isocyanide Barton Zard type reactions 1,3-dipolar cycloaddition halopyrroles cross coupling direct arylation Vilsmeier reaction enantioselective alkylation lamellarins distamycin prodigiosin netropsin 2013 Updated Section 2013 Completely Revised Contributions New New Contributions

12 Abstracts IX 2013 p Cinnolines R. Krishnamoorthy This chapter is an update to the earlier published Science of Synthesis report on the synthesis of cinnolines. The literature on cinnolines published from 2000 onwards is covered. 1. TFA, ipr(ch 2 ) 2 N MeCN, 0 o C, 0.5 h F 2. PhSH, 0 o C, 5 h F 87% NH 2 N N F = Bu, s-bu Keywords: cinnolines fused cinnolines diazotization cyclization arenediazonium salts arylhydrazones alkynyltriazenes N-oxides Richter reaction Suzuki reaction Sonogashira reaction 2013 p Diphosphinines J. W. Lippert, III This chapter is an update to the earlier Science of Synthesis contribution describing the methods for the preparation of various diphosphinines. The focus is on the literature published in the period (C) 5 W P Et Me TMS toluene, 110 o C, 20 h 62% P (C) 5 W TMS Et Me Pd(PPh 3 ) 4 toluene TMS TMS 85 o C, overnight (C) 5 W P P W(C) 5 70% Et Et Keywords: diphosphinines dimerization palladium complexes 2013 Updated Section 2013 Completely Revised Contributions New New Contributions

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14 XI Science of Synthesis Knowledge Updates 2013/1 Preface.... Abstracts... V VII Table of Contents.... XIII Product Subclass 1: Tin Hydrides K. Tchabanenko Grignard Reagents with Transition Metals (Update 2013) Z. Song and T. Takahashi Product Class 7: Calcium Compounds M. Hatano H-Pyrroles (Update 2013) W. D. Lubell, D. J. St-Cyr, J. Dufour-Gallant, R. Hopewell, N. Boutard, T. Kassem, A. Dçrr, and R. Zelli Cinnolines (Update 2013) R. Krishnamoorthy Diphosphinines (Update 2013) J. W. Lippert, III Author Index Abbreviations

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