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 etarenes (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 METD etc etc etc. VARIATI 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 Science of Synthesis Reference Library, The Science of Synthesis Reference Library comprises 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. Volumes in the Science of Synthesis Reference Library focus on subjects of particular current interest with content that is evaluated by experts in their field. Science of Synthesis, including the Knowledge Updates and the Reference Library, is the complete information source for the modern synthetic chemist. Classical Transformations Advances rganic Synthesis Applications Structures Techniques

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 Editor Senior Scientific Editors M. F. Shortt de ernandez K. M. Muirhead-ofmann M.. Smith Scientific Editors T. B. Reeve A. G. Russell M. Sainsbury I. M. Thomas M. J. White F. Wuggenig Scientific Consultant J. P. Richmond b Georg Thieme Verlag KG Stuttgart ew York

6 Science of Synthesis Asymmetric rganocatalysis 1 Lewis Base and Acid Catalysts Volume Editor B. List Authors T. D. Beeson M. Benohoud J. W. Bode S. Chen M. Christmann P.-C. Chiang D. A. DiRocco Y. C. Fan T. Furuta P. García-García S. atakeyama Y. ayashi J. Jia T. Kawabata. J. Kerrigan. Kwon Y. Liu D. W. C. MacMillan. Mase P. Melchiorre S. Mukherjee A. Piisola P. M. Pihko T. A. Ramirez T. Rovis E. C. Salo Y. Shi A. D. Smith K. Suzuki. Takikawa X.-W. Wang Y. Wang A. J. B. Watson. A. Wong P. A. Woods S. M. Yliniemelä-Sipari b 2012 Georg Thieme Verlag KG Stuttgart ew York

7 IV 2012 Georg Thieme Verlag KG Rüdigerstrasse 14 D Stuttgart Printed in Germany Typesetting: Ziegler + Müller, Kirchentellinsfurt Printing and Binding: AZ Druck und Datentechnik Gmb, Kempten Bibliographic Information published by Die Deutsche Bibliothek Die Deutsche Bibliothek lists this publication in the Deutsche ationalbibliografie; detailed bibliographic data is available on the internet at < Library of Congress Card o.: applied for British Library Cataloguing in Publication Data A catalogue record for this book is available from the British Library Date of publication: December 28, 2011 Copyright and all related rights reserved, especially the right of copying and distribution, multiplication and reproduction, as well as of translation. o 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. ISB 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. owever, 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 ouben 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, ouben 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 Asymmetric rganocatalysis Volumes Asymmetric rganocatalysis 1 Lewis Base and Acid Catalysts Volume Editor: B. List Asymmetric rganocatalysis 2 Brønsted Base and Acid Catalysts, and Additional Topics Volume Editor: K. Maruoka

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12 IX Abstracts Enamine Catalysis of Intramolecular Aldol Reactions X.-W. Wang, Y. Wang, and J. Jia p1 In this review, organocatalytic intramolecular aldol reactions are classified into three different types according to their enolization mode: enolendo aldolizations, enolexo aldolizations, and transannular aldolizations. The enantioselective enamine catalysis of these reactions using chiral, enantiomerically pure primary and secondary amines as catalysts is discussed. Following the logic of this volume, the chapter focuses on the more synthetically useful approaches. enolendo aldolization n n enolexo aldolization n n n transannular aldolization n m m Keywords: intramolecular aldol enamine catalysis enolendo enolexo transannular Enamine Catalysis of Intermolecular Aldol Reactions S. M. Yliniemelä-Sipari, A. Piisola, and P. M. Pihko p35 This review discusses enamine catalysis of intermolecular aldol reactions. The organocatalytic approach to these carbon-carbon bond-forming reactions between enolizable carbonyl compounds and aldehydes or ketones is discussed from a practical standpoint, and is illustrated with examples from the literature. The scope and the current limitations of the protocols are presented. The origins of the limitations, based on chemoselectivity problems related to the activation of starting materials, are also described. donor + R 3 R 4 acceptor X (cat.) R 4 R 3 Keywords: intermolecular aldol reaction asymmetric synthesis enamine catalysis organocatalysis

13 X Abstracts Enamine Catalysis of Mannich Reactions M. Benohoud and Y. ayashi p73 Chiral primary and secondary amines catalyze the Mannich reaction of imines and carbonyl compounds to diastereoselectively generate â-amino carbonyl compounds with excellent enantioselectivity. The design of amine catalysts and the judicious choice of the substituent on the nitrogen of the imine allows the selective formation of the syn- or anti-mannich products. The imine component can be preformed or generated in situ from an amine and an aldehyde or by desulfonylation of Æ-amido sulfones. Imines can bear aromatic, carbamate, or sulfonate -substituents. Since the initial development of amine-catalyzed Mannich reactions, the scope of carbonyl compounds has been extended from simple acetone to cyclic ketones, ketones substituted with heteroatoms, and aldehydes such as acetaldehyde, which is known to be difficult to handle because of its high reactivity. Mannich adducts formed in these asymmetric organocatalyzed processes are generally obtained with good yields and high diastereo- and enantioselectivities. There are several noteworthy features of this reaction: (1) the reactions are operationally simple; (2) water and air do not need to be strictly excluded; (3) amine catalysts are available, or can be prepared, in both enantiomeric forms; (4) in several procedures the catalyst loading can be reduced to <5 mol%; and (5) high enantioselectivities can be obtained. The asymmetric amine-catalyzed Mannich reaction is a practical and useful method for the synthesis of nitrogen-containing chiral molecules. R4 + R4 R 3 R 5 X or R 5 R3 syn R4 anti R3 Keywords: asymmetric Mannich reaction chiral amines enamines imines â-amino carbonyls Enamine Catalysis of Michael Reactions. Mase p135 This chapter addresses significant achievements in asymmetric synthesis focusing on enamine-based organocatalytic direct Michael reactions. The description of methods for Michael reactions is subdivided on the basis of various classes of intramolecular, intermolecular, and domino reactions. In addition, these are further subdivided on the basis of donors (nucleophiles) and acceptors (electrophiles): ketones and aldehydes as the donors and Æ,â-unsaturated carbonyl compounds, nitroalkenes, vinyl sulfones, and vinylphosphonates as the acceptors.

14 Abstracts XI R 3 + R 5 EWG organocatalyst Michael reaction R 4 R 4 R 3 R 5 EWG EWG R 3 R 4 R 5 enamine catalysis Keywords: conjugate addition reactions domino reactions enamine catalysis enamines iminium catalysis intermolecular reactions intramolecular reactions Michael acceptors Michael addition Michael donors one-pot process organocatalysis reductive Michael reactions Enamine Catalysis of Æ-Functionalizations and Alkylations S. Mukherjee p217 Since the turn of this century, asymmetric enamine catalysis has given rise to a plethora of synthetically useful transformations. This section describes some of the most efficient and practical methods for enamine catalyzed asymmetric Æ-functionalizations and alkylations. The first part of this review deals with the introduction of different heteroatom functionalities (e.g., nitrogen, oxygen, halogens, sulfur, or selenium) at the Æ-position of aldehydes and ketones, whereas methods for the formation of C-C bonds (e.g., alkylation, allylation, or arylation) are described in the latter part. R 3 R 4 R 3 R enamine X + α-functionalization (R 5 ) + α-alkylation X high ee R 5 high ee Keywords: alkylation allylation arylation asymmetric catalysis enamine Æ-functionalization organocatalysis SM and Radical Chemistry in rganocatalysis D. W. C. MacMillan and T. D. Beeson p271 This chapter describes the design and development of singly occupied molecular orbital (SM) catalysis. This new mode of organocatalytic activation is founded upon the mechanistic hypothesis that the one-electron oxidation of a transient enamine intermediate, derived from a carbonyl compound and a chiral amine catalyst, will render a 3ð-electron SM radical cation that is subject to enantiofacial discrimination. This chiral SM-activated species can readily combine with SM nucleophiles in unique asymmetric bond constructions to enable previously unknown transformations. Many SM nucleophiles have been shown to participate with radical cations and, correspondingly, a diverse range

15 XII Abstracts of chemistry, such as carbon-carbon and carbon-heteroatom bond formations, formal [4+2] cycloadditions, and polyene cyclizations, has been implemented. carbonyl + Bn Me catalyst Bu t [] ketone α-functionalization Me Bn Bu t R2 = sp 3 sp 2 bond-forming reactions R 3 radical cation = = = = Cl C X bond-forming reactions Ph sp 3 sp 3 bond-forming reactions S formal [4 + 2] cycloadditions C bond-forming reactions Keywords: SM nucleophile radical cation iminium enamine aldehydes ketones carbon-carbon bond formation carbon-heteroatom bond formation cycloaddition cyclization Iminium Catalysis D. W. C. MacMillan and A. J. B. Watson p 309 Chiral amine catalysts condense with Æ,â-unsaturated carbonyl compounds to generate transient chiral iminium ions. These activated intermediates are then able to participate in enantioselective carbon-carbon and carbon-heteroatom bond formation with a broad range of nucleophilic partners.