Advanced Organic Chemistry_ Part A_ Structure and Mechanisms ( PDF

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1、Advanced OrganicChemistryFIFTHEDITIONPart A: Structure and MechanismsAdvanced Organic ChemistryPART A: Structure and MechanismsPART B: Reactions and SynthesisAdvanced OrganicChemistryFIFTHEDITIONPart A: Structure and MechanismsFRANCIS A. CAREYand RICHARD J. SUNDBERGUniversity of VirginiaCharlottesvi

2、lle, Virginia123Francis A. Carey Richard J. SundbergDepartment of Chemistry Department of ChemistryUniversity of Virginia University of VirginiaCharlottesville, VA 22904 Charlottesville, VA 22904Library of Congress Control Number: 2006939782ISBN-13: 978-0-387-44897-8 (hard cover) e-ISBN-13: 978-0-38

3、7-44899-3ISBN-13: 978-0-387-68346-1 (soft cover)Printed on acid-free paper.2007 Springer Science+Business Media, LLCAll rights reserved. This work may not be translated or copied in whole or in part without the writtenpermission of the publisher (Springer Science+Business Media, LLC, 233 Spring Stre

4、et, New York,NY 10013, USA), except for brief excerpts in connection with reviews or scholarly analysis. Use inconnection with any form of information storage and retrieval, electronic adaptation, computer software, orby similar or dissimilar methodology now know or hereafter developed is forbidden.

5、The use in this publication of trade names, trademarks, service marks and similar terms, even if they arenot identified as such, is not to be taken as an expression of opinion as to whether or not they are subjectto proprietary rights.98765432(corrected 2nd printing, 2008)PrefaceThis Fifth Edition m

6、arks the beginning of the fourth decade that Advanced OrganicChemistry has been available. As with the previous editions, the goal of this text is toallow students to build on the foundation of introductory organic chemistry and attaina level of knowledge and understanding that will permit them to c

7、omprehend muchof the material that appears in the contemporary chemical literature. There have beenmajor developments in organic chemistry in recent years, and these have had a majorinfluence in shaping this new edition to make it more useful to students, instructors,and other readers.The expanding

8、application of computational chemistry is reflected by amplifieddiscussion of this area, especially density function theory (DFT) calculations inChapter 1. Examples of computational studies are included in subsequent chaptersthat deal with specific structures, reactions and properties. Chapter 2 dis

9、cusses theprinciples of both configuration and conformation, which were previously treated intwo separate chapters. The current emphasis on enantioselectivity, including devel-opment of many enantioselective catalysts, prompted the expansion of the section onstereoselective reactions to include exam

10、ples of enantioselective reactions. Chapter 3,which covers the application of thermodynamics and kinetics to organic chemistry,has been reorganized to place emphasis on structural effects on stability and reactivity.This chapter lays the groundwork for later chapters by considering stability effects

11、 oncarbocations, carbanions, radicals, and carbonyl compounds.Chapters 4 to 7 review the basic substitution, addition, and elimination mecha-nisms, as well as the fundamental chemistry of carbonyl compounds, including enolsand enolates. A section on of the control of regiochemistry and stereo- chemi

12、stry ofaldol reactions has been added to introduce the basic concepts of this important area. Amore complete treatment, with emphasis on synthetic applications, is given in Chapter2 of Part B.Chapter 8 deals with aromaticity and Chapter 9 with aromatic substitution, empha-sizing electrophilic aromat

13、ic substitution. Chapter 10 deals with concerted pericyclicreactions, with the aromaticity of transition structures as a major theme. This part ofthe text should help students solidify their appreciation of aromatic stabilization as afundamental concept in the chemistry of conjugated systems. Chapte

14、r 10 also considersvviPrefacethe important area of stereoselectivity of concerted pericyclic reactions. Instructorsmay want to consider dealing with these three chapters directly after Chapter 3, andwe believe that is feasible.Chapters 11 and 12 deal, respectively, with free radicals and with photoc

15、hemistryand, accordingly, with the chemistry of molecules with unpaired electrons. The latterchapter has been substantially updated to reflect the new level of understanding thathas come from ultrafast spectroscopy and computational studies.As in the previous editions, a significant amount of specif

16、ic information isprovided in tables and schemes. These data and examples serve to illustrate the issuesthat have been addressed in the text. Instructors who want to achieve a broad coverage,but without the level of detail found in the tables and schemes, may choose to advisestudents to focus on the

17、main text. In most cases, the essential points are clear fromthe information and examples given in the text itself.We have made an effort to reduce the duplication between Parts A and B. Ingeneral, the discussion of basic mechanisms in Part B has been reduced by cross-referencing the corresponding d

18、iscussion in Part A. We have expanded the discussionof specific reactions in Part A, especially in the area of enantioselectivity and enantios-elective catalysts.We have made more extensive use of abbreviations than in the earlier editions.In particular, EWG and ERG are used throughout both Parts A

19、and B to designateelectron-withdrawing and electron-releasing substituents, respectively. The intent isthat the use of these terms will help students generalize the effect of certain substituentssuch as C=O, CN, NO2, and RSO2as electron withdrawing and R (alkyl) and RO(alkoxy) as electron releasing.

20、 Correct use of this shorthand depends on a solid under-standing of the interplay between polar and resonance effects in overall substituenteffects. This matter is discussed in detail in Chapter 3 and many common functionalgroups are classified.Several areas have been treated as “Topics”. Some of th

21、e Topics discuss areas thatarestillinaformativestage,suchastheeffortstodevelopDFTparametersasquantitativereactivity indices. Others, such as the role of carbocations in gasoline production, havepracticalimplications.We have also abstracted information from several published computational studiesto p

22、resent three-dimensional images of reactants, intermediates, transition structures,and products. This material, including exercises, is available at the publishers web site,and students who want to see how the output of computations can be applied may wantto study it. The visual images may help towa

23、rd an appreciation of some of the subtleeffects observed in enantioselective and other stereoselective reactions. As in previouseditions, each chapter has a number of problems drawn from the literature. A newfeature is solutions to these problems, which are also provided at the goal is to present a

24、broad and fairly detailed view of the core area of organicreactivity. We have approached this goal by extensive use of both the primary andreview literature and the sources are referenced. Our hope is that the reader whoworks through these chapters, problems, topics, and computational studies either

25、 in anorganized course or by self-study will be able to critically evaluate and use the currentliterature in organic chemistry in the range of fields in which is applied, includingthe pharmaceutical industry, agricultural chemicals, consumer products, petroleumchemistry, and biotechnology. The compa

26、nion volume, Part B, deals extensively withorganic synthesis and provides many more examples of specific reactions.Acknowledgmentand Personal StatementThe revision and updating of Advanced Organic Chemistry that appears as the FifthEdition spanned the period September 2002 through December 2006. Eac

27、h chapterwas reworked and updated and some reorganization was done, as described in thePrefaces to Parts A and B. This period began at the point of conversion of libraryresources to electronic form. Our university library terminated paper subscriptions tothe journals of the American Chemical Society

28、 and other journals that are availableelectronically as of the end of 2002. Shortly thereafter, an excavation mishap at anadjacent construction project led to structural damage and closure of our departmentallibrary. It remained closed through June 2007, but thanks to the efforts of Carol Hunter,Bet

29、h Blanton-Kent, Christine Wiedman, Robert Burnett, and Wynne Stuart, I was ableto maintain access to a few key print journals including the Journal of the AmericanChemical Society, Journal of Organic Chemistry, Organic Letters, Tetrahedron, andTetrahedron Letters. These circumstances largely complet

30、ed an evolution in the sourcefor specific examples and data. In the earlier editions, these were primarily the resultof direct print encounter or search of printed Chemical Abstracts indices. The currentedition relies mainly on electronic keyword and structure searches. Neither the formernor the lat

31、ter method is entirely systematic or comprehensive, so there is a considerableelement of circumstance in the inclusion of specific material. There is no intent thatspecific examples reflect either priority of discovery or relative importance. Rather,they are interesting examples that illustrate the

32、point in question.Several reviewers provided many helpful corrections and suggestions, collatedby Kenneth Howell and the editorial staff of Springer. Several colleagues providedvaluable contributions. Carl Trindle offered suggestions and material from his courseon computational chemistry. Jim Marsha

33、ll reviewed and provided helpful commentson several sections. Michal Sabat, director of the Molecular Structure Laboratory,provided a number of the graphic images. My co-author, Francis A. Carey, retiredin 2000 to devote his full attention to his text, Organic Chemistry, but continued toprovide valu

34、able comments and insights during the preparation of this edition. Varioususers of prior editions have provided error lists, and, hopefully, these corrections haveviiviiiAcknowledgmentand Personal Statementbeen made. Shirley Fuller and Cindy Knight provided assistance with many aspectsof the prepara

35、tion of the manuscript.This Fifth Edition is supplemented by the Digital Resource that is available The Digital Resource summarizes the results of severalcomputational studies and presents three-dimensional images, comments, and exercisesbased on the results. These were developed with financial supp

36、ort from the TeachingTechnology Initiative of the University of Virginia. Technical support was provided byMichal Sabat, William Rourk, Jeffrey Hollier, and David Newman. Several studentsmade major contributions to this effort. Sara Higgins Fitzgerald and Victoria Landrycreated the prototypes of man

37、y of the sites. Scott Geyer developed the dynamicrepresentations using IRC computations. Tanmaya Patel created several sites anddeveloped the measurement tool. I also gratefully acknowledge the cooperation of theoriginal authors of these studies in making their output available. Problem Responseshav

38、e been provided and I want to acknowledge the assistance of R. Bruce Martin,David Metcalf, and Daniel McCauley in helping work out some of the specific kineticproblems and in providing the attendant graphs.It is my hope that the text, problems, and other material will assist new studentsto develop a

39、 knowledge and appreciation of structure, mechanism, reactions, andsynthesis in organic chemistry. It is gratifying to know that some 200,000 studentshave used earlier editions, hopefully to their benefit.Richard J. SundbergCharlottesville, VirginiaMarch 2007IntroductionThis volume is intended for s

40、tudents who have completed the equivalent of atwo-semester introductory course in organic chemistry and wish to expand their under-standing of structure and reaction mechanisms in organic chemistry. The text assumesbasic knowledge of physical and inorganic chemistry at the advanced undergraduateleve

41、l.Chapter 1 begins by reviewing the familiar Lewis approach to structure andbonding. Lewiss concept of electron pair bonds, as extended by adding the ideas ofhybridization and resonance, plus fundamental atomic properties such as electroneg-ativity and polarizability provide a solid foundation for q

42、ualitative descriptions oftrends in reactivity. In polar reactions, for example, the molecular properties of acidity,basicity, nucleophilicity, and electrophilicity can all be related to information embodiedin Lewis structures. The chapter continues with the more quantitative descriptions ofmolecula

43、r structure and properties that are obtained by quantum mechanical calcula-tions. Hckel, semiempirical, and ab initio molecular orbital (MO) calculations, as wellas density functional theory (DFT) are described and illustrated with examples. Thismaterial is presented at a level sufficient for studen

44、ts to recognize the various methodsand their ranges of application. Computational methods can often provide insightinto reaction mechanisms by describing the structural features of intermediates andtransition structures. Another powerful aspect of computational methods is their abilityto represent e

45、lectron density. Various methods of describing electron density, includinggraphical representations, are outlined in this chapter and applied throughout theremainder of the text. Chapter 2 explores the two structural levels of stereochemistryconfiguration and conformation. Molecular conformation is

46、important in its own right,but can also influence reactivity. The structural relationships between stereoisomers andthe origin and consequences of molecular chirality are discussed. After reviewing theclassical approach to resolving racemic mixtures, modern methods for chromatographicseparation and

47、kinetic resolution are described. The chapter also explores how stereo-chemistry affects reactivity with examples of diastereoselective and enantioselectivereactions, especially those involving addition to carbonyl groups. Much of todays workin organic chemistry focuses on enantioselective reagents

48、and catalysts. The enantio-selectivity of these reagents usually involves rather small and sometimes subtle differ-ences in intermolecular interactions. Several of the best-understood enantioselectiveixxIntroductionreactions, including hydrogenation, epoxidation of allylic alcohols, and dihydroxylat

49、ionof alkenes are discussed. Chapter 3 provides examples of structure-stability relation-ships derived from both experimental thermodynamics and computation. Most of thechapter is about the effects of substituents on reaction rates and equilibria, how they aremeasured, and what they tell us about re

50、action mechanisms. The electronic character ofthe common functional groups is explored, as well as substituent effects on the stabilityof carbocations, carbanions, radicals, and carbonyl addition intermediates. Other topicsin this chapter include the Hammett equation and related linear free-energy r