Advanced Organic Chemistry

Abstract

The methods of organic synthesis have continued to advance rapidly and we have made an effort to reflect those advances in this Fifth Edition. Among the broad areas that have seen major developments are enantioselective reactions and transition metal catalysis. Computational chemistry is having an expanding impact on synthetic chemistry by evaluating the energy profiles of mechanisms and providing structural representation of unobservable intermediates and transition states. The organization of Part B is similar to that in the earlier editions, but a few changes have been made. The section on introduction and removal of protecting groups has been moved forward to Chapter 3 to facilitate consideration of protecting groups throughout the remainder of the text. Enolate conjugate addition has been moved from Chapter 1 to Chapter 2, where it follows the discussion of the generalized aldol reaction. Several new sections have been added, including one on hydroalumination, carboalumination, and hydrozirconation in Chapter 4, another on the olefin metathesis reactions in Chapter 8, and an expanded discussion of the carbonyl-ene reaction in Chapter 10. Chapters 1 and 2 focus on enolates and other carbon nucleophiles in synthesis. Chapter 1 discusses enolate formation and alkylation. Chapter 2 broadens the discussion to other carbon nucleophiles in the context of the generalized aldol reaction, which includes the Wittig, Peterson, and Julia olefination reactions. The chapter considers the stereochemistry of the aldol reaction in some detail, including the use of chiral auxiliaries and enantioselective catalysts. Chapters 3 to 5 focus on some fundamental functional group modification reactions. Chapter 3 discusses common functional group interconversions, including nucleophilic substitution, ester and amide formation, and protecting group manipulations. Chapter 4 deals with electrophilic additions to double bonds, including the use of hydroboration to introduce functional groups. Chapter 5 considers reductions by hydrogenation, hydride donors, hydrogen atom donors, and metals and metal ions. Chapter 6 looks at concerted pericyclic reactions, including the Diels-Alder reaction, 1,3-dipolar cycloaddition, [3,3]- and [2,3]-sigmatropic rearrangements, and thermal elimination reactions. The carbon-carbon bond-forming reactions are emphasized and the stereoselectivity of the reactions is discussed in detail.