Additions to and Substitutions at C-C &pgr;-Bonds
- M.F. Semmelhack, Princeton University, NJ, USA
Volume 4 focuses on additions and the resulting substitutions at carbon-carbon &pgr;-bonds. Part 1 includes processes generally considered as simple polar reactions, reactive electrophiles and nucleophiles adding to alkenes and alkynes. A major topic is Michael-type addition to electron deficient &pgr;-bonds, featured in the first six chapters. In part 2 are collected the four general processes leading to nucleophilic aromatic substitution, including radical chain processes and transition metal activation through to &pgr;-complexation. Metal-activated addition (generally by nucleophiles) to alkenes and polyenes is presented in part 3, including allylic alkylation catalyzed by palladium. The coverage of nonpolar additions in part 4 includes radical additions, organometal addition (Heck reaction), carbene addition, and 1,3-dipolar cycloadditions.
Published: January 1992
- Polar Additions to Activated Alkenes and Alkynes. Stabilized nucleophiles with electron deficient alkenes and alkynes. Conjugate additions of reactive carbanions to activated alkenes and alkynes. Conjugate additions of carbon ligands to activated alkenes and alkynes mediated by Lewis acids. Organocuprates in the conjugate addition reaction. Asymmetric nucleophilic addition to electron deficient alkenes. Nucleophilic addition-electrophilic coupling with a carbanion intermediate. Addition of H-X reagents to alkenes and alkynes. Electrophilic addition of X-Y reagents to alkenes and alkynes. Electrophilic heteroatom cyclizations. Nucleophilic Aromatic Substitutions. Arene substitution via nucleophilic addition to electron deficient arenes. Nucleophilic coupling with aryl radicals. Nucleophilic coupling with arynes. Nucleophilic addition to arene-metal complexes. Polar Additions to Alkenes and Alkynes. Heteroatom nucleophiles with metal-activated alkenes and alkynes. Carbon nucleophiles with alkenes and alkynes. Nucleophiles with allyl-metal complexes. Nucleophiles with cationic pentadienyl-metal complexes. Carbon electrophiles with dienes and polyenes promoted by transition metals. Nonpolar Additions to Alkenes and Alkynes. Radical addition reactions. Radical cyclizations and sequential radical reactions. Vinyl substitutions with organopalladium intermediates. Carbometallation of alkenes and alkynes. Hydroformylation and related additions of carbon monoxide to alkenes and alkynes. Methylene and nonfunctionalized alkylidene transfer to form cyclopropanes. Formation and further transformations of 1,1-dihalocyclopropanes. Addition of ketocarbenes to alkenes, alkynes and aromatic systems. Intermolecular 1,3-dipolar cycloadditions. Intramolecular 1,3-dipolar cycloadditions. Author index. Subject index.