yq有机Chapt-13-1共轭体系.pptVIP

Chapt 13 Conjugated Unsaturated systems Introduction Conjugated unsaturated systems: systems that have a p orbital on an atom adjacent to a double bond ––– molecules with delocalized p bonds allyl radical CH2 CHCH2? ?have a single electron allyl cation CH2 CHCH2+ ? be vacant allyl anion CH2 CHCH2:– ? have a pair of electrons 1,3-butadiene CH2 CH–CH CH2 ? another double bond Allylic Substitution and the allyl Radical Allylic substitution: any reaction in which an allylic hydrogen atom is replaced. Allylic Chlorination High Temperature Allylic Bromination with N-Bromosuccinimide Propene undergoes allylic bromination when treated with N-bromosuccinimide NBS in CCl4 in the presence of peroxides or light. The Allyl Cation The allyl cation CH2 CHCH2+ is an unusually stable carbocation. Alkadienes and Polyunsaturated Hydrocarbons Alkadiene and alkatriene ? diene and triene; Alkadiyne and alkenyne ? diyne and enyne. Cumulenes 累积二烯 1,3-Butadiene: Electron Delocalization Bond Length of 1,3-Butadiene Electrophilic Attack on Conjugated Dienes 1,3-butadiene reacts with one molar equivalent of HCl 1,3-Butadiene shows 1,4-addition reactions with electrophilic reagents other than HCl. Reactions of this type are quite general with other conjugated dienes. Conjugated trienes often show 1,6-addition. Kinetic Control Versus Thermodynamic Control The addition of HBr to 1,3-butadiene The Diels-Alder reaction 1, 4-Cycloaddition reaction of dienes Factors favoring the Diels-Alder Reaction Diene: electron-releasing groups Dienophole:electron-withdrawing groups Stereochemistry of the Diels-Alder Reaction Diels-Alder Reaction is highly stereospecific: Syn Addition and the configuration of the dienophile is retained in the product. Diels-Alder Reaction occurs primarily in an endo 内型 rather than an exo 外型 fashion when the reaction is kinetically controlled. Asymmetric Diel-Alder Reaction Using chiral Lewis acid catalysts P616 13.16 a d g 13.17 1