Nickel-catalyzed conjugate addition of alkynyl groups to. alpha.,. beta.-unsaturated ketones

• Main Authors: Schwartz, Jeffrey, Carr, Denise B, Hansen, Robert T, Dayrit, Fabian M
• Format: text
• Published: Archīum Ateneo 1980
• Subjects: Chemistry; Organic Chemistry
• Online Access: https://archium.ateneo.edu/chemistry-faculty-pubs/96; https://pubs.acs.org/doi/pdf/10.1021/jo01303a024
• Institution: Ateneo De Manila University

The complex formed by reaction of Ni (acac) 2 and DiBAH (1: 1) catalyzesconjugate addition of dialkylaluminum acetylides to, ß enones;; on hydrolysis, 3-alkynyl ketones are produced in high yield. Through this procedureconjugate addition of alkynyl groups to either S-cis or S-trans enones can be effected. This procedure is thefirst one which permits conjugate addition of terminal alkynyl units to ordinary S-trans enones. In cases wheremore than one stereochemical outcome is possible, conjugate addition of alkynyl units gives only one of these.Only 1,4-addition is observed and this only of the alkynyl unit. Complications arising from oxygen substitutionin the alkynyl side chain are described.