Transition Metal-Catalyzed Oxygenative α-Addition and β-Alkylation of Terminal Alkynes

Disubstituted rhodium vinylidene;Metalloketene;β-Alkylation;Oxygenative α-addition;5-Membered ring synthesis;Carbonyl synthesis;540

자연과학대학 화학부 ;

University:서울대학교 대학원

关键词: Disubstituted rhodium vinylidene;    Metalloketene;    β-Alkylation;    Oxygenative α-addition;    5-Membered ring synthesis;    Carbonyl synthesis;    540;   

Others  :  http://s-space.snu.ac.kr/bitstream/10371/134947/1/000000140706.pdf

美国|英语

来源: Seoul National University Open Repository

【 摘 要 】

Described in this dissertation is the development of the transition metal-catalyzed cyclization and oxygenative nucleophilic addition of terminal alkynes which gives cyclopentane and cyclohexane carboxylic acid derivatives as products. Using terminal alkynes tethered with electrophiles such as alkyl halides, aldehydes, imines, and Michael acceptors, the reaction can be carried out with a broad range of nucleophiles such as alcohols and amines in the presence of a suitable base, oxidant and rhodium catalyst. The proposed mechanism involves the formation of a disubstituted metal vinylidene intermediate via β-alkylation followed by transfer oxygenation to form a metalloketene which then undergoes nucleophilic addition. This transformation can provide diverse ester and amide products while forming a 5- and 6-membered ring moiety.