氧金屬催化親和性醯基取代反應與酯基交換反應

Nucleophilic Acyl Substitutions of Anhydrides and Esters eith Protic Nucleophiles Catalyzed by Water Tolerent, Amphoteric, Oxometallic Species

郭仁皇(Jen-Huang Kuo)

指導教授 ： 陳建添 博士

國立臺灣師範大學/理學院/化學系/博士(2003年)

摘要

無資料

關鍵字

催化 ； 氧金屬 ； 親和性醯基取代反應 ； 酯基交換反應 ； 兩性特質 ； 水相安定

並列摘要

英文摘要
Among twenty-four different oxo-metallic species examined, vanadyl triflate, dioxomolybdenum dichloride and oxomolybdenum tetrachloride were the most efficient catalysts to facilitate nucleophilic acyl substitution (NAS) of anhydrides with a myriad array of alcohols, amines, and thiols in high yields and high chemoselectivity. The catalytic NAS tolerates virtually all kinds of functional groups and was unprecedented in view of the well-recognized redox chemical behaviors associated with oxomolybdenum (VI) species. By using benzoic anhydride as a mediator for in-situ generation of an incipient mixed-anhydride with a given functional alkanoic acid, one can achieve oleate, dipeptide, diphenylmethyl, N-Fmoc-α-amino, pyruvic, and tert-butylthio ester, N-tert-butylamide and trityl acrylate syntheses with appropriate protic nucleophiles. Similar to vanadyl species, the amphoteric character of the Mo=O unit in oxomolybdenum chlorides was proven by 1H NMR kinetic experiments to be responsible for the catalytic NAS profile.

並列關鍵字

Nucleophilic Acyl Substitutions ； Protic Nucleophiles ； Oxometallic Species ； Amphoteric ； Water Tolerent ； Catalyzed