过渡金属活化炔基参与的环化反应研究-有机合成专业论文.docxVIP

兰州大学博士学位论文 兰州大学博士学位论文 石赞 Abstract Recently,much attention has been paid to the activation of alkynes with transition metal compounds as powerful and useful methods to construct structurally complex molecules．In this context,we summarized the most significant recent reported transformations of propargylic esters，including rhodium，ruthenium，nickel，gold and platinum metal catalyst． A simple and tandem synthetic approach,which offers all efficient,direct route to highly substituted indenes，has been developed by palladium or nickel—catalyzed cyclization of propargylic compounds and nitrogen nucleophiles．The reaction takes place under mild conditions，and a possible mechansim is proposed．The structure WaS definitively secured by an X-ray crystal structure analysis． The diverse and rich reactivity of the readily available propargylic esters has continued to attract the interest of different research groups．We report herein a gold (III)-catalyzed【3+3]-cycloaddition of propargyl esters and azomethine imines．This report represents the first example of a formal eycloaddition between alkenyl metal carbenoids and 1，3-dipoles．In contrast to the previously reported cycloadditions，this reaction highlights the difference in the reactivity of alkenyl Fischer carbenes and the alkenyl Au-carbenoids generated from the rearrangement of propargyl esters． Keywords：transition metal catalyzed，cyclization，tandem reaction，propargylic esters， 1，3-dipoles lI 兰州大学博士学位论文 兰州大学博士学位论文 石赞 缩写对照表(LIST OF ABBREVIATIONS) DMF N，N．二甲基甲酰胺 DBU l，8一二氦x2N[5．4．0】-7一十一烯 THF 四氢呋喃 TLC 薄层色谱 Ts 对甲苯磺酰基 DMAP 4．(--甲基氨基)吡啶 TBDPS 叔丁基二苯基硅基 TMS 三甲基硅基 de 非对映体过量 ∞ 对映体过量 Ac 乙酰基 acac 乙酰丙酮基 aq． 水溶液 Bu 正丁基 Bz 苯甲酰基 Cat． 催化 CBz 苄氧羰基 Cp 环戊二烯基 Cy 环己基 DABCO 二氮杂双环【2．2．2】辛烷 DEA 二乙胺 DME 二甲醚 dppf 双(二苯基膦基)二茂铁 dppp 双(二苯基膦基)丙烷 dba 苄叉丙酮 HMPA 六甲基磷酸三胺 mCPBA 间氯过氧化苯甲酸 Mes 均三甲苯基 Ms 甲基磺酰基(保护羟基用) NBS N．溴代丁二酰亚胺 NMP N．甲