三种二茂铁苄基叔胺合成及其环金属化（hg、pd）反应.pdf

中文摘要乙酰基二茂铁与取代的苄胺进行亲核加成一消除反应得到中间体化合物一席夫碱[(矿-CsHs)Fe[rf—CsH4C(CH3)=NCH2C6H4-R)],R=4-MeO(a),4-Me(b),H(c), 席夫碱在乙醇(甲醇)/硼氢化钠或四氢呋喃/氢化铝锂的还原作用下得到含二茂铁乙基的系列仲胺化合物[()Fe[r/J—C5I-14CH(CH3)NHCH2C6H4-R)], R=4-MeO(a),4-Me(b),H(c),该系列化合物在乙腈/氰基硼氢化钠与37%的甲醛溶液的还原甲基化作用下,得到含二茂铁乙基的叔胺系列化合物【()Fe- [rf-CsH4CH(CH3)N(CH3)CH2C6H4一R)],R=4一MeO(a),4-Me(b),H(c)。以醋酸汞、四氯钯钠作为邻位汞化、环钯化试剂分别对上述叔胺类化合物进行邻位汞化、环钯化反应,得到了邻位汞化产物[()Fe( CH(CH3)(HgCl)N(CH3)CH2. c6H4一R)],R=4一MeO(a),4-Me(b),H(c)和环钯化产物伊[Pd{(矿-CsHs)Fe(矿一CsH3CH 一(CH3)N(CH3)CH2C6H4-R)}]CI(PPh3),R=4·MeO(a),4-Me(b),H(c)。-H键活化的立体选择性进行了讨论。上述化合物的结构均通过元素分析、IR、1H-、一个汞化物的单晶进行了结构测试。关键词: 二茂铁苄叔胺邻位汞化反应环钯化反应立体选择性 ABSTRACT ’Condensanon ofacetylferrocene and series substituted benzyl annnes inether at room temperature resulmd inferrocenylaldimines[(矿一CsHs)Fe[rt-CsH4C(CH3)=N CH2C6H4-R)],R=4-MeO(a),4一Me(b),H(c)in moderate of these imines with sodium borohydride inmethanol orlithiumaluminum hydride inTHF produced quantitative secondary ferrocenylamines[(矿-CsHs)Fe[矿一CsH4CH(CH3) NHCH2C6H4-R)],R=4一MeO(a),4-Me(b),H(c).Reductive methylation ofsecondary ferrocenylamines asmentioned above丽th sodium cyanoborohydride,formaldehyde inacetic acid gave out thecorresponding tertiaryferrocenylamines【(矿一CsHs)Fe f矿-CsH4CH(CH3)N(CH3)CH2C6H4-R)],R=4-MeO(a),4—Me(b),H(c). Ortho-mercuration ofthesetertiary amines afforded plexes inwhich anintramolecular N—Hg coordination pattern was ofthese amines led to racemic plexes inlow stereoselective C-H activation was structures pounds as mentioned before were characterized by elemental analysis,IR and 1H- addition,the structures of three plexes and one plex were alsoconfmned byX-Ray singlecrystal diffraction. KEY ,Benzylamines,Cyclopalladation,Ortho—mercuration, Stereoselectivity 独创性声明本人声明所呈交的学位论文是本人在导师指导下进行的研究工作和取得的研究成果,除了文中特别加以标注和致谢之处外,论文中不包含其他人已经发表或撰写过的研究成果,也不包含为获得苤叠盘堂或其他教育机构的学位或证书而使用过的材料。与我一同工作