【作者】 张岳花；

【导师】 李金恒；

【作者基本信息】 湖南师范大学 ， 应用化学， 2009， 硕士

【摘要】 本论文主要研究了醋酸钯/β-羰基胺催化体系催化Suzuki-Miyaura交叉偶联反应,N-芳基炔酰胺的亲电自位环化反应以及1-（2-碘苄基）-螺[4.5]三烯-8-酮的分子内Heck反应。Suzuki-Miyaura交叉偶联反应、亲电自位环化反应和Heck反应都是有机合成中构建新的C-C键的重要方法。论文主要研究内容如下:（1）对钯催化Suzuki-Miyaura交叉偶联反应和Heck反应的近几年的研究进展作了综述。主要从配体、催化剂、助催化剂和机理等四个方面详细地对Suzuki-Miyaura交叉偶联反应和Heck反应的进展进行了介绍和讨论。（2）发展了醋酸钯/β-羰基胺催化体系高效催化卤代芳烃与芳基硼酸的Suzuki-Miyaura交叉偶联反应。在醋酸钯和N-（4-甲氧基苯基）-3-羰基丁酰胺作用下,卤代芳烃与芳基硼酸能够在温和的条件下发生偶联反应,以高的产率得到相应的偶联产物,催化效率也很高（TONs=950 000,TOFs=79 167）。实验证明,N-（4-甲氧基苯基）-3-羰基丁酰胺是一种价廉且高效的配体。（3）研究了芳基炔酰胺在NBS亲电试剂的作用下,发生亲电自位环化反应。我们发现N-邻碘苄基-芳基炔酰胺在NBS的亲电试剂作用下,通过分子内亲电自位环化反应,生成了螺[4,5]三烯-8-酮类化合物。（4）研究了1-（2-碘苄基）-螺[4,5]三烯-8-酮在两种不同催化体系中的Heck反应:（1）在醋酸钯、三苯基膦和NaHCO₃的作用下、温度为120℃的氩气氛中迅速反应,反应物中的碘原子进攻螺环上6-位碳原子,在分子内部形成一种带六元环结构的新物质;（2）在PdCl₂（Ph₃P）₂、TBAB和Et₃N的作用下,温度为120℃的氩气氛中反应12小时,反应物中的碘原子进攻螺环上6-位碳原子,同时螺环上的6-位双键被还原成单键,在分子内部形成另一种带六元环的新物质。更多还原

【Abstract】 The contents of this thesis include（ⅰ） the Pd（OAc）₂/β-Oxo amides catalyze Suzuki-Miyaura cross-coupling reaction,（ⅱ） ipso-cyclizations of 1-（2-iodobenzyl）-1-azaspiro[4.5]-triene-8-ones,and（ⅲ） the Heck reactions of 1-（2-iodobenzyl）-1-azaspiro[4.5]-triene-8-ones.The Suzuki-Miyaura reaction,ipso-cyclization reaction and Heck reaction are the important methods for the construction of new C-C bonds in organic synthesis.1.Progress in the palladium-catalyzed Suzuki-Miyaura cross-coupling reaction and Heck reaction are summarized.We discussed the effects of ligands,catalysts,and additives on the Suzuki-Miyaura cross-coupling reaction and Heck reaction detailedly.The mechanisms are also reviewed.2.The Suzuki-Miyaura cross-coupling reaction of aryl halides and arylboronic acids has been developed using Pd（OAc）₂/β-Oxo amides as the catalytic system.In the presence of Pd（OAc）₂ and N-（4-methoxyphenyl）-3-oxobutanamide,a variety of aryl halides were coupled with arylboronic acids successfully in moderate to excellent yields provding high turnover numbers（maximum TONs=950 000 and TOFs= 79 167）.The results showed that N-（4-methoxyphenyl）-3-oxobutanamide was an inexpensive and efficient ligand. 3.ipso-Cyclization of N-arylpropiolamides was studied in the presence of NBS.We found that N-（2-iodobenzyl）-N-aryl-3-phenyl propiolamides could undergo the intramolecular electrophilic ipsocyclization with NBS to synthesize the corresponding spiro[4,5]trine-8-ones in good yields.4.Two catalytic systems for the Heck reactions of 1-（2-iodobenzyl） -1-azaspiro[4.5]-triene-8-ones have been developed:（1） Pd（OAc）₂ combined with PPh₃ and NaHCO₃ was found to be an efficient catalytic system for the Heck reactions of 1-（2-iodobenzyl）-1-azaspiro[4.5]-triene-8-ones at 120℃under the argon atmosphere.1-（2-Iodobenzyl）-1-azaspiro[4,5]-triene-8-ones underwent the intramoleecular Heck reaction with this catalytic system smoothly to construct a new six-membered ring. （2） Another efficient catalytic system has also been developed,in the presence of PdCl₂（PPh3）2/TBAB/Et₃N,the Heck reactions of 1-（2-iodobenzyl）-1-azaspiro[4.5]-triene-8-ones were conducted successfully at 120℃under the atmosphere of argon,followed by protonation to afford the crossponding six-membered-ring products.更多还原