钯催化suzuki-miyaura交叉偶联反应和分子内heck反应的研究.pdf

湖南师范大学硕士学位论文钯催化Suzuki-Miyaura交叉偶联反应和分子内Heck反应的研究姓名:张岳花申请学位级别:硕士专业:应用化学指导教师:李金恒 20090501 摘要本论文主要研究了醋酸钯/肛羰基胺催化体系催化 ,Ⅳ-芳基炔酰胺的亲电自位环化反应以及l一(2一碘苄基).螺[】。Suzuki-Miyaura 交叉偶联反应、。论文主要研究内容如下:. (1)。主要从配体、催化剂、。(2)发展了醋酸钯/Ⅳ_(4一甲氧基苯基),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,Ⅳ.(4一甲氧基苯基)一3-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Ⅳ-,通过分子内亲电自位环化反应,生成了螺[4,51-。(4)研究了1.()一螺[4,5]--:(1)在醋酸钯、三苯基膦和NaHC03的作用下、温度为120℃的氩气氛中迅速反应,,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,,,在分子内部形成另一种带六元环的新物质。关键词:偶联反应;卤代芳烃;芳基硼酸;螺环化合物; 亲电自位环化反应。 ABSTRACT The contents ofthisthesisinclude(i)thePd(OAc)2/fl-Oxo amides catalyze Suzuki—Miyaura cross·coupling reaction,(ii)ipso—cyclizations of 1-(2·iodobenzyl)-1一azaspiro[】-triene一8·ones,and(iii)the Heck reactions ofl-(2一iodobenzyl)一1一azaspiro[】一triene一8- Suzuki— Miyaura reaction,ipso—cyclization reaction and Heck reaction are the important methods forthe construction ofnew C—C bonds anic synthesis. in the palladium-catalyzed Suzuki—Miyaura cross—coupling reaction and Heck reaction discussed the effects ofligands,catalysts,and additives on theSuzuki·Miyaura cross—coupling reaction and Heck reaction mechanisms Suzuki—Miyaura cross—coupling reaction ofaryl halidesand arylboronic acids has been developed usingPd(OAc)2/fl-Oxo amides as the catalytic the presence of Pd(OAc)2 andⅣ-(4一 methoxyphenyl)一3-oxobutanamide,a variety ofaryl halides were coupled with arylboronic acids essfully inmoderate to excellent yields provding hi曲turnover numbers(maximum TONs=950 000 andTOFs。 79 167).The resu