新颖的钯催化的烯丙基化反应研究.pdf.pdf

大连理工大学硕士学位论文新颖的钯催化的烯丙基化反应研究姓名:高群峰申请学位级别:硕士专业:应用化学指导教师:包明 20090629 大连理工大学硕士学位论文摘要烯丙基醇、胺等烯丙基类化合物是有机合成的重要中间体,通过钯催化形成该类化合物的方法在天然产物合成、药物合成等领域起着重要的作用。本文主要研究了新型的通过钯催化形成烯丙基类化合物的反应,主要有两部分内容: 、三丁基烯丙基锡和活化双键的三组分反应。以往合成类似化合物要经过自由基反应完成,而自由基反应条件苛刻、官能团兼容性不好、原料浪费严重。这些不符合当今绿色化学的要求。通过研究,我们发现在THF 溶剂中以5 t001%Pd(PPh3)4作为催化剂,氮气保护下50 oC反应24 h,可以很好的完成这类三组分反应,而且没有得到可能出现脱芳构化反应和Stille偶联反应产物。该体系操作简单、反应条件温和。 、、酮和亚胺的亲核加成反应,只得到烯丙基加成产物。研究发现催化剂的量为5 m01%Pd2(dba)3,炔丙基溴的量为10 m01% 时,加成反应达到了最佳的催化效果。该方法对醛、亚胺都表现出了很好的反应活性, 值得一提的是对酮类化合物也有很好的反应活性。通过本文的研究,进一步揭示了兀- 炔丙基、。关键词:三组分反应;亲核加成反应;矿烯丙基钯;烯丙基醇新颖的钯催化的烯丙基化反应研究 Novel Palladium Catalyzed Allylation Reactions Abstract Allyl amine and theirdeftvatives are important intermediates anic —catalyzed allylation toachieve pounds plays animportant role in natural product synthesis and drug thiswork,new methods for pounds synthesis bypalladium—catalysis are main content issummarized below: type ponent reaction catalyzed bypalladium,using benzyl halides, allyltributyltin and activated olefines was thepast,pounds were synthesized by the radical reaction,but thereaction conditions were notmildand had low functional patibility,SO alotofmaterials were conditions do not meet therequirements ofmodern environmentally conscious thispaper,it Was found that inthepresence of5m01%Pd(PPh3)4 and TI{F assolvent,reasonable tomoderate yields were obtained at50 oC for 24 dearomatization product and Stillecoupling product were not developed method was carried out withsimple operation under mildconditions. thispaper,the nucleophilic additionreactivity ofrc-propargyl,兀-allyl palladium intermediate toaldehydes,ketones and imines Wasfound thatonly the 7c-allylgroup could undergo nucleophilic addition toproduce homoallyl alcohols andamines. Bestyields were obtained when 5m01%Pd2(dba)3 and 10m