金催化的以ph2so为氧化剂通过分子内反应进行的环丙烷炔类物质的 .docVIP

金催化的以Ph2SO为氧化剂通过分子内反应进行的环丙烷炔类物质的扩环反应 马艳娜 刘瑞雄* 杨尚东* 摘要：在这里，我要给介绍的是金催化的环丙烷炔类物质的扩环反应，所用的氧化剂是Ph2SO，而且是发生在分子内的反应。我们知道当给电子基团和吸电子基团位于环丙烷的临位时,三元环容易发生环的断裂反应。 关键词：环丙烷炔；金催化；Ph2SO；开环反应。 Introduction Metal-catalyzed reactions are important tools to construct complex molecular framework. Bcause they are environmental frendliness,clean and energy conservation. Nowadays ,gold-catalyzed has been an important way in metal-catalyzed. The reasons as below: (1) High activity and mild reaction conditions (2) Reactive in some special reactions (3) Environmental friendliness Cyclopropane compounds are prone to ring-cleavage when the donor and acceptor groups are present as vicinal substituents at the cyclopropane ring. Here, I will report a gold-catalyzed oxidative ring-expansion of alkynylcyclopropanes using Ph2SO as an oxidant. The substrate is alkynylcyclopropanes. Experimental Sections Preparation of zhe substrate (1) S1 S2 Pd(PPh3)2Cl2（300mg, 0.42mmol),CuI(80mg, 0.84mmol) and 4-iodoanisode(2.00g, 8.55mol) were placed in a 100ml round-bottom flask. The flask was sealed and flushed with nitrogen, then triethylamine was added to the mixture, and was stirred for 10 min before triethylsilylacetylene (1.33ml, 9.40mol) was added dropwise. The mixture was stirred for 17h, and the solution was concentrated in vacuo. The residue was chromato-graphed on a silica column (EA-hexane=1:20) to give the TM(1.70g,8.35mmol,97.7%). (2) S2 S3 The S2 was dissolved in a mixture of CH2Cl2 and MeOH(1:1), and treated with K2CO3. The mixture was stirred until the S2 disappeared(about 3h). Then the water(10ml) was added and the reaction mixture was extracted with CH2Cl2, dried over MgSO4, Finally, the resulting solution was concentrated in vacuo to give S3(8.33mmol,99.7%). (3) S3 S4 S5 To a triethylamine solu