金及銠金屬催化1,6-烯炔化合物與重氮化合物合成四氫-1H-環戊烯併呋喃衍生物之反應

Gold and Rhodium-Catalyzed Synthesis of Tetrahydro-1H-cyclopenta[c]furans from 1,6-Enynes and Diazo Compounds

李信甫(Lee, Hsin Fu)

指導教授 ： 劉瑞雄

國立清華大學/理學院/化學系/碩士(2016年)

摘要

我們發展出了一套能將1,6-烯炔化合物及重氮化合物，在溫和條件金金屬催化下，可以合成出E/Z form乙烯基二環[3.1.0]己烷衍生物。接下來藉由銠金屬催化E/Z form乙烯基二環[3.1.0]己烷衍生物，依據基質特性的不同，會生成兩種不同形式的產物，銠金屬會先插入三元環的碳碳鍵中，若此時中間體發生1,3–位移反應，則會生成四氫-1H-環戊烯併呋喃衍生物；若中間體發生β-氫消除反應則會生成含有共軛雙烯結構的產物，且兩者都有不錯的產率。

關鍵字

金金屬催化 ； 銠金屬催化 ； 烯炔化合物 ； 重氮化合物

並列摘要

The reaction of a variety of unsaturated bond-containing 1,6-enynes with diazo compounds in the presence of [(IPr)AuBF4] as catalyst precursor at room temperature leads to the general formation of alkenylbicyclo[3.1.0]hexane derivatives with good yields, which were, afterwards, when heated in o-xylene solvent in the presence of [Rh(CO)2Cl]2 as catalyst at 150 0C affords two types of product, depending on the type of tether in alkenylbicyclo[3.1.0]hexane derivatives. In the first case, rhodium insertion into three member ring followed by 1,3-shift gives tetrahydro-1H-cyclopenta[c]furan. Whereas, in the second case, rhodium insertion and beta-hydride elimination affords conjugate diene compound. Both cases give good yields.

並列關鍵字

Gold-Catalyzed ； Rhodium-Catalyzed ； 1,6-Enyne ； diazo

參考文獻

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