吲哚与乙烯三羧酸盐的催化对映选择性傅克/迈克尔加成反应。
Catalytic enantioselective Friedel-Crafts/Michael addition reactions of indoles to ethenetricarboxylates.
作者信息
Yamazaki Shoko, Iwata Yuko
机构信息
Department of Chemistry, Nara University of Education, Takabatake-cho, Nara 630-8528, Japan.
出版信息
J Org Chem. 2006 Jan 20;71(2):739-43. doi: 10.1021/jo052041p.
[reaction: see text] The Friedel-Crafts reaction is an important reaction for the formation of new C-C bonds. Recently, catalytic enantioselective Friedel-Crafts reaction of alkylidene malonates has been reported. However, the substituents in alkylidene malonates are limited. To explore new substituents such as carboxyl and carbonyl groups, catalytic enantioselective Friedel-Crafts reactions of reactive ethenetricarboxylates and acyl-substituted methylenemalonates 1 were investigated. The reaction of 1 with indoles in the presence of catalytic amounts of chiral bisoxazoline copper(II) complex (10%) in THF at room temperature gave alkylated products in high yields and up to 95% ee. The enantioselectivity can be explained by the secondary orbital interaction on approach of indole to the less hindered side of the 1-Cu(II)-ligand complex.
[反应：见正文]傅-克反应是形成新碳-碳键的重要反应。最近，已报道了亚烷基丙二酸酯的催化对映选择性傅-克反应。然而，亚烷基丙二酸酯中的取代基是有限的。为了探索诸如羧基和羰基等新的取代基，研究了活性乙烯三羧酸酯和酰基取代的亚甲基丙二酸酯1的催化对映选择性傅-克反应。在室温下，1与吲哚在四氢呋喃中，在催化量的手性双恶唑啉铜（II）配合物（10%）存在下反应，得到高产率且对映体过量高达95%的烷基化产物。对映选择性可以通过吲哚接近1-铜（II）-配体配合物位阻较小一侧时的次级轨道相互作用来解释。
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