利用一價銠金屬催化不對稱環化反應合成具全碳四級立體中心之掌性茚化合物

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2021

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本篇論文探討利用一價銠金屬試劑與掌性雙環[2.2.1]雙烯配基L1i配位形成之催化劑,於反應溫度60 ℃且使用1,4-二噁烷及水,比例為10:1為溶劑,並加入2當量碳酸鈉為添加劑的條件下,催化不同芳基硼酯1與不同炔烴化合物2進行不對稱環化反應,成功合成一系列具有含全碳四級立體中心的掌性茚化合物3,共有24個例子,產率65−96%,鏡像超越值高達98%。此外,以芳基硼酯1h及苯基丙炔2f進行反應,生成掌性茚化合物3hf,區域選擇性比例為9.4:1。
This thesis describes an enantioselective annulation of arylboronate esters 1 with internal alkynes 2 in 1,4-dioxane and water at 60 ℃ with 2 equiv of sodium carbonate as an additive in the presence of 3.0 mol % of Rh(I)-catalyst in situ generated from the [RhCl(C2H4)2]2 and chiral bicyclo[2.2.1]heptadiene ligand L1i, affording a series of chiral indene products 3 bearing an all-carbon quaternary stereogenic center in 65−96% yields with up to 98% ee.In addition, the reaction with aryl boron ester 1h and phenylpropyne 2f produces chiral indene 3hf with a regioselectivity ratio of 9.4:1

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一價銠金屬催化, 不對稱環化反應, 掌性雙環[2.2.1]雙烯配基, 全碳四級立體中心, 掌性茚, Rhodium(I)-catalyzed, Asymmetric annulation, chiral bicyclo[2.2.1]diene ligands, all-carbon quaternary stereocenter, chiral indenes

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