經由一價銠金屬催化聯繼芳基環化與β-乙醯氧基消去反應合成具全碳四級立體中心之掌性茚化合物
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2022
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Abstract
本篇論文使用一價銠金屬及含醯胺取代的掌性雙環[2.2.1]雙烯配位基L2a形成之催化劑，並加入三乙胺作為添加劑，以甲醇作為溶劑，於反應溫度40 ℃之條件下，催化炔類化合物2與芳基硼酯化合物1進行不對稱聯繼芳基環化與β-乙醯氧基消去反應，最終生成一系列具全碳四級立體中心的掌性茚化合物3。總共有27個例子，產物產率介於17–99%，鏡像超越值最高達98%，產物位置選擇性最佳比例則為20:1。
This thesis describes an enantioselective tandem arylative cyclization of arylboronates derivatives 1 with internal alkynes 2 in MeOH at 40 °C employing triethylamine as an additive in presence of 3.0 mol% of Rh(I)-catalyst in situ generated from the [Rh(C2H4)2Cl]2 and the chiral bicyclo[2.2.1]heptadiene ligand bearing a benzylamide group L2a. This synthetic protocol offers a facile way to provide a series of chiral indene derivatives 3 with an all-carbon quaternary stereocenter in 17–99% yields, up to 98% ee and with up to regioselective ratio of 20:1.
This thesis describes an enantioselective tandem arylative cyclization of arylboronates derivatives 1 with internal alkynes 2 in MeOH at 40 °C employing triethylamine as an additive in presence of 3.0 mol% of Rh(I)-catalyst in situ generated from the [Rh(C2H4)2Cl]2 and the chiral bicyclo[2.2.1]heptadiene ligand bearing a benzylamide group L2a. This synthetic protocol offers a facile way to provide a series of chiral indene derivatives 3 with an all-carbon quaternary stereocenter in 17–99% yields, up to 98% ee and with up to regioselective ratio of 20:1.
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一價銠金屬催化, 不對稱芳基環化反應, 全碳四級立體中心, 掌性茚化合物, β-乙醯氧基消去反應, 含有醯胺基的掌性雙環[2.2.1]雙烯配基, Rhodium(I)-catalyzed, asymmetric arylative cyclization, an all-carbon quaternary stereocenter, chiral indenes, β-acetoxy elimination, bicyclo[2.2.1]heptadiene ligand