銠金屬(I)/掌性雙烯配體催化進行區域選擇性苯並環丁醇開環與重氮酯之不對稱碳烯插入與分子內醛醇反應
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2017
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Abstract
本論文的研究主要是使用本實驗室所開發的掌性雙環 [2.2.1] 雙烯配基L1C與五莫耳百分率的一價銠金屬催化劑 (5 mol% of Rhodium) ，對苯並環丁醇 (Benzocyclobutenol) 進行選擇性開環，再與重氮酯 (Diazoester) 形成銠碳烯 (Rhodium carbene) 、並進行碳烯插入 (Carbene insertion) 反應得到銠烯醇鹽離子 (Rhodium enolate) ，接著進行分子內醛醇反應 (Intramolecular Aldol reaction) 得到具有連續兩個立體中心的茚醇 (Indanol) 化合物。反應在60 °C、以甲苯為溶劑的反應條件，並根據其不同的反應基質可得到高達82%的產率以及高達95% ee的鏡像超越值。
In this thesis, a Rh(I)-catalyzed regioselective ring cleavage of benzocyclobutenols 7 followed by enantioselective rhodium carbene insertion with various diazoesters 8 , and subsequent intramolecular aldol reaction via the thus obtained rhodium enolates is described. This transformation proceeds at 60 °C, in the presence 5 mol% of Rh(I) / L1C catalyst, to offer the corresponding products possessing two contiguous quaternary stereo-centers with up to 82% yield, and 95% ee.
In this thesis, a Rh(I)-catalyzed regioselective ring cleavage of benzocyclobutenols 7 followed by enantioselective rhodium carbene insertion with various diazoesters 8 , and subsequent intramolecular aldol reaction via the thus obtained rhodium enolates is described. This transformation proceeds at 60 °C, in the presence 5 mol% of Rh(I) / L1C catalyst, to offer the corresponding products possessing two contiguous quaternary stereo-centers with up to 82% yield, and 95% ee.
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銠金屬催化, 掌性雙烯配基, 銠插入反應, 茚醇, Rh(I)-catalyst, Chiral diene ligand, Rh(I) carbene insertion, indanol