銠金屬(I)/掌性雙環[2.2.1]雙烯配體催化進行不對稱1,4-加成反應:合成掌性γ-胺基酸及γ-胺基膦酸之應用 Enantioselective Synthesis of γ-Amino Acids and γ-Amino Phosphonic Acids via Rhodium Catalyzed Asymmetric 1,4-Conjugate Addition Reactions

Date
2016
Authors
黃志浩
Huang, Chih-Hao
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Abstract
本論文研究主題為利用本實驗室所開發的掌性雙環[2.2.1]雙烯配體與一價銠金屬形成之催化劑催化芳香基硼酸與γ-位胺基及膦酸酯取代之α , β-不飽和酯類進行不對稱1,4-加成反應。使用三莫耳百分率的銠金屬試劑(3 mol% of Rh)及L1e或L1f配體催化加成反應進行,生成的產物其產率有26–>99%,鏡像超越值為90–>99.5% ee。這個合成方法可利用來合成balcofen及phaclofen藥物分子。
This thesis describes an efficient synthesis of highly enantioenriched 4-amino-3-aryl-butanoates and 4-phosphoryl-3-aryl-butanoates via an enantioselective 1,4-addition of an array of aryboronic acids to γ-amino-α , β-unsaturated esters and γ-phosphoryl-α , β-unsaturated esters. In the presence of 3 mol% of the Rh(I)/ chiral diene L1e or L1f as catalyst, the conjugate addition adducts were isolated in 26–>99% yield and 90–>99.5% ee. The synthetic usefulness of the developed method was demonstrated in the syntheses of baclofen and phalcofen.
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銠金屬催化試劑, 掌性雙烯配基, α, β-不飽和羧酸酯, Rhodium, Chiral diene ligand, α, β-Unsaturated esters
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