N-亞柳胺基酸衍生之掌性氧釩錯合物催化 β-酮基酯類進行不對稱 1,4-共軛加成反應之研究

Applications of Chiral Oxidovanadium(V) Methoxides Bearing Chiral N-Salicylidine tert-butylglycinates in Enantioselective 1,4-Conjugate Addition

余韋廷(Wei-Tyng Yu)

指導教授 ： 陳建添

國立清華大學/理學院/化學系/碩士(2013年)

https://doi.org/10.6843/NTHU.2013.00098

摘要

延續了本實驗室的系統，我們合成了一系列 C-5 位置為硝基取代，C-3 位置為不同的雙取代基之芳香取代，包含甲氧基、甲基及苯基等，以這一系列之 N-亞柳胺基酸衍生之希夫鹼，進一步和硫酸氧釩化合物於氧氣飽和之甲醇溶劑中形成具掌性之正五價氧釩金屬錯合物，並以此氧釩錯合物作為催化劑去進行不對稱之 1,4-共軛加成反應。
　　我們主要以 2-酮基環戊烷甲酸苄酯作為 Michael donor，另外也試著以文獻中較少出現之 2-酮基-1-苯駢環戊烷甲酸苄酯作為 Michael donor，在 Michael acceptor 方面，一共使用了甲基乙烯基酮、環己烷基乙烯基酮、磷酸酯類化合物的四乙基亞乙基二磷酸酯、炔基酮類化合物的甲基乙炔基酮及苯基乙炔基酮、乙烯基碸化合物的乙烯基苯基碸及乙烯基苯基硒代碸等，其中以 2-酮基環戊烷甲酸苄酯及甲基乙烯基酮的例子為最佳結果，當使用 1a 作為掌性催化劑時可得 75% 之加成產物，其鏡像選擇性為 84% ee。

關鍵字

N-亞柳胺基酸衍生之掌性氧釩錯合物 ； 不對稱 1,4-共軛加成反應

並列摘要

A series of chiral oxidovanadium(V) methoxides were prepared from 3-disubstituted (included methoxy, methyl, and phenyl, etc.) aromatic substituted-5-nitro-N-salicylidene L-tert-butylglycinates and vanadyl sulfate in oxygen-saturated methanol. These complexes serve as highly enantioselective catalysts for asymmetric 1,4-conjugate addition.

We used benzyl 2-oxocyclopentanecarboxylate as a major Michael donor. Besides, we also used Benzyl 2-oxo-1-indanecarboxylate, which is rarely mentioned in literature, as a Michael donor. For Michael acceptor, we used methyl vinyl ketone, cyclohexanyl vinyl ketone, tetraethyl ethylidene bisphosphonate of phosphate compounds, methyl ethylnl ketone and phenyl ethylnl ketone of alkynyl ketones, vinyl phenyl sulfone and vinyl phenyl selenone etc. The best results were obtained from 2-oxocyclopentanecarboxylate and methyl vinyl ketone, when using 1a as a chiral catalyst for asymmetric 1,4-conjugated addition, affording the Michael adduct in 75% yields and up to 82% ee.

並列關鍵字

Chiral Oxidovanadium(V) Methoxides Bearing Chiral N-Salicylidine tert-butylglycinates ； Enantioselective 1,4-Conjugate Addition

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