Highly enantioselective electrophilic amination and michael addition of cyclic β-ketoesters induced by lanthanides and (S,S)-ip-pybox:: The mechanism
Highly enantioselective electrophilic amination and michael addition of cyclic β-ketoesters induced by lanthanides and (S,S)-ip-pybox:: The mechanism
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DOI：
10.1021/jo0622678
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发表时间：
2007-03-16
影响因子：
3.6
通讯作者：
Roces-Fernandez, Laura
中科院分区：
文献类型：
--
作者：
Comelles, Josep;Pericas, Alex;Roces-Fernandez, Laura
在三氟甲磺酸镧和（S，S）-ip-pybox存在下，在环状β-酮酯的Michael加成中获得高对映选择性。通过ESI质谱和NMR实验检测到基于镧系元素同时与（S，S）-ip-box和β-酮酯（以酮和烯醇化物形式）配位的中间体，并通过理论计算提出了可能的机理。
High enantioselection is obtained in Michael additions of cyclic beta-ketoesters in the presence of lanthanium triflates and (S,S)-ip-pybox. Intermediates based on simultaneous coordination of the lanthanide to both (S,S)-ip-box and beta-ketoester (in keto and enolate forms) are detected by means of ESI mass spectrometry and NMR experiments, and a possible mechanism is proposed through theoretical calculations.