Highly enantioselective copper-bisoxazoline-catalyzed allylic oxidation of cyclic olefins with tert-butyl p-nitroperbenzoate
Highly enantioselective copper-bisoxazoline-catalyzed allylic oxidation of cyclic olefins with tert-butyl p-nitroperbenzoate
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DOI：
10.1021/ja026266i
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发表时间：
2002-07-31
影响因子：
15
通讯作者：
Zhou, ZN
中科院分区：
文献类型：
--
作者：
Andrus, MB;Zhou, ZN
使用丙二酰衍生的双恶唑啉和对硝基过苯甲酸叔丁酯的铜(I)络合物，首次以非常高的对映选择性 (94−99% ee) 发生环状烯烃的催化不对称烯丙氧化，以中等产率得到苯甲酸烯丙酯。将 15 mol% 的铜配合物与过量的烯烃以及一当量的过酸酯一起在 -20 °C 的乙腈中使用较长时间（5-12 d）。 S-酯是根据先前针对(S,S)-双恶唑啉配体提出的模型生成的。在烯烃存在下使用配合物的低温 13 C NMR 排除了 η2 中间体。
Catalytic asymmetric allylic oxidation of cyclic olefins ocurrs for the first time in very high (94−99% ee) enantioselectivity using copper(I) complexes of malonyl derived bisoxazolines andtert-butylp-nitroperbenzoate giving allyl benzoates in moderate yield. The copper complex, 15 mol %, was used in acetonitrile at −20 °C over an extended period, 5−12 d, with excess olefin together with one equivalent of perester. TheS-esters were generated in accord with the model proposed previously for the (S,S)-bisoxazoline ligand. An η2intermediate was ruled out using low-temperature13C NMR with the complex in the presence of olefin.