Regioselective Domino Metathesis of Unsymmetrical 7-Oxanorbornenes with Electron-Rich Vinyl Acetate toward Biologically Active Glutamate Analogues.
Regioselective Domino Metathesis of Unsymmetrical 7-Oxanorbornenes with Electron-Rich Vinyl Acetate toward Biologically Active Glutamate Analogues.
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DOI：
10.1002/ejoc.200900580
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发表时间：
2009-11-01
影响因子：
2.8
通讯作者：
Sakai, Ryuichi
中科院分区：
文献类型：
--
作者：
Oikawa, Masato;Ikoma, Minoru;Sasaki, Makoto;Gill, Martin B.;Swanson, Geoffrey T.;Shimamoto, Keiko;Sakai, Ryuichi
在这篇文章中，区域选择性的多米诺复分解反应的不对称7-氧杂降冰片烯，容易通过串联的Ugi/Diels-Alder反应作为一个关键步骤，由Hoveyda-Grubbs第二代催化剂促进的存在下，富电子的乙酸乙烯酯作为交叉复分解（CM）底物的报道。研究了CM反应中观察到的异常高的区域选择性的机理，并提出了Fischer型卡宾[“Ru”= CH（OAc）]产生空间相互作用的反应过程。复分解产物进一步转化为四种人工谷氨酸类似物，其结构受到天然衍生的兴奋性谷氨酸类似物dysiherbaine和neodysiherbaine的启发。有趣的是，其中一种合成类似物（28 a）在小鼠中诱导了僵住状态。进一步的电生理研究表明，28 a可能通过一种未知的间接途径抑制兴奋性突触传递。
In this article a regioselective domino metathesis reaction of unsymmetrical 7-oxanorbornenes, readily available by a tandem Ugi/Diels–Alder reaction as a key step, promoted by the Hoveyda–Grubbs second-generation catalyst in the presence of electron-rich vinyl acetate as a cross metathesis (CM) substrate is reported. The mechanism for the unusually high regioselectivity observed in the CM reaction was investigated, and a reaction course where a Fischer-type carbene [“Ru”= CH(OAc)] generates a steric interaction is proposed. The metathesis products were further converted to four artificial glutamate analogues whose structures were inspired by naturally derived excitatory glutamate analogues, dysiherbaine and neodysiherbaine. Interestingly, one of the synthetic analogues (28a) induced a cataleptic state in mice. Further electrophysiological studies suggest that 28a might inhibit excitatory synaptic transmission by a yet unknown indirect pathway.
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