The first enantioenriched metalated nitrile possessing macroscopic configurational stability
The first enantioenriched metalated nitrile possessing macroscopic configurational stability
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DOI：
10.1021/ol070149g
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发表时间：
2007-03-29
期刊：
影响因子：
5.2
通讯作者：
Zhang, Yiqun
中科院分区：
文献类型：
--
作者：
Carlier, Paul R.;Zhang, Yiqun
对映体环丙基溴二腈5在-100℃下进行1分钟的镁溴交换，然后用D2O淬火，在81%ee(保留率)下得到重离子腈；额外的捕集实验建立了t(1/2)(Rac)=11.4 h在-100℃下。这些实验提供了第一次窥探镁-溴交换的立体化学方面的信息。形成的中间体是第一个被证明具有宏观构型稳定性的金属化丁腈。
Magnesium-bromine exchange on enantiopure cyclopropyl bromonitrile 5 at -100 degrees C for 1 min followed by a D2O quench gives the deuterionitrile in 81% ee (retention); additional trapping experiments establish t(1/2)(rac) = 11.4 h at -100 degrees C. These experiments provide the first glimpse into the stereochemical aspects of Mg-Br exchange. The intermediate formed is the first metalated nitrile demonstrated to possess macroscopic configurational stability.