Mechanism of an Elusive Solvent Effect in Organozinc Reagent Synthesis.
Mechanism of an Elusive Solvent Effect in Organozinc Reagent Synthesis.
复制标题
DOI：
10.1002/chem.202002214
复制
发表时间：
2020-11-26
期刊：
影响因子：
--
通讯作者：
Blum SA
中科院分区：
文献类型：
--
作者：
Hanada EM;Jess K;Blum SA
溶剂效应往往是难以理解的情况下，反应中间体，因此，他们在不同的溶剂中的差异行为，是不能直接观察到的传统的合奏分析技术。在此，单粒子荧光显微镜的灵敏度独特地使有机锌中间体和溶剂对它们的建立和持久性的影响能够直接观察。当与NMR光谱相结合时，这些成像数据精确地指出了广泛使用的有机锌试剂合成中溶剂效应的先前难以捉摸的机械起源。这些研究结果的特点是加速氧化加成的起始有机碘化物在DMSO中的锌金属的表面相对于THF，但一旦形成，表面中间体显示类似的持久性在任一溶剂。目前的研究是第一次展示了一种高灵敏度的单粒子荧光显微镜技术，以查明合成化学中难以捉摸的溶剂效应。灵敏的单粒子荧光显微镜实验能够通过直接观察以前“不可观察”的有机金属表面中间体来理解溶剂效应。结合这种显微镜技术与1H NMR光谱表征溶剂效应的合成广泛使用的有机锌试剂。
Solvent effects are often difficult to understand in cases where reaction intermediates, and thus their differential behaviour in different solvents, are not directly observable by traditional ensemble analytical techniques. Herein, the sensitivity of single-particle fluorescence microscopy uniquely enables direct observation of organozinc intermediates and solvent effects on their build-up and persistence. When combined with NMR spectroscopy, these imaging data pinpoint the previously elusive mechanistic origin of solvent effects in the synthesis of widely used organozinc reagents. These findings characterize the acceleration of oxidative addition of the starting organoiodide to the surface of zinc metal in DMSO relative to THF, but once formed, surface intermediates display similar persistence in either solvent. The current studies are the first demonstration of a highly sensitive, single-particle fluorescence microscopy technique to pinpoint otherwise elusive solvent effects in synthetic chemistry. Sensitive single-particle fluorescence microscopy experiments enable understanding solvent effects by direct observation of previously “unobservable” organometallic surface intermediates. Combination of this microscopy technology with 1H NMR spectroscopy characterizes the solvent effect on the synthesis of widely used organozinc reagents.
登录
查看更多内容
影响因子：
16.6
作者：
Krasovskiy, Arkady;Malakhov, Vladimir;Knochel, Paul
通讯作者：
Knochel, Paul
影响因子：
5.2
作者：
Huo, SQ
通讯作者：
Huo, SQ
影响因子：
5.2
作者：
Kobayashi, Koji;Naka, Hiroshi;Kondo, Yoshinori
通讯作者：
Kondo, Yoshinori
影响因子：
15
作者：
Uchiyama, M;Koike, M;Sakamoto, T
通讯作者：
Sakamoto, T
影响因子：
3.6
作者：
WINKLE, MR;RONALD, RC
通讯作者：
RONALD, RC