Formation of Epoxides from Pentacoordinated Organoarsenic Compounds with aβ-Hydroxyethyl Group
Formation of Epoxides from Pentacoordinated Organoarsenic Compounds with aβ-Hydroxyethyl Group
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具有 β-羟乙基的五配位有机砷化合物形成环氧化物
DOI：
10.1039/c0nj00035c
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发表时间：
2010
期刊：
影响因子：
--
通讯作者：
Y. Yamamoto
中科院分区：
文献类型：
--
作者：
X.-D. Jiang;S. Matsukawa;Y. Fukuzaki;Y. Yamamoto
合成了一系列含β-羟乙基的五配位有机砷化合物（arsoranes）（4a，6a和6 b）。通过单晶X射线分析确定了晶体结构。用KH处理这些arsoranes几乎定量地得到相应的环氧化物。用1H和19 F NMR在CD 3CN中监测了具有未取代的β-羟乙基的4a与KH的反应，表明形成六配位砷阴离子作为中间体。然而，进一步的立体化学研究的环氧化物的形成表明，该反应进行的SN 2的方式，而不是在中间体六配位砷阴离子的配体偶联反应（LCR）。
A series of pentacoordinated organoarsenic compounds (arsoranes) bearing a β-hydroxyethyl group (4a, 6a and 6b) was synthesized. The crystal structures were determined by single crystal X-ray analysis. Treatment of these arsoranes with KH almost quantitatively gave the corresponding epoxide. The reaction of 4a having an unsubstituted β-hydroxyethyl group with KH was monitored by 1H and 19F NMR in CD3CN, suggesting that a hexacoordinate arsenic anion was formed as the intermediate. However, a further stereochemical study of the epoxide formation suggested that the reaction proceeded in the SN2 manner and not in the ligand coupling reaction (LCR) of the intermediate hexacoordinate arsenic anion.