磷原子空间位阻减小对氧杂膦环配合物稳定性和反应性的影响。
Effects of diminished steric protection at phosphorus on stability and reactivity of oxaphosphirane complexes.
机构信息
Institut für anorganische Chemie der Universität Bonn, Gerhard-Domagk-Straße 1, 53121 Bonn, Germany.
出版信息
Dalton Trans. 2018 Jul 17;47(28):9347-9354. doi: 10.1039/c8dt01979g.
Readily available P-tBu substituted Li/Cl phosphinidenoid complexes react with carbonyl compounds to furnish sterically almost unhindered oxaphosphirane complexes that reveal new and surprisingly facile intra- and intermolecular ring expansion reactions. 1,3,2-Dioxaphosphole complex formation is explained by DFT calculations through diastereoselective carbonyl group-induced ring cleavage of an oxaphosphirane intermediate.
易于获得的 P-tBu 取代的 Li/Cl 膦烯配合物与羰基化合物反应，生成空间位阻几乎不受阻碍的氧杂磷杂环戊烷配合物，这些配合物揭示了新的、令人惊讶的易于进行的分子内和分子间环扩张反应。通过 DFT 计算，通过羰基诱导的氧杂磷杂环戊烷中间体的非对映选择性环裂解，解释了 1,3,2-二氧杂磷杂环戊烷配合物的形成。
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