Direct Functionalization of White Phosphorus to Cyclotetraphosphanes: Selective Formation of Four P-C Bonds
Direct Functionalization of White Phosphorus to Cyclotetraphosphanes: Selective Formation of Four P-C Bonds
复制标题
白磷直接官能化为环四膦：四个 P-C 键的选择性形成
DOI：
10.1021/jacs.9b02628
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发表时间：
2019-05-01
影响因子：
15
通讯作者：
Xi, Zhenfeng
中科院分区：
文献类型：
--
作者：
Du, Shanshan;Yang, Jimin;Xi, Zhenfeng
Converting elemental white phosphorus directly into organophosphorus or polyphosphorus is meaningful, challenging and attractive. The ate-complexes of aluminacyclopentadienes 1a,b react with P-4 to afford selectively the cyclotetraphosphanes 2a,b featuring four newly formed P-C bonds and a planar square cyclo-P 4 ring. Density functional theory calculations show that the conversion of tetrahedral P-4 to planar cyclo-P-4 moiety undergoes through an unexpected 1,1-P-insertion/Diels-Alder reaction/isomerization cascade process. The reaction of 2a with iodomethane or p-benzoquinone afforded the P-methylation product 3 and the metal-free cyclotetraphosphane 4, respectively. Interestingly, reduction of 4 generated the phospholyl anions 5 and 6 while treatment of 4 with iodomethane afforded the phospholyl cation 7.
