Direct Functionalization of White Phosphorus to Cyclotetraphosphanes: Selective Formation of Four P–C Bonds

Converting elemental white phosphorus directly into organophosphorus or polyphosphorus is meaningful, challenging and attractive. The ate-complexes of aluminacyclopentadienes 1a,b react with P4 to afford selectively the cyclotetraphosphanes 2a,b featuring four newly formed P–C bonds and a planar squ...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2019-05, Vol.141 (17), p.6843-6847
Main Authors: Du, Shanshan, Yang, Jimin, Hu, Jingyuan, Chai, Zhengqi, Luo, Gen, Luo, Yi, Zhang, Wen-Xiong, Xi, Zhenfeng
Format: Article
Language:English
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Summary:Converting elemental white phosphorus directly into organophosphorus or polyphosphorus is meaningful, challenging and attractive. The ate-complexes of aluminacyclopentadienes 1a,b react with P4 to afford selectively the cyclotetraphosphanes 2a,b featuring four newly formed P–C bonds and a planar square cyclo-P4 ring. Density functional theory calculations show that the conversion of tetrahedral P4 to planar cyclo-P4 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.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.9b02628