Gene

Catalysis

Isomerization

Polymer chemistry

Density functional theory

Phosphorus

Biochemistry

Stereochemistry

Physical chemistry

Medicinal chemistry

White (mutation)

Combinatorial chemistry

Organic chemistry

White Phosphorus

Surface modification

Computational chemistry

Double bond

Chemistry

Moiety

Ring (chemistry)

Journal of the American Chemical Society

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.

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