Bridgehead diphosphines in the bicyclo[3.3.3]undecane and bicyclo[4.4.4]tetradecane series: synthesis, structure and properties
作者:Roger W. Alder、Dianne D. Ellis、Rolf Gleiter、Christopher J. Harris、Holger Lange、A. Guy Orpen、David Read、Peter N. Taylor
DOI:10.1039/a800595h
日期:——
4-bis(1-phospholan-1-yl)butane. These included reaction of hydride adduct 15b with BunLi, and debenzylations of 1-benzyl-1-phosphonia-6-phosphabicyclo[4.4.4]tetradecane trifluoromethanesulfonate 16b and 1,6-dibenzyl-1,6-diphosphoniabicyclo[4.4.4]tetradecane bromide triflate 21 with LiAlH4. Reaction of cis-1,5-dibenzyl-1,5-diphosphacyclooctane with CH2(CH2OTf)2 gives 1,5-dibenzyl-1,5-diphosphoniabicyclo[3.3
通过1,k + 2-二磷酸双环[ k]的反应制备几种丙二酮二phosph盐8 。l .0]链烷烃6与α,ω-链烷二醇双三氟甲磺酸酯[双(三氟甲磺酸盐)];它们的性质在很大程度上取决于环的大小。1,6-二膦三环[4.4.4.0]十四烷双-三氟甲磺酸酯8d在酸性水溶液中稳定,并与亲核试剂[X = F –,MeO –,H –(来自BH 4 –)和R –(来自Grignard和烷基锂试剂)],得到13–18的部分X–P–P +键合时,氢氧根离子可生成一氧化二膦12b,但即使这样仍可保留某些P-P键合。但是,1,5-二膦三环[3.3.3.0]十一烷双-三氟甲磺酸酯8a不可逆地水解,并且比其[4.4.4.0]水解快得多。1,6-二膦三环[4.4.3.0]十三烷双-三氟甲磺酸酯8c与NaBH 4反应,得到氢化物加合物15a,该氢化物被Bu n Li去质子化,得到1,6-二磷双环[4.4.3]十三烷9c。然而,制备1,6-二磷酸双环[4