Ready Approach to Organophosphines from ArCl via Selective Cleavage of C–P Bonds by Sodium
作者:Jingjing Ye、Jian-Qiu Zhang、Yuta Saga、Shun-ya Onozawa、Shu Kobayashi、Kazuhiko Sato、Norihisa Fukaya、Li-Biao Han
DOI:10.1021/acs.organomet.0c00295
日期:2020.7.27
mechanism of sodium phosphide R2PNa and other alkali metal phosphides R2PM (M = Li and K) have been studied. R2PNa could be prepared, accurately and selectively, via the reactions of SD (sodium finely dispersed in mineral oil) with phosphinites R2POR′ and chlorophosphines R2PCl. R2PNa could also be prepared from triarylphosphines and diarylphosphines via the selective cleavage of C–P bonds. Na was superior
研究了磷化钠R 2 PNa和其他碱金属磷化物R 2 PM(M = Li和K)的制备,应用和反应机理。R 2 PNa可以通过SD(精细分散在矿物油中的钠)与次膦酸酯R 2 POR'和氯膦R 2 PC1的反应准确而选择性地制备。R 2 PNa也可以通过选择性裂解C–P键由三芳基膦和二芳基膦制备。在这些反应中,Na优于Li和K。R 2 PNa与多种ArCl反应以有效产生R 2PAr。ArCl优于ArBr和ArI,因为它们只会降低产品收率。另外,Ph 2 PNa优于Ph 2 PLi和Ph 2 PK,因为Ph 2 PLi不产生与PhCl的偶联产物,而Ph 2 PK仅产生低产率的产物。ArCl苯环上的吸电子基团极大地促进了与R 2 PNa的反应,而烷基降低了反应活性。氯乙烯和烷基氯RC1也有效地反应。当t-BuCl没有产生相应的产物,金刚烷基卤化物可以高产率得到相应的膦。通过这种方法,由相应的氯化物制备了多种膦。还可以方便地从Ph