5068-16-6Relevant articles and documents
Palladium-Catalyzed C-P(III) Bond Formation by Coupling ArBr/ArOTf with Acylphosphines
Chen, Xingyu,Wu, Hongyu,Yu, Rongrong,Zhu, Hong,Wang, Zhiqian
, p. 8987 - 8996 (2021/06/30)
Palladium-catalyzed C-P bond formation reaction of ArBr/ArOTf using acylphosphines as differential phosphination reagents is reported. The acylphosphines show practicable reactivity with ArBr and ArOTf as the phosphination reagents, though they are inert to the air and moisture. The reaction affords trivalent phosphines directly in good yields with a broad substrate scope and functional group tolerance. This reaction discloses the acylphosphines' capability as new phosphorus sources for the direct synthesis of trivalent phosphines.
Ready Approach to Organophosphines from ArCl via Selective Cleavage of C-P Bonds by Sodium
Ye, Jingjing,Zhang, Jian-Qiu,Saga, Yuta,Onozawa, Shunya,Kobayashi, Shu,Sato, Kazuhiko,Fukaya, Norihisa,Han, Li-Biao
, p. 2682 - 2694 (2020/07/30)
The preparation, application, and reaction 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 to Li and K for these reactions. R2PNa reacted with a variety of ArCl to efficiently produce R2PAr. ArCl is superior to ArBr and ArI since they only gave low yields of the products. In addition, Ph2PNa is superior to Ph2PLi and Ph2PK since Ph2PLi did not produce the coupling product with PhCl, while Ph2PK only gave a low yield of the product. An electron-withdrawing group on the benzene ring of ArCl greatly accelerated the reactions with R2PNa, while an alkyl group reduced the reactivity. Vinyl chloride and alkyl chlorides RCl also reacted efficiently. While t-BuCl did not produce the corresponding product, admantyl halides could give the corresponding phosphine in high yields. A wide range of phosphines were prepared by this method from the corresponding chlorides. Unsymmetric phosphines could also be conveniently generated in one pot starting from Ph3P. Chiral phosphines were also obtained in good yields from the reactions of menthyl chlorides with R2PNa. Possible mechanistic pathways were given for the reductive cleavage of R3P by sodium generating R2PNa and the substitution reactions of R2PNa with ArCl generating R2PAr.
An efficient heterogeneous cross-coupling of aryl iodides with diphenylphosphine catalyzed by copper (I) immobilized in MCM-41
Fang, Zhiqiang,Cai, Mingzhong,Lin, Yang,Zhao, Hong
, (2018/07/31)
The heterogeneous cross-coupling reaction of aryl iodides with diphenylphosphine was achieved in toluene at 115?°C in the presence of 10?mol% of phenanthroline-functionalized MCM-41-supported copper (I) complex (Phen-MCM-41-CuI) with Cs2CO3 as base, yielding various unsymmetric triarylphosphines in good to excellent yields. This protocol can tolerate a wide range of functional groups and does not need the use of expensive additives or harsh reaction conditions. This heterogeneous Cu (I) catalyst exhibited the same catalytic activity as homogeneous CuI/Phen system, and could easily be recovered by a simple filtration of the reaction solution and recycled up to seven times without significant loss of activity.
