6190-28-9Relevant articles and documents
Redox-Neutral P(O)-N Coupling between P(O)-H Compounds and Azides via Dual Copper and Photoredox Catalysis
Wu, Yanan,Chen, Ken,Ge, Xia,Ma, Panpan,Xu, Zhiyuan,Lu, Hongjian,Li, Guigen
supporting information, p. 6143 - 6149 (2020/07/30)
We report a redox-neutral P(O)-N coupling reaction of P(O)-H compounds with azides via photoredox and copper catalysis, providing new access to useful phosphinamides, phosphonamides, and phosphoramides. This transformation tolerates a wide range of nucleophilic functionalities including alcohol and amine nucleophiles, which makes up for the deficiency of classical nitrogen nucleophilic substitution reactions. As a demonstration of the broad potential applications of this new methodology, late-stage functionalization of a diverse array of azido-bearing natural products and drug molecules, a preliminary asymmetric reaction, and a continuous visible-light photoflow process have been developed.
The Chan-Evans-Lam N-arylation of phosphonic/phosphinic amides
Xu, Yuqin,Su, Qiong,Dong, Wanrong,Peng, Zhihong,An, Delie
, p. 4602 - 4609 (2017/07/10)
A stoichiometric copper(II)-mediated arylation protocol of phosphinamides and phosphonamides was herein demonstrated. Various unreported N-aryl phosphinamides and phosphonamides were successfully prepared through Chan-Evans-Lam reaction with high efficiency (up to 88% yields) and good functional groups tolerance (30 examples) in the absence of any ligands or co-catalysts.
Kinetics and mechanism of the anilinolyses of aryl dimethyl, methyl phenyl and diphenyl phosphinates
Dey, Nilay Kumar,Kim, Chan Kyung,Lee, Hai Whang
, p. 717 - 724 (2011/04/16)
The reactions of Z-aryl dimethyl (1), methyl phenyl (2), and diphenyl (3) phosphinates with X-anilines in dimethyl sulfoxide at 60.0 °C are studied kinetically. Kinetic results yield the primary normal deuterium kinetic isotope effects (DKIEs) involving deuterated aniline (XC6H4ND 2) nucleophiles, kH/kD = 1.03-1.17, 1.15-1.29, and 1.24-1.51, and the cross-interaction constants (CICs), ρXZ = 0.37, 0.34, and 0.65 for 1, 2, and 3, respectively. The steric effects of the ligands (R1 and R2) on reaction rates play a role, but are relatively much smaller compared to other phosphinate systems. A stepwise mechanism with a rate-limiting leaving group expulsion from the intermediate is proposed on the basis of the CICs positive signs. The dominant frontside nucleophilic attack through a hydrogen-bonded, four-center-type transition state is proposed on the basis of primary normal DKIEs and large magnitudes of the CICs for 2 and 3, while both frontside and backside attack are proposed on the basis of relatively small primary normal DKIEs for 1.
