6190-28-9Relevant academic research and scientific papers
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.
Ligand-free copper-catalyzed denitrogenative arylation of phosphorylamides with arylhydrazines
Zhu, Qiao,Che, Shiying,Luo, Zhenghong,Zhao, Zijian
, p. 947 - 957 (2020/02/27)
A straightforward arylation of phosphorylamides with arylhydrazines hydrochloride was herein demonstrated. The protocol proceeded in the presence of a catalytic loading of Cu(OAc)2 as the catalyst, DTBP as the external oxidant and Cs2CO3 as the base, but without any ligands. And a series of N-aryl phosphorylamides were successfully obtained in high efficiency (up to 93% yields) with good substituents compatibility (up to 30 examples). Free radical mechanism was proposed for the facile methodology based on the results of control reactions and literature explorations.
Rhodium(III)-Catalyzed Enantiotopic C?H Activation Enables Access to P-Chiral Cyclic Phosphinamides
Sun, Yang,Cramer, Nicolai
, p. 364 - 367 (2016/12/30)
Compounds with stereogenic phosphorus atoms are frequently used as ligands for transition-metal as well as organocatalysts. A direct catalytic enantioselective method for the synthesis of P-chiral compounds from easily accessible diaryl phosphinamides is presented. The use of rhodium(III) complexes equipped with a suitable atropochiral cyclopentadienyl ligand is shown to enable an enantiodetermining C?H activation step. Upon trapping with alkynes, a broad variety of cyclic phosphinamides with a stereogenic phosphorus(V) atom are formed in high yields and enantioselectivities. Moreover, these can be reduced enantiospecifically to P-chiral phosphorus(III) compounds.
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.
Labile P-C bonds: P-(phosphinoyl)methyl-λ5-phosphazenes and related compounds
Alajarín, Mateo,López-Leonardo, Carmen,Llamas-Lorente, Pilar
, p. 1041 - 1043 (2007/10/03)
N-Aryl-P,P-diphenyl-P-(diphenylphosphinoyl)methyl-λ5-pho sphazenes undergo smooth acid-catalysed hydrolysis with concomitant P-C bond fission yielding N-aryl-P,P-diphenylphosphinamides and diphenylmethylphosphane oxide. A tentative mechanistic explanation is given.
Photolysis of Diphenyl- and t-Butyl(phenyl)-phosphinic Azides: Dimethyl Sulphide as a Nitrene Trap, and Its Influence on the Curtius-like Rearrangement
Harger, Martin J.P.,Westlake, Sally
, p. 2351 - 2356 (2007/10/02)
Photolysis of Ph2P(O)N3 in benzene containing MeOH gives a high yield (72percent) of the phosphonamidate PhP(O)(OMe)NHPh (3) resulting from Curtius-like rearrangement.When some of the benzene solvent is replaced by Me2S the yield of the rearrangement prod
PHOTOLYTIC REARRANGEMENT OF PHOSPHORUS AZIDE : EVIDENCE FOR A TRANSIENT METAPHOSPHONIMIDATE.
Bertrand, Guy,Majoral, Jean-Pierre,Baceiredo, Antoine
, p. 5015 - 5018 (2007/10/02)
Photolysis of the oxide of diphenylphosphine azide gives rise to a transient metaphisphonimidate, a new tricoordinated pentavalent phosphorus compound.Evidence for this species was given by trapping reactions on a variety of substrates.
Hydrolysis of Diarylphosphinic Amides in Acidic Solution: Steric Inhibition and Mechanism
Harger, Martin J. P.
, p. 154 - 160 (2007/10/02)
The pseudo-first-order rate constants for the hydrolysis of diphenylphosphinic amide Ph2P(O)NH2 and its di-p-tolyl, di-o-tolyl, and dimesityl analogues (106kψ 3 630, 2 340, 81.0, and 3.27 s-1 respectively with H(1+) 0.0662M and T 30.2 deg C) in water-dioxan (9:1 v/v) containing perchloric acid show that reaction is sterically hindered by ortho-methyl substituents in the P-aryl groups.Steric inhibition is as great, or greater, in the hydrolysis of the corresponding (N-phenyl)diarylphosphinic amides (106kψ 5 440, 4 470, 54.9 and 0.88 s-1 respectively with H(1+) 1.36M and T 39.9 deg C) and (N-p-nitrophenyldiarylphosphinic amides (106kψ 724, 702, 6.57, and 0.098 s-1 respectively with H(1+) 2.58M and T 39.9 deg C) even though the departing amine is less nucleophilic.Such sensitivity to steric hindrance is consistent with associative (A2) mechanism for the hydrolysis of all the substrates.
