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
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.
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.
