1666-10-0Relevant articles and documents
On the rearrangement of N-aryl-N-Boc-phosphoramidates to N-Boc-protected o-aminoarylphosphonates
Kuliszewska, Edyta,Hammerschmidt, Friedrich
, p. 87 - 98 (2017/12/06)
Abstract: Various arylamines were converted in two steps to N-Boc-N-arylphosphoramidates. LiTMP and LDA induced directed ortho-metalation at temperatures from ?78 to 0?°C. The ensuing [1,3]-migration of the phosphorus atom with its substituents from the n
Trichloroisocyanuric Acid as an Efficient Reagent for the Synthesis of Phosphoroamidates via Atherton-Todd Reaction under Base-Free Conditions
Kaboudin, Babak,Donyavi, Atousa,Kazemi, Foad
, p. 170 - 174 (2017/09/28)
A simple, efficient, and novel method is developed for the synthesis of phosphoroamidates via an Atherton-Todd coupling reaction of amines with dialkyl H-phosphite using trichloroisocyanuric acid as an efficient and safe reagent. Treatment of amines with dialkyl H-phosphite and trichloroisocyanuric acid under base-free conditions gives phosphoroamidates in moderate to good yields. The reaction proceeded effectively to afford the corresponding phosphoroamidates via a dehydrogenative coupling of H-phosphonates with amines. This method is easy, rapid, and good-yielding for the synthesis of phosphoroamidates.
Optimization of Phosphoramidates Synthetic Conditions
Khan,Khan
, p. 564 - 565 (2018/04/23)
An optimized catalytic oxidative cost effective process of dehydrogenative coupling of diisopropyl phosphite with arylamines led to formation of the corresponding phosphoramidates. Structures of products were elucidated from NMR and ESI-MS data.
Phosphoramidate tantalum complexes for room-temperature C-H functionalization: Hydroaminoalkylation catalysis
Garcia, Pierre,Lau, Ying Yin,Perry, Mitchell R.,Schafer, Laurel L.
, p. 9144 - 9148 (2013/09/12)
A cooled reaction: Phosphoramidate-ClTaMe3 complexes promote the first example of room-temperature hydroaminoalkylation catalysis. This reaction can be realized under solvent-free conditions and with challenging substrates such as styrenes and dialkyl amines. When using a vinylsilane substrate, for the first time the linear regioisomer is obtained preferentially using a Group5 metal. TBS=tert-butyldimethylsilyl, TMS=trimethylsilyl. Copyright
Copper-catalyzed aerobic oxidative cross-coupling of arylamines and dialkylphosphites leading to N-arylphosphoramidates
Wang, Gao,Yu, Qing-Ying,Chen, Shan-Yong,Yu, Xiao-Qi
supporting information, p. 6230 - 6232 (2013/10/22)
An efficient method to generate N-P bonds directly from N-H and P-H bonds is described. Various arylamines and dialkylphosphites were directly oxidized to the corresponding N-arylphosphoramidates at room temperature in moderate to good yields by using an inexpensive catalyst-oxidant (CuBr/air) system.
Kinetics and mechanism of the anilinolysis of dibutyl chlorophosphate in acetonitrile
Hoque, Md. Ehtesham Ul,Lee, Hai Whang
scheme or table, p. 663 - 669 (2012/05/19)
The nucleophilic substitution reactions of dibutyl chlorophosphate (3) with substituted anilines (XC6H4NH2) and deuterated anilines (XC6H4ND2) are investigated kinetically in acetonitrile at 55.0 °C. The obtained deuterium kinetic isotope effects (DKIEs; kH/kD) are secondary inverse (kH/kD = 0.86-0.97) with the strongly basic anilines while primary normal (kH/kD = 1.04-1.10) with the weakly basic anilines. The DKIEs, steric effects of the two ligands, activation parameters, cross-interaction constants, variation trends of the kH/kD values with X, and mechanism are discussed for the anilinolyses of the nine (R1O)(R2O)P(=O)Cl-type chlorophosphates. A concerted mechanism is proposed with a backside nucleophilic attack transition state for the strongly basic anilines and with a frontside attack involving a hydrogen-bonded four-center-type transition state for the weakly basic anilines on the basis of the magnitudes, secondary inverse and primary normal, and variation trends of the kH/kD values with X.
Kinetics and mechanism of anilinolysis of phenyl n-phenyl phosphoramidochloridate in acetonitrile
Ul Hoque, Md. Ehtesham,Lee, Hai Whang
, p. 3274 - 3278 (2013/01/15)
The kinetic studies on the reactions of phenyl N-phenyl phosphoramidochloridate (8) with substituted anilines (XC6H 4NH2) and deuterated anilines (XC6H 4ND2) have been carried out in acetonitrile at 60.0 oC. The obtained deuterium kinetic isotope effects (DKIEs; kH/kD) are huge secondary inverse (kH/kD = 0.52-0.69). A concerted mechanism is proposed with a backside attack transition state (TS) on the basis of the secondary inverse DKIEs and the variation trends of the kH/kD values with X. The degree of bond formation in the TS is really extensive taking into account the very small values of the DKIEs. The steric effects of the two ligands on the rates are extensively discussed for the aminolyses of the chlorophosphate-type substrates on the basis of the Taft equation.
Kinetics and mechanism of the anilinolysis of diisopropyl chlorophosphate in acetonitrile
Ul Hoque, Md. Ehtesham,Lee, Hai Whang
experimental part, p. 3245 - 3250 (2012/01/17)
The nucleophilic substitution reactions of diisopropyl chlorophosphate (3) with substituted anilines (XC6H4NH2) and deuterated anilines (XC6H4ND2) are investigated kinetically in acetonitrile at 55.0 oC. The anilinolysis rate of 3 is rather slow to be rationalized by the conventional stereoelectronic effects. The obtained deuterium kinetic isotope effects (DKIEs; kH/kD) are secondary inverse (kH/kD = 0.71-0.95) with maximum magnitude at X = H. A concerted mechanism involving predominant backside nucleophilic attack is proposed on the basis of the secondary inverse DKIEs.
THE APPLICATION OF DIALKYLPHOSPHITE AS THE AMINO PROTECTION REAGENT IN ORGANIC SYNTHESIS
Zhao, Yu-Fen,Ji, Gai-Jiao,Xi, She-Kang,Tang, Hue-Gong,Song, Ai-Teng,Wei, Shou-Zuo
, p. 155 - 158 (2007/10/02)
The acid hydrolysis of N-phenyl-N-dialkyl-phosphoramidates was studied by HPLC, the N-phenyl-N-diisopropylphosphoramidate has half life 53 min in 6N HCl at 50 deg C.The P-N bonds of these phosphoryl derivatives also show a relative stability in organic and Lewis acids.
