20684-82-6Relevant articles and documents
Synthesis of functionalized 1,4-cyclohexadienes through intramolecular anionic dearomatization of N-alkyl-N-benzyldiphenylphosphinamides. Insight into the reaction mechanism
Fernandez, Ignacio,Forcen-Acebal, Angela,Garcia-Granda, Santiago,Lopez-Ortiz, Fernando
, p. 4472 - 4485 (2003)
A generalization of the intramolecular nucleophilic dearomatization-electrophilic alkylation reactions of N-alkyl-N-benzyldiphenylphosphinamide anions is presented. The process has been optimized by analyzing the effects of metalation and quench times, additives, the nature of the electrophiles used (MeI, CF3SO3Me, Me3O+BF4-, AllylBr, PhCH2Br, BrCH2CO2Me, and RCH=O, where R = Ph, 4-Cl-C6H4, 4-MeO-C6H4, and iPr), and the alkyl substituent linked to the nitrogen of the phosphinamide. Both HMPA and DMPU act as catalysts. The latter proved to be much more efficient for obtaining high yields of substituted tetrahydrobenzo[c] [1,2]-1λ5-phospholes containing a 1,4-cyclohexadiene system with very high regio- and diastereoselectivity. Steric effects in the neighborhood of the benzylic anion tend to decrease the stereoselectivity of the anionic cyclization. The optimization study also served to shed light on the reaction mechanism of the dearomatization process by identifying several intermediate species and showing the reversibility of the anionic cyclization step as well as of the reaction with aldehydes.
Monoacylphosphine oxides with substituents in the phosphonyl moiety as Norrish I photoinitiators: Synthesis, photoinitiattion properties and mechanism
Duan, Haodong,Gao, Jun,Han, Yuxi,Leng, Kangwei,Li, Qianmin,Liu, Dayong,Wang, Zhongwei,Xu, Xiaolei,Yu, Qing
, (2021/09/07)
In order to study the effect of the substituents in the phosphonyl moiety of monoacylphosphine oxide (MAPO) on its stability and initiation performance, (2,4,6-trimethylphenyl)(phenyl)(benzoyl)phosphine oxide (TMBPO), (4-tolyl)(phenyl)(2,4,6-trimethylbenzoyl)phosphine oxide (4-MTPO) and (2,4-xylyl)(phenyl)(2,4,6-trimethylbenzoyl)phosphine oxide (2,4-DMTPO) were designed and prepared. Studies on TMBPO showed that the introduction of methyl groups into the phosphonyl moiety of MAPO significantly enhanced its stability and light absorption abilities. The photopolymerization of trimethylolpropane triacrylate (TMPTA) showed that the initiation efficiency of 4-MTPO and 2,4-DMTPO were higher than that of TPO, regardless of whether it was initiated upon LED at 385 nm or 420 nm. In addition, the migration rates of 4-MTPO and 2,4-DMTPO in cured TMPTA were approximately 1/2 and 1/4 that of TPO, respectively.
O-Phosphination of Aldehydes/Ketones toward Phosphoric Esters: Experimental and Mechanistic Studies
Qian, Yanyan,Dai, Qiang,Li, Zhiming,Liu, Yu,Zhang, Junliang
, p. 4742 - 4748 (2020/06/29)
Addition of P-H species to carbonyl groups, namely the Pudovik reaction, normally delivers hydroxyl phosphorus compounds, along with phosphate byproducts in some cases. A few controllable systems starting from phosphites were set up to mainly provide the phosphates. Herein, we present a highly selective protocol starting from phosphonate precursors leading to phosphinate derivatives. Enantioenriched phosphinates were successfully achieved from chiral phosphine oxide precursors. Experimental and theoretical investigations were conducted to understand the mechanistic details.
Fast and Chemoselective Addition of Highly Polarized Lithium Phosphides Generated in Deep Eutectic Solvents to Aldehydes and Epoxides
Cicco, Luciana,Fombona-Pascual, Alba,Sánchez-Condado, Alba,Carriedo, Gabino A.,Perna, Filippo M.,Capriati, Vito,Presa Soto, Alejandro,García-álvarez, Joaquín
, p. 4967 - 4973 (2020/08/21)
Highly polarized lithium phosphides (LiPR2) were synthesized, for the first time, in deep eutectic solvents as sustainable reaction media, at room temperature and in the absence of protecting atmosphere, through direct deprotonation of both ali
