20684-82-6Relevant academic research and scientific papers
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.
Three-component 3-(phosphoryl)methylindole synthesis from indoles, H-phosphine oxides and carbonyl compounds under metal-free conditions
Pan, Jiaoting,Zhao, Runmin,Guo, Jiami,Ma, Dumei,Xia, Ying,Gao, Yuxing,Xu, Pengxiang,Zhao, Yufen
, p. 792 - 797 (2019)
The first facile and efficient acid-catalyzed three-component reaction of indoles, H-phosphine oxides and carbonyl compounds has been developed, providing a general, one-pot approach to structurally diverse C3-alkylated indole derivatives accompanied by concurrent C-P/C-C bond formation with remarkable functional group tolerance and excellent regioselectivity.
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.
Benzyl phosphine oxide compound as well as preparation method and application thereof
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Paragraph 0046-0051, (2021/08/25)
The invention discloses a benzyl phosphine oxide compound as well as a preparation method and application thereof. The benzyl phosphine oxide compound has heterocyclic aromatic phosphine oxide and high-activity hydroxyl, so that the benzyl phosphine oxide compound has high biological activity, can be effectively used as a medical intermediate, and has wide application prospects in the field of medicines. The benzyl phosphine oxide compound is easy to prepare and has high conversion rate under mild conditions, and the highest yield of the product can reach 81%.
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
Hydrophosphination of Activated Alkenes by a Cobalt(I) Pincer Complex
Nolla-Saltiel, Roberto,Geer, Ana M.,Taylor, Laurence J.,Churchill, Olivia,Davies, E. Stephen,Lewis, William,Blake, Alexander J.,Kays, Deborah L.
, p. 3148 - 3157 (2020/06/08)
Herein we report the synthesis of three heteroleptic first-row transition metal(II) complexes containing carbazolido NNN pincer ligands and conversion to the corresponding metal(I)-carbonyl complexes via a reductive carbonylation route. These complexes are precatalysts for the hydrophosphination of activated alkenes, affording a cobalt-catalysed hydrophosphination process that solely and selectively yields the β addition (anti-Markovnikov) product. The scope of this transformation has been investigated using a variety of activated alkenes. Isolation and characterisation of substrate-coordinated intermediates reveal available coordination sites, which provide insight into the proposed catalytic cycle. (Figure presented.).
Selective P?C(sp3) Bond Cleavage and Radical Alkynylation of α-Phosphorus Alcohols by Photoredox Catalysis
Jia, Kunfang,Li, Junzhao,Chen, Yiyun
, p. 3174 - 3177 (2018/02/09)
Herein the first P?C(sp3) bond cleavage and radical alkynylation of α-phosphorus alcohols to construct phosphonoalkynes is reported. The phosphorus radical is generated upon P?C bond cleavage reaction via the alkoxyl radical through photoredox catalysis with cyclic iodine(III) reagents. Various arylphosphinoyl-, alkylphosphinoyl-, phosphonate-, and phosphonic amide alcohols serve as radical phosphorus precursors to construct phosphonoalkynes for the first time.
Phosphono-replaced methyl alcohol derivative, and preparation method and application thereof
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Paragraph 0016, (2017/08/28)
The invention discloses a phosphono-replaced methyl alcohol derivative, and a preparation method and application thereof. The phosphono-replaced methyl alcohol derivative has the advantages that a (hetero) aryl methyl alcohol derivate serves as an initiator, and raw materials are easy to get and have great varieties; products obtained according to the preparation method have various types and wide application ranges, and serve as ligands which coordinate with rhodium to obtain various aldehydes through catalyzed synthesis; the phosphono-replaced (hetero) aryl methyl alcohol can be transformed into phosphonic compounds conveniently; the phosphonic compounds serving as photoinitiators can be widely applied to production of high polymer materials, paint, binders, adhesive tapes and the like. The preparation method has the advantages that reactions are achieved in the air, reaction conditions are mild, yield of target products is high, pollution is small, reaction operations and post-treatment processes are simple, and the preparation method is suitable for industrial production.
Iron-catalyzed clean dehydrogenative coupling of alcohols with P(O)-H compounds: A new protocol for ROH phosphorylation
Li, Chunya,Chen, Tieqiao,Han, Li-Biao
, p. 14893 - 14897 (2016/10/11)
An efficient oxygen-phosphoryl bond-forming reaction via iron-catalyzed cross dehydrogenative coupling has been developed. This transformation proceeds efficiently under oxidant- and halide-free reaction conditions with H2 liberation, and represents a straightforward method to prepare valuable organophosphoryl compounds from the readily available alcohols and P(O)-H compounds.
