219501-33-4

Upstream product

• 762-04-9 phosphonic acid diethyl ester 
• 768-60-5 4-methoxyphenylacetylen 
• 3179-10-0 (E)-1-methoxy-4-(2-nitrovinyl)benzene 
• 122-52-1 triethyl phosphite 
• 123-11-5 4-methoxy-benzaldehyde 
• 5720-07-0 4-methoxyphenylboronic acid 
• 243137-79-3 1,1,2,2,3,3,4,4,4-nonafluoro-butane-1-sulfonic acid 1-(diethoxy-phosphoryl)-vinyl ester 
• 100-06-1 1-(4-methoxyphenyl)ethanone 
• 919-19-7 diethyl acetylphosphonate 
• 1309980-37-7 diethyl 1-[(4-methylbenzenesulfonyl)oxy]ethene-alpha-phosphonate 
• 75-52-5 nitromethane 
• 3179-10-0 1-methoxy-4-(2-nitro-vinyl)-benzene 
• 219501-23-2 dithiophosphoric acid S-[2-(4-methoxy-phenyl)-2-oxo-ethyl] ester O,O'-dimethyl ester 
• 55991-65-6 [1-(4-methoxyphenyl)vinyloxy]trimethylsilane 

Downstream Products

• 884489-22-9 diethyl 2-formyl-1-(4-methoxyphenyl)ethylphosphonate 
• 1391866-03-7 1-(4-methoxyphenyl)vinylphosphonic acid 

Relevant academic research and scientific papers

Lewis Acid Enables Ketone Phosphorylation: Synthesis of Alkenyl Phosphonates

An efficient Lewis acid enabled ketones phosphonylation to synthesize vinylphosphonates has been developed. This method relays on ketone hydrophosphonylation/α-hydroxy phosphonates unimolecular elimination (E1) dehydration cascade reaction sequence. Vario

Markovnikov-addition of H-phosphonates to terminal alkynes under metal- And solvent-free conditions

An addition of H-phosphonates to aryl alkynes was realized under solvent- and metal-free conditions, affording Markovnikov-selective α-vinylphosphonates in moderate to good yields. A wide range of aryl alkynes could be applied for the reaction. A tentative mechanism of addition-substitution was proposed based onin situ31P {1H} NMR studies.

Preparation method of alkenyl phosphonate compound

The invention discloses a preparation method of an alkenyl phosphonate compound, which comprises the following steps: mixing ketone, phosphite, a catalyst, an additive and a solvent, stirring at 40-120 DEG C for 8-36 hours to completely convert ketone through reaction, and carrying out column chromatography separation on the reaction solution to obtain the alkenyl phosphonate compound. The methodis mild in reaction condition and high in reaction efficiency, and 1H NMR detection shows that the yield is 5%-94%. Compared with the prior art, cheap ketone is used as a raw material, a byproduct inthe reaction is water, the catalyst and the additive do not contain heavy metals, the problems of heavy metal pollution and the like do not exist, and the method is green, environmentally friendly andgood in atom economy.

α-Phosphonovinyl Arylsulfonates: An Attractive Partner for the Synthesis of α-Substituted Vinylphosphonates through Palladium-Catalyzed Suzuki Reactions

It has been demonstrated that a variety of α-phosphonovinyl arylsulfonates with electron-neutral, -donating, and -withdrawing groups on the phenyl ring could be conveniently and efficiently prepared. In the presence of a Pd(OAc)2/SPhos-based catalyst, various organoboron compounds could be employed as the nucleophilic coupling partners, such as organoboronic acids, boronate esters, and organotrifluoroborates. The newly developed O-centered electrophiles could couple with a multitude of aryl, heteroaryl, and alkylboron reagents, to give α-substituted vinylphosphonates in moderate to excellent yields. Generally, the Suzuki reaction is tolerant of extensive substitution at the aromatic ring of both electrophilic and nucleophilic coupling partners. As in the case of the Suzuki reaction of 8-quinolineboronic acid, proper choice of α-phosphonovinyl arylsulfonates is critical to efficient coupling. Moreover, the prospect for application of this method to complex synthesis has been demonstrated through the coupling of estrone-derived arylborons. The present protocol also features mild conditions and high efficiency. A new and attractive coupling partner for the synthesis of α-substituted vinylphosphonates through Suzuki reactions has been developed. The developed O-centered electrophiles couple with various organoboron reagents to give α-substituted vinylphosphonates in moderate to excellent yields. This protocol features broad substrate scope, mild conditions, and high efficiency.

Pd-Catalyzed Synthesis of α-Aryl Vinylphosphonates via Suzuki Arylation of α-Phosphonovinyl Nonaflates

The first palladium-catalyzed method for the arylation of α-phosphonovinyl nonaflates is described. Using a catalyst comprised of Pd(OAc)2 and SPhos, terminal and internal α-aryl vinylphosphonates could be efficiently accessed under mild condit

Applications of α-phosphonovinyl tosylates in the synthesis of α-arylethenylphosphonates via suzuki-miyaura cross-coupling reactions

It has been demonstrated for the first time that α-phosphonovinyl tosylates could efficiently couple with a range of arylboronic acids to access α-arylethenylphosphonates. The unprecedented procedure exhibits excellent functional group tolerance, giving the terminal vinylphosphonates in good to excellent isolated yields (60-99%) under mild reaction conditions.

A simple and efficient method for one-pot, three-component synthesis of terminal vinylphosphonates using a task-specific ionic liquid

A convenient and practical method for the one-pot, three-component synthesis of terminal vinylphosphonates from readily available starting materials (aryl/alkyl/heteroaryl aldehydes, nitromethane and trialkylphosphites) through a tandem Henry-Michael reaction followed by nitro elimination in the presence of 5-hydroxypentylammonium acetate (5-HPAA) as a task-specific ionic liquid, is described. This method offers several advantages such as the use of a reusable and inexpensive ionic liquid, which is an environmentally benign reaction medium, and a simple reaction setup that does not require specialized equipment. The approach offers good yields of the products under mild reaction conditions. Georg Thieme Verlag Stuttgart New York.

Rh(I)-catalyzed enantioselective hydrogenation of α-substituted ethenylphosphonic acids

A class of chiral Rh(I) catalysts containing monodentate phosphorous acid diesters tautomerized from the corresponding secondary phosphine oxides was discovered by serendipitous hydrolysis of phosphoramidite ligands. The evolved catalysts demonstrated unprecedented enantioselectivities (98-99% ee) and high catalytic activities (as low as 0.01 mol% catalyst loading) in asymmetric hydrogenations of a wide variety of α-aryl-/alkyl-substituted ethenylphosphonic acids, providing a facile approach to the corresponding enantiopure phosphonic acids with significant biological importance.

Synthesis of vinylphosphonates and its first exploration of bioactivity

Phosphonation of β-nitro-alkene with triethyl phosphite was achieved under microwave irradiation using CH2Cl2 as the solvent in the absence of catalyst with moderate to high yields (up to 90%). This method of formation of carbonphosphor bonds is simple, mild, convenient and effective. Synchronously, a number of vinylphosphonates derivatives were synthesized and evaluated biologically preliminary.

Enantioselective synthesis of chiral α-aryl or α-alkyl substituted ethylphosphonates via Rh-catalyzed asymmetric hydrogenation with a P-stereogenic BoPhoz-type ligand

(Chemical Equation Presented) An enantioselective synthesis of optically active 1-aryl or 1-alkyl substituted ethylphosphonates, based on the first Rh-catalyzed asymmetric hydrogenation of corresponding α,β- unsaturated precursors with a P-stereogenic BoPhoz-type ligand under the mild condition, was developed, in which a wide range of 1-aryl or 1-alkyl substituted ethylphosphonates were achieved in up to 98% ee.