Photoredox catalysis harvesting multiple photon or electrochemical energies

• Mattia Lepori,
• Simon Schmid and
• Joshua P. Barham

Beilstein J. Org. Chem. 2023, 19, 1055–1145, doi:10.3762/bjoc.19.81

An alternative C–P cross-coupling route for the synthesis of novel V-shaped aryldiphosphonic acids

• Stephen J. I. Shearan,
• Enrico Andreoli and
• Marco Taddei

Beilstein J. Org. Chem. 2022, 18, 1518–1523, doi:10.3762/bjoc.18.160

• Abstract The synthesis of phosphonate esters is a topic of interest for various fields, including the preparation of phosphonic acids to be employed as organic linkers for the construction of metal phosphonate materials. We report an alternative method that requires no solvent and involves a different

• three novel aryl diphosphonate esters which were subsequently transformed to phosphonic acids through silylation and hydrolysis. Keywords: arylphosphonic acids; cross-coupling reaction; phosphonate esters; transition-metal catalysis; Introduction Phosphonates and phosphonic acids are a very

• mmol), 4.0 g (12.2 mmol) or 3.0 g (7.4 mmol) of substrate. Once the phosphonate esters had been successfully obtained and characterized by 1H, 31P, 13C NMR and mass spectrometry (see experimental section and Supporting Information File 1), they were then subjected to silylation and subsequent

Development of N-F fluorinating agents and their fluorinations: Historical perspective

• Teruo Umemoto,
• Yuhao Yang and
• Gerald B. Hammond

Beilstein J. Org. Chem. 2021, 17, 1752–1813, doi:10.3762/bjoc.17.123

• ], electron-rich alkenes (entry 3) [65][66], alkyl sulfides (entry 4) [65][67], 1,3-dicarbonyl compounds [65][68], phosphonate esters (entry 5) [65], steroidal silyl enol ethers and enol acetates (entry 6) [65], pyrimidine bases and nucleosides (entry 7) [67][69], phenylalkynes (entry 8) [70], anthraquinones

1,2,3-Triazoles as leaving groups in S_NAr–Arbuzov reactions: synthesis of C6-phosphonated purine derivatives

• Kārlis-Ēriks Kriķis,
• Irina Novosjolova,
• Anatoly Mishnev and
• Māris Turks

Beilstein J. Org. Chem. 2021, 17, 193–202, doi:10.3762/bjoc.17.19

• to optimize the Cl→N3 SNAr process at the purine C2 position, and that way, the isopropyl phosphonate 2b was also obtained. It is known that both chloride and azide can cleave phosphonate esters [25][26][27][28], but the chloride source would not interfere with the SNAr process at C2. Hence, we

The McKenna reaction – avoiding side reactions in phosphonate deprotection

• Katarzyna Justyna,
• Joanna Małolepsza,
• Damian Kusy,
• Waldemar Maniukiewicz and
• Katarzyna M. Błażewska

Beilstein J. Org. Chem. 2020, 16, 1436–1446, doi:10.3762/bjoc.16.119

• phosphonate esters into bis(trimethylsilyl)esters, which are then easily converted into the target acids. However, the versatile character of the McKenna reaction is not always used to its full extent, due to formation of side products. Herein, demonstrated by using model examples we have not only analyzed

• for the reaction of compound 12 in the presence of diisopropyl phosphonoacetate 8c, even with TEA (10 equiv) added (Table 2, entry 4). However, it could not be excluded that this positive outcome would be observed for dimethyl phosphonate esters, due to the low boiling point of methyl bromide (≈4 °C

• reflux promotes the removal of EtBr from the reaction mixture. For the purpose of this study, we used the polar aprotic solvent acetonitrile due to its good solubilizing properties. The reactions were usually carried out at 35 °C for 24 h, based on our experience with different types of phosphonate

Copper-catalyzed O-alkenylation of phosphonates

• Nuria Vázquez-Galiñanes,
• Mariña Andón-Rodríguez,
• Patricia Gómez-Roibás and
• Martín Fañanás-Mastral

Beilstein J. Org. Chem. 2020, 16, 611–615, doi:10.3762/bjoc.16.56

• chemistry [1][2][3]. In particular, O-alkenyl phosphonate esters (i.e., enol phosphonates) have been described as potent insecticides and show antifungal activity [4]. While several methods are available for the preparation of cyclic enol phosphonates [5][6][7][8][9][10], the synthesis of the acyclic

• . Interestingly, the copper-catalyzed alkenylation of phosphonates followed the same reactivity trend as the one described for the arylation reaction [32] with the diisopropyl phosphonates being more efficient than the dimethyl phosphonate esters. It is also important to remark that, in sharp contrast to the

Synthesis of C-glycosyl phosphonate derivatives of 4-amino-4-deoxy-α-ʟ-arabinose

• Lukáš Kerner and
• Paul Kosma

Beilstein J. Org. Chem. 2020, 16, 9–14, doi:10.3762/bjoc.16.2

• α-ʟ-anomeric arabino- and ribo-configured methyl phosphonate esters. In addition, the monomethyl phosphonate glycal intermediates were converted into n-octyl derivatives followed by subsequent selective removal of the methyl phosphonate ester group and hydrogenation to give the octylphosphono

Relay cross metathesis reactions of vinylphosphonates

• Raj K. Malla,
• Jeremy N. Ridenour and
• Christopher D. Spilling

Beilstein J. Org. Chem. 2014, 10, 1933–1941, doi:10.3762/bjoc.10.201

• bromide, increasing the amount of TBAI and prolonged heating times, either at reflux or in a microwave reactor. The ratio of di- to mono-allyl phosphonate esters increases with the duration of reaction. A subsequent reaction of vinylphosphonate 12b employing 5 equivalents of allyl bromide, 5 mol % TBAI

• and 18 hours at reflux resulted in 87% conversion with 1.2:1 ratio of mono- to diallyl ester (14a and 14b). The products were isolated by silica gel chromatography to give 31% yield of mono-allyl and 25% yield of diallyl phosphonate esters. Similarly, THF-substituted vinylphosphonate 19 was treated

• diallyl phosphonate esters. Finally, THP-vinylphosphonate 5 was subjected to transesterification by reaction with 20 mol % of TBAI and 5 equivalents of allyl bromide in toluene solution and heating in a microwave reactor for 5.5 hours. The reaction proceeded to 96% conversion and gave 1:1.8 ratio of mono

Synthesis of isoprenoid bisphosphonate ethers through C–P bond formations: Potential inhibitors of geranylgeranyl diphosphate synthase

• Xiang Zhou,
• Jacqueline E. Reilly,
• Kathleen A. Loerch,
• Raymond J. Hohl and
• David F. Wiemer

Beilstein J. Org. Chem. 2014, 10, 1645–1650, doi:10.3762/bjoc.10.171

• dialkyl bisphosphonate 5, and gave the desired tetraethyl O,C-digeranylbisphosphonate 10. Hydrolysis of the phosphonate esters proceeded under standard McKenna conditions [24], but only a limited amount of the product 6 was recovered after precipitation from acetone/water. A parallel hydrolysis of

Methylidynetrisphosphonates: Promising C₁ building block for the design of phosphate mimetics

• Vadim D. Romanenko and
• Valery P. Kukhar

Beilstein J. Org. Chem. 2013, 9, 991–1001, doi:10.3762/bjoc.9.114

• ]. Review Preparation of methylidynetrisphosphonates Synthesis via a Michaelis–Arbuzov reaction Phosphonate esters are often prepared through Michaelis–Arbuzov reaction of a trialkyl phosphite with an alkyl halide [9]. However, contrary to the early patent claims, trisphosphonate esters cannot be derived

• dephosphonylation than the parent trisphosphonate esters, HC(PO3R2)3, or their α-carbo-substituted derivatives. In particular, in the case of aminotrisphosphonate ester 1a all standard synthetic routes to phosphonic acids (A–C) via acidic hydrolysis of phosphonate esters lead to the elimination of one phosphonyl

Synthesis of novel (1-alkanoyloxy- 4-alkanoylaminobutylidene)-1,1-bisphosphonic acid derivatives

• Petri A. Turhanen and
• Jouko J. Vepsäläinen

Beilstein J. Org. Chem. 2006, 2, No. 2, doi:10.1186/1860-5397-2-2

• have also recently described the method for the preparation of (1-alkoxycarbonyloxyethylidene)-1,1-bisphosphonic acid derivatives [20] and novel fatty acid derivatives of etidronate [21] which may represent prodrugs of etidronate. In the case of etidronic acid, we have shown that simple phosphonate

• esters like P(O)-O-Me as well as an acyl group at the tertiary alcohol group are stable against enzymatic hydrolysis. [18] However, the latter decomposed gradually due to chemical hydrolysis. Because of the extreme hydrophilic character of HABBPA, its solubility and reactivity in organic solvents is very