The surprising reaction of (chloro- and methanesulfonyloxy)(phenyl)methylphosphonates and –(phenyl)methylphosphine oxides with potassium diphenylphosphide followed by oxidation

• Zsuzsanna Szalai,
• Janka Bednárik,
• András Miskó,
• Angéla Takács,
• László Kőhidai,
• László Drahos and
• György Keglevich

Beilstein J. Org. Chem. 2026, 22, 1160–1167, doi:10.3762/bjoc.22.93

• )(diaryl)phosphine oxides with potassium diphenylphosphide followed by oxidation took place in a clear-cut manner providing, with one exception, the corresponding α-phosphinylated α-hydroxyphosphine oxides that could also be synthesized by direct phosphinylation of the starting α-hydroxyphosphine oxide

• P-phenyl rings. Keywords: hydroxyphosphonate derivatives; phosphinylation; potassium diphenylphosphide; rearrangement; reversibility; Introduction α-Hydroxyphosphonates and α-hydroxyphosphine oxides represent a prominent class of compounds due to three reasons [1]. Their synthesis by the Pudovik

• . Beside the above approach marked as “method A”, products 8a–e completed with 8f could also be prepared by the direct phosphinylation of the starting (hydroxy(aryl)methyl)(diaryl)phosphine oxides 14a–f (Scheme 5, “method B”). The new products (14b, 16b–d, 15f, 8b–f) were fully characterized by 31P, 13C

Synthetic strategies of phosphonodepsipeptides

• Jiaxi Xu

Beilstein J. Org. Chem. 2021, 17, 461–484, doi:10.3762/bjoc.17.41

• dichlorophosphites followed by alcoholysis with hydroxy esters, the phosphinylation of hydroxy esters with phosphonochloridites followed by oxidation, and the carbene insertion of N-protected amino acids with 1-diazoalkylphosphonates. This review includes the synthesis of α-, β-, and γ-phosphonodepsipeptides and

• the phosphinylation of hydroxy esters 2 with N-protected aminoalkylphosphonochloridites 9 followed by oxidation (method V) (Figure 2). This review focuses on the synthetic methods of phosphonodepsipeptides and phosphonodepsipeptides with C-1-hydroxyalkylphosphonic acids, excluding peptides with side

• methyl or tert-butyl chloroacetate 192, and hydrogenolysis, the target phosphonodepsipeptides 194 were obtained (Scheme 35) [8][9][13]. Synthesis of phosphonodepsipeptides via phosphinylation of hydroxy esters with phosphonochloridites followed by oxidation Hammer’s group developed a new route to prepare

Synthesis of ([1,2,4]triazolo[4,3-a]pyridin-3-ylmethyl)phosphonates and their benzo derivatives via 5-exo-dig cyclization

• Aleksandr S. Krylov,
• Artem A. Petrosian,
• Julia L. Piterskaya,
• Nataly I. Svintsitskaya and
• Albina V. Dogadina

Beilstein J. Org. Chem. 2019, 15, 1563–1568, doi:10.3762/bjoc.15.159

• the phosphoryl fragment widens the range of practical applications of such compounds. In this regard, Marchenko and co-workers [15] have reported the direct P(III)-phosphinylation of [1,2,4]triazolopyridines. The introduction of chlorethynylphosphonates in reactions with 2-hydrazinylpyridines allows

Sigmatropic rearrangements of cyclopropenylcarbinol derivatives. Access to diversely substituted alkylidenecyclopropanes

• Guillaume Ernouf,
• Jean-Louis Brayer,
• Christophe Meyer and
• Janine Cossy

Beilstein J. Org. Chem. 2019, 15, 333–350, doi:10.3762/bjoc.15.29

• rearrangement would require high temperatures incompatible with such thermally labile strained substrates (Scheme 6) [37]. Interestingly, the authors detected traces of methylenecyclopropanes 7a/7’a when phosphinylation of alcohol 5a was conducted at room temperature for several hours which led them to consider

• that the amine could play a role in promoting the [2,3]-sigmatropic rearrangement. After a screening of different tertiary amines, Rubin et al. found that DBU could be used as a base in the phosphinylation reaction but also as an efficient catalyst for the subsequent [2,3]-sigmatropic rearrangement of

A new method for the synthesis of α-aminoalkylidenebisphosphonates and their asymmetric phosphonyl-phosphinyl and phosphonyl-phosphinoyl analogues

• Anna Kuźnik,
• Roman Mazurkiewicz,
• Mirosława Grymel,
• Katarzyna Zielińska,
• Jakub Adamek,
• Ewa Chmielewska,
• Marta Bochno and
• Sonia Kubica

Beilstein J. Org. Chem. 2015, 11, 1418–1424, doi:10.3762/bjoc.11.153

• -phosphinylation or α-phosphinoylation of 1-(N-acylamino)alkylphosphonates, that, in turn, are easily accessible from N-acyl-α-amino acids. Effective electrophilic activation of the α-position of 1-(N-acetylamino)alkylphosphonates was achieved by electrochemical α-methoxylation of these compounds in methanol

• -(dimethylamino)methyl]dipropylphosphine oxide [(Pr)2POCH(NMe2)OEt] with diethyl phosphite in 74% yield [35]. In the present paper we report a novel method for α-phosphonylation, α-phosphinylation or α-phosphinoylation of 1-(N-acetylamino)alkylphosphonates that enables effective transformation of the starting

• reactions enables α-phosphonylation, α-phosphinylation or α-phosphinoylation of 1-(N-acylamino)alkylphosphonates. Experimental General methods: IR spectra were measured on a FTIR spectrophotometer (ATR method). 1H and 13C NMR spectra were recorded at operating frequencies of 400 or 600 MHz and 100 MHz

Phosphinate-containing heterocycles: A mini-review

• Olivier Berger and
• Jean-Luc Montchamp

Beilstein J. Org. Chem. 2014, 10, 732–740, doi:10.3762/bjoc.10.67

• -Dieckmann condensation. Palladium-catalyzed oxidative arylation. Tandem cross-coupling/Dieckmann condensation. Rhodium-catalyzed double [2 + 2 + 2] cycloaddition. Silver oxide-mediated alkyne–arene annulation. Silver acetate-mediated alkyne–arene annulation. Cyclization through phosphinylation/alkylation 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

• phosphinylation of the bisphosphonate anion with diethyl chlorophosphite, ClP(OEt)2, followed by in situ oxidation with atmospheric oxygen of the presumed phosphinate intermediate to the trisphosphonate 6 was successful (Scheme 4) [25]. An improved version of this method includes oxidation of the phosphinate

• 12a–f a three-step protocol including synthesis of alkylidene-1,1-bisphosphonates 11 from tetraethyl methylenebisphosphonate (10), phosphinylation and oxidation has been developed (Scheme 6) [26]. Propargyl-substituted trisphosphonate 15 was prepared by conjugate addition of sodium acetylide to

• ethenylidenebisphosphonate 13 and the subsequent phosphinylation and oxidation (Scheme 7). This compound has been used in an elegant construction (“click” chemistry) of triazole derivatives (see Scheme 17) [26][28]. Synthesis via 7,7-bisphosphonoquinone methides A unique route to trisphosphonate 18 via addition of diethyl