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

• could act as an electron shuttle (potentially via a π-stacking assembly). The synthetic scope was extended to C(sp2)–P bond formations by trapping with phosphines or phosphites (Figure 12B), and in all these cases DIPEA was used as the electron donor (0.5–5 equiv). Arylphosphonium chlorides 20 that are

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

• aryl halides and trialkyl phosphites [23]. Some of the most studied C–P coupling reactions involving aryl substrates are those employing catalysts, which are required in order to lower the energy barrier of the reaction and overcome the poor reactivity between aryl halides and trialkyl phosphites [24

Synthesis and electrochemical properties of 3,4,5-tris(chlorophenyl)-1,2-diphosphaferrocenes

• Almaz A. Zagidullin,
• Farida F. Akhmatkhanova,
• Mikhail N. Khrizanforov,
• Robert R. Fayzullin,
• Tatiana P. Gerasimova,
• Ilya A. Bezkishko and
• Vasili A. Miluykov

Beilstein J. Org. Chem. 2022, 18, 1338–1345, doi:10.3762/bjoc.18.139

• -acceptor properties closer to phosphites P(OR)3 [8][9]. Since the P atom in phosphaferrocenes retains an electron lone pair, phosphaferrocenes have been used as P-donor ligands [10][11][12] as well as nucleophilic catalysts [13][14]. Recently, the pentaphosphaferrocene Cp*Fe(η5-P5) has been used as a

A comprehensive review of flow chemistry techniques tailored to the flavours and fragrances industries

• Guido Gambacorta,
• James S. Sharley and
• Ian R. Baxendale

Beilstein J. Org. Chem. 2021, 17, 1181–1312, doi:10.3762/bjoc.17.90

DNA with zwitterionic and negatively charged phosphate modifications: Formation of DNA triplexes, duplexes and cell uptake studies

• Yongdong Su,
• Maitsetseg Bayarjargal,
• Tracy K. Hale and
• Vyacheslav V. Filichev

Beilstein J. Org. Chem. 2021, 17, 749–761, doi:10.3762/bjoc.17.65

• TsN3 in MeCN or 0.7 M 4-(azidosulfonyl)-N,N,N-trimethylbutan-1-aminium iodide in DMF) was introduced as replacement of a standard iodine/pyridine oxidation step to react with 3',5'-dinucleoside β-cyanoethyl phosphites (Scheme 1, I), forming the N-modified iminophosphorane (Scheme 1, II). ONs bearing

Synthetic strategies of phosphonodepsipeptides

• Jiaxi Xu

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

• -hydroxyglutarate (84) in a Mitsunobu reaction to generate the γ-phosphonodepsipeptide 79 in a high yield of 66% (Scheme 27) [28]. Synthesis of phosphonodepsipeptides via the multicomponent condensation of amides, aldehydes, and phosphites followed by alcoholysis with hydroxy esters Previously, the Mannich-type

• reaction of benzyl carbamate, aldehydes, and trialkyl phosphites in acetyl chloride gave rise to N-Cbz-1-aminoalkylphosphonates [40]. When the reactions were conducted in benzene followed by an aminolysis or alcoholysis, phosphonamidates [41], phosphonopeptide [42], and mixed esters [43][44] were obtained

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

• sluggish in substitution reactions with NaN3, and the burdensomely obtained (2-azido-9H-purin-6-yl)phosphonates fail to undergo CuAAC reactions. The developed SNAr–Arbuzov reaction between 2,6-bistriazolylpurine derivatives and trialkyl phosphites is C6-regioselective, as proved by single-crystal X-ray

Oxidative radical ring-opening/cyclization of cyclopropane derivatives

• Yu Liu,
• Qiao-Lin Wang,
• Zan Chen,
• Cong-Shan Zhou,
• Bi-Quan Xiong,
• Pan-Liang Zhang,
• Chang-An Yang and
• Quan Zhou

Beilstein J. Org. Chem. 2019, 15, 256–278, doi:10.3762/bjoc.15.23

• moderate to good yields (Scheme 6) [57]. Additionally, using benzeneselenol instead of benzenethiol under the standard conditions generated the corresponding products in 31% yields. In the same year, Huang’s group also reported a similar ring-opening and cyclization of MCPs 1 with diethyl phosphites 21 for

• diethyl phosphites. Organic-selenium induced radical ring-opening and cyclization of MCPs derivatives (cyclopropylaldehydes). Copper(I)-catalyzed oxidative radical trifluoromethylation/ring-opening/cyclization of MCPs with Togni reagent II. Ag(I)-mediated trifluoromethylthiolation/ring-opening/cyclization

Pd-Catalyzed microwave-assisted synthesis of phosphonated 13α-estrones as potential OATP2B1, 17β-HSD1 and/or STS inhibitors

• Rebeka Jójárt,
• Szabolcs Pécsy,
• György Keglevich,
• Mihály Szécsi,
• Réka Rigó,
• Csilla Özvegy-Laczka,
• Gábor Kecskeméti and
• Erzsébet Mernyák

Beilstein J. Org. Chem. 2018, 14, 2838–2845, doi:10.3762/bjoc.14.262

• dialkyl phosphites (H-phosphonates) as the reagents, Pd(PPh3)4 as the catalyst and Et3N as the base [26]. Variations of the reaction have recently been published to prepare diverse functionalized phosphonates [27][28]. The C–P couplings have been performed not only under traditional thermal conditions

• [29]; namely, 1 equiv in the case of Pd(PPh3)4 and 1.3 equiv when using Pd(OAc)2. It was earlier established that in the microwave-assisted Pd(II)-catalyzed C–P coupling of aryl bromides and dialkyl phosphites, an excess of the applied dialkyl phosphite may serve as phosphorus ligand and reducing

Aminosugar-based immunomodulator lipid A: synthetic approaches

• Alla Zamyatina

Beilstein J. Org. Chem. 2018, 14, 25–53, doi:10.3762/bjoc.14.3

Effect of uridine protecting groups on the diastereoselectivity of uridine-derived aldehyde 5’-alkynylation

• Raja Ben Othman,
• Mickaël J. Fer,
• Laurent Le Corre,
• Sandrine Calvet-Vitale and
• Christine Gravier-Pelletier

Beilstein J. Org. Chem. 2017, 13, 1533–1541, doi:10.3762/bjoc.13.153

• diastereoselective addition of a nucleophile on a carbonyl group. The latter can involve either the reduction of a ketone at C-5’ [12][33][34][35], or the addition on an aldehyde of various nucleophiles such as enolates [15][36][37][38], allylborane [39], dialkyl phosphites [40], TMSCN [41] or Grignard reagents [12

The synthesis of α-aryl-α-aminophosphonates and α-aryl-α-aminophosphine oxides by the microwave-assisted Pudovik reaction

• Erika Bálint,
• Ádám Tajti,
• Anna Ádám,
• István Csontos,
• Konstantin Karaghiosoff,
• Mátyás Czugler,
• Péter Ábrányi-Balogh and
• György Keglevich

Beilstein J. Org. Chem. 2017, 13, 76–86, doi:10.3762/bjoc.13.10

• and α-aryl-α-aminophosphine oxides was synthesized by the microwave-assisted solvent-free addition of dialkyl phosphites and diphenylphosphine oxide, respectively, to imines formed from benzaldehyde derivatives and primary amines. After optimization, the reactivity was mapped, and the fine mechanism

• at all. In the current paper, we wished to develop a facile catalyst and solvent-free MW-assisted method for the synthesis of α-aryl-α-aminophosphonates and α-aryl-α-aminophosphine oxides by the addition of dialkyl phosphites or diphenylphosphine oxide to the double bond of imines, and aimed at the

• aniline at room temperature under solvent-free conditions (Scheme 1). Then, the reaction of N-benzylidene(butyl)amine (1a) with four different dialkyl phosphites and diphenylphosphine oxide was investigated under MW-assisted solvent-free conditions searching for the optimum temperature and reaction time

First DMAP-mediated direct conversion of Morita–Baylis–Hillman alcohols into γ-ketoallylphosphonates: Synthesis of γ-aminoallylphosphonates

• Marwa Ayadi,
• Haitham Elleuch,
• Emmanuel Vrancken and
• Farhat Rezgui

Beilstein J. Org. Chem. 2016, 12, 2906–2915, doi:10.3762/bjoc.12.290

• Montpellier Cedex 5, France 10.3762/bjoc.12.290 Abstract An efficient synthesis of a series of γ-ketoallylphosphonates through a direct conversion of both primary and secondary Morita–Baylis–Hillman (MBH) alcohols by trialkyl phosphites with or without DMAP, used as additive, and under solvent-free

• step protocol involves firstly the mesylation of corresponding alcohols and then the conversion of the intermediate mesylates into their halides. Further an Arbuzov reaction of alkyl phosphites with such halides affords the phosphonates. Interestingly, a direct conversion of common allyl alcohols into

• , followed by thermal Arbuzov rearrangement of the intermediate allyl phosphites (Scheme 1, reaction 1). Recently, an efficient protocol for the conversion of common allyl and benzyl alcohols into the corresponding phosphonates through their treatment with triethyl phosphite and ZnI2, was described [16

Synthesis of medronic acid monoesters and their purification by high-performance countercurrent chromatography or by hydroxyapatite

• Elina Puljula,
• Jouko Vepsäläinen and
• Petri A. Turhanen

Beilstein J. Org. Chem. 2016, 12, 2145–2149, doi:10.3762/bjoc.12.204

• of medronic acid monoesters. Several methods have been utilized for the production of mixed tetraesters of medronic acid (Scheme 1). One option is to build the tetraester from monophosphonates and phosphites with the desired alkyl groups. The most commonly used reactions are Michaelis–Becker

Microwave-assisted synthesis of (aminomethylene)bisphosphine oxides and (aminomethylene)bisphosphonates by a three-component condensation

• Erika Bálint,
• Ádám Tajti,
• Anna Dzielak,
• Gerhard Hägele and
• György Keglevich

Beilstein J. Org. Chem. 2016, 12, 1493–1502, doi:10.3762/bjoc.12.146

• diphenylphosphine oxide to an isonitrile (Scheme 4b) [36][42]. In this paper, we wish to report the results of our investigations on the synthetic protocol utilizing the three-component condensations of primary or secondary amines, orthoformates and >P(O)H species, such as dialkyl phosphites or diphenylphosphine

Multicomponent reactions: A simple and efficient route to heterocyclic phosphonates

• Mohammad Haji

Beilstein J. Org. Chem. 2016, 12, 1269–1301, doi:10.3762/bjoc.12.121

• phosphite. When butanediones 128 with a larger substituent than Me were used, only monophosphonates 129 were obtained. The second method comprises a one-pot four-component reaction of diamines 130, ketones 131 and phosphites 132 in the presence of FeCl3 as a catalyst to give benzodiazepinylphosphonates 133

• -dioxohexahydropyrimidines 311 via a three-component reaction [102]. This method involved the one-pot reaction of N,N'-dimethylurea (310) and dialkyl acetylenedicarboxylates 309 in the presence of trialkyl phosphites 308 at room temperature (Scheme 64). The desired products were obtained in high yields between 84 and 94

• -catalyzed Kabachnik–Fields reaction of isatin with dialkyl phosphites and aniline. The Mg(ClO4)2-catalyzed Kabachnik–Fields reaction of 1-tosylpiperidine-4-one. An asymmetric version of the Kabachnik–Fields reaction for the synthesis of α-amino-3-piperidinylphosphonic acids. A classical Kabachnik–Fields

Synthesis, fluorescence properties and the promising cytotoxicity of pyrene–derived aminophosphonates

• Jarosław Lewkowski,
• Maria Rodriguez Moya,
• Anna Wrona-Piotrowicz,
• Janusz Zakrzewski,
• Renata Kontek and
• Gabriela Gajek

Beilstein J. Org. Chem. 2016, 12, 1229–1235, doi:10.3762/bjoc.12.117

• solution was to apply phosphites simultaneously as solvents and reactants, which however forced to use them in a high excess. This necessity resulted in troubles with purification, implicating a particular approach to each case. Dimethyl aminophosphonates 3Aa–Ah were purified by washing their

Chiral cyclopentadienylruthenium sulfoxide catalysts for asymmetric redox bicycloisomerization

• Barry M. Trost,
• Michael C. Ryan and
• Meera Rao

Beilstein J. Org. Chem. 2016, 12, 1136–1152, doi:10.3762/bjoc.12.110

• , entry 5). In general, untethered, exogenous sulfoxides are poorer ligands to ruthenium than phosphines or phosphites. As the reaction temperature is lowered to 40 °C, however, one begins to see a significant decrease in reaction rate and conversion (Table 1, entry 6). The enantioselectivity of the

[2.2]Paracyclophane derivatives containing tetrathiafulvalene moieties

• Laura G. Sarbu,
• Lucian G. Bahrin,
• Peter G. Jones,
• Lucian M. Birsa and
• Henning Hopf

Beilstein J. Org. Chem. 2015, 11, 1917–1921, doi:10.3762/bjoc.11.207

• 1,3-dithiolium perchlorates 5a–c in the presence of tetrafluoroboric acid led to the degradation of the substrate. The second approach for the synthesis of tetrathiafulvalenes involves the desulfurative coupling of 1,3-dithiol-2-thiones in the presence of alkyl phosphites. 1,3-Dithiol-2-thiones are

Ruthenium indenylidene “1^st generation” olefin metathesis catalysts containing triisopropyl phosphite

• Stefano Guidone,
• Fady Nahra,
• Alexandra M. Z. Slawin and
• Catherine S. J. Cazin

Beilstein J. Org. Chem. 2015, 11, 1520–1527, doi:10.3762/bjoc.11.166

• ” cis-complexes. These have been used in olefin metathesis reactions. The cis-Ru species exhibit noticeable differences with the trans-Ru parent complexes in terms of structure, thermal stability and reactivity. Experimental data underline the importance of synergistic effects between phosphites and L

• [10][11][12][13][24]. In order to reduce the cost of the Ru-based pre-catalyst, our group has investigated the use of phosphites as an economical alternative to phosphines. The reaction of triisopropyl phosphite with the pyridine-containing indenylidene complex [RuCl2(Ind)(SIMes)(py)] (SIMes = N,N

• the mixed NHC/phosphite cis-Caz-1 suggest the importance of synergistic effects involving phosphites, an inexpensive alternative to phosphines for Ru-based pre-catalysts, and the L-type ligands, a concept that can be used to incite further improvements in catalyst design. Experimental Synthesis and

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

• , mediated with NaCl, followed by displacement of the methoxy group with triphenylphosphonium tetrafluoroborate to give hitherto unknown 1-(N-acetylamino)-1-triphenylphosphoniumalkylphosphonate tetrafluoroborates. The latter compounds react smoothly with trialkyl phosphites, dialkyl phosphonites or alkyl

• doublets of phosphorus atoms in the ranges of 11.7–16.5 and 28.5–37.0 ppm (J = 33–48 Hz) in the 31P NMR spectra. Finally, it was demonstrated that diethyl 1-(N-acetylamino)-1-triphenylphosphoniumalkylphosphonate tetrafluoroborates 7 react smoothly with trialkyl phosphites, dialkyl phosphonites or alkyl

• compounds with trialkyl phosphites, dialkyl phosphonites or alkyl phosphinites in the presence of Hünig’s base and methyltriphenylphosphonium iodide gave the expected alkylidenebisphosphonates, 1-phosphinylalkylphosphonates or 1-phosphinoylalkylphosphonates, respectively, in good yields. The reported set of

Highly selective palladium–benzothiazole carbene-catalyzed allylation of active methylene compounds under neutral conditions

• Antonio Monopoli,
• Pietro Cotugno,
• Carlo G. Zambonin,
• Francesco Ciminale and
• Angelo Nacci

Beilstein J. Org. Chem. 2015, 11, 994–999, doi:10.3762/bjoc.11.111

• overreactions giving the diallylated compounds [23][24], the need for catalysts that are tedious to prepare [18][19], and the use of toxic or expensive ligands such as phosphanes or phosphites [3][25]. Therefore, the careful selection of a suitable ligand capable for replacing phosphines and improving palladium

Hydrogenation of unactivated enamines to tertiary amines: rhodium complexes of fluorinated phosphines give marked improvements in catalytic activity

• Sergey Tin,
• Tamara Fanjul and
• Matthew L. Clarke

Beilstein J. Org. Chem. 2015, 11, 622–627, doi:10.3762/bjoc.11.70

• issue with the strong π-acceptor ligand triphenylphosphite. We note here that an earlier attempt by some of us using chiral phosphites in this type of reaction gave very low conversions to product under these conditions. The ligand electronic effect clearly supports our earlier proposal of the reductive

Diastereoselective and enantioselective conjugate addition reactions utilizing α,β-unsaturated amides and lactams

• Katherine M. Byrd

Beilstein J. Org. Chem. 2015, 11, 530–562, doi:10.3762/bjoc.11.60

• the 1,4-addition of phosphites provides a direct route for accessing chiral phosphonates, there are only a few examples of this reaction [259][260][261][262][263][264]. In 2009, Wang and co-workers reported one of the first catalytic, enantioselective 1,4-addition of phosphites to α,β-unsaturated N

An unusually stable chlorophosphite: What makes BIFOP–Cl so robust against hydrolysis?

• Roberto Blanco Trillo,
• Jörg M. Neudörfl and
• Bernd Goldfuss

Beilstein J. Org. Chem. 2015, 11, 313–322, doi:10.3762/bjoc.11.36

• , in Pd catalysts. Keywords: chirality; hydrolysis; phosphorus; rearrangements; terpenoids; Introduction Phosphorus halides are highly reactive intermediates for the synthesis of phosphites and phosphoramidites [1][2][3][4][5], which are widely used, for example, as ligands in catalysts [6][7][8][9