A review of recent advances in electrochemical and photoelectrochemical late-stage functionalization classified by anodic oxidation, cathodic reduction, and paired electrolysis

• Nian Li,
• Ruzal Sitdikov,
• Ajit Prabhakar Kale,
• Joost Steverlynck,
• Bo Li and
• Magnus Rueping

Beilstein J. Org. Chem. 2024, 20, 2500–2566, doi:10.3762/bjoc.20.214

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

Organophosphorus chemistry: from model to application

• György Keglevich

Beilstein J. Org. Chem. 2023, 19, 89–90, doi:10.3762/bjoc.19.8

• . elaborated a Lewis acid-catalyzed one-pot synthesis of phosphinates and phosphonates staring from pyridinecarboxaldehydes and diarylphosphine oxides [2]. This protocol is the analogy of the Pudovik reaction, followed by the phospha-Brook rearrangement applied mainly for the synthesis of phosphoric ester

Lewis acid-catalyzed Pudovik reaction–phospha-Brook rearrangement sequence to access phosphoric esters

• Jin Yang,
• Dang-Wei Qian and
• Shang-Dong Yang

Beilstein J. Org. Chem. 2022, 18, 1188–1194, doi:10.3762/bjoc.18.123

• Herein, we report a Lewis acid-catalyzed Pudovik reaction–phospha-Brook rearrangement sequence between diarylphosphonates or -phosphinates and α-pyridinealdehydes to access valuable phosphoric ester compounds. This transformation provides an extended substrate scope that is complementary to similar

• with diarylphosphonates and -phosphinates (Scheme 1b). The present method is simple and efficient, providing an extended substrate scope that is complementary to classical similar base-prompted reactions. Results and Discussion We used diphenylphosphine oxide (1a) and 2-pyridinecarboxaldehyde (2a) as

• heterocycle, such as a benzothiophene (in 1l) or a benzofuran unit (in 1m), could smoothly be transformed into the desired products 3al and 3am, respectively, in moderate yield. Phosphinates 3an and 3ao could both be prepared under this Pudovik reaction–phospha-Brook rearrangement sequence in moderate to good

Synthetic strategies for the preparation of γ-phostams: 1,2-azaphospholidine 2-oxides and 1,2-azaphospholine 2-oxides

• Jiaxi Xu

Beilstein J. Org. Chem. 2022, 18, 889–915, doi:10.3762/bjoc.18.90

• method was more efficient than the DCC coupling one. The similar treatment of alkyl 2-aminobenzyl(phenyl)phosphinates 53 and 63 gave 1-alkyl-2-phenyl-1,3-dihydrobenzo[d][1,2]azaphosphole 2-oxides 56 in 51–65% yield through the alkyl transfer from the O to the N atom followed by dehydration under heating

• ]azaphosphole 2-oxides from 2-aminobenzyl(methyl/phenyl)phosphinic acids, alkyl 2-aminobenzyl(phenyl)phosphinates, and dimethyl 2-aminobenzylphosphonate (61). Synthesis of ethyl 2-methyl-1,2-azaphospholidine-5-carboxylate 2-oxide 69 from 2-amino-4-(hydroxy(methyl)phosphoryl)butanoic acids 68. Synthesis of 2

Interactions of cyclodextrins and their derivatives with toxic organophosphorus compounds

• Sophie Letort,
• Sébastien Balieu,
• William Erb,
• Géraldine Gouhier and
• François Estour

Beilstein J. Org. Chem. 2016, 12, 204–228, doi:10.3762/bjoc.12.23

• commercial impacts during the last decades, phosphates, phosphonates, phosphinates, or phosphines being prominent in several fields. As an example, drugs bearing an organophosphorus moiety hold a significant place in chemotherapy for the treatment of various diseases. Nevertheless, the high polarity of these

Synthesis of γ-hydroxypropyl P-chirogenic (±)-phosphorus oxide derivatives by regioselective ring-opening of oxaphospholane 2-oxide precursors

• Iris Binyamin,
• Shoval Meidan-Shani and
• Nissan Ashkenazi

Beilstein J. Org. Chem. 2015, 11, 1332–1339, doi:10.3762/bjoc.11.143

• Iris Binyamin Shoval Meidan-Shani Nissan Ashkenazi Department of Organic Chemistry, IIBR-Israel Institute for Biological Research, P.O. Box 19, Ness Ziona, 74100, Israel 10.3762/bjoc.11.143 Abstract The synthesis of P-chirogenic (±)-phosphine oxides and phosphinates via selective nucleophilic

• ; oxaphospholanes; phosphinates; phosphine oxides; Introduction Organophosphorus compounds containing phosphorus to carbon bond(s) are widely used in organic transformations. Textbook examples are the Wittig and the Horner–Wadsworth–Emmons reactions. Moreover, the vast majority of ligands used in organometallic

• various Grignard reagents. Indeed, in all cases, the attack on the phosphorus atom led exclusively to ring opening via endocyclic P–O bond cleavage and formation of a new P–C bond, yielding phosphinates and phosphine oxides with three different substituents on the phosphorus atom. Results and Discussion

Atherton–Todd reaction: mechanism, scope and applications

• Stéphanie S. Le Corre,
• Mathieu Berchel,
• Hélène Couthon-Gourvès,
• Jean-Pierre Haelters and
• Paul-Alain Jaffrès

Beilstein J. Org. Chem. 2014, 10, 1166–1196, doi:10.3762/bjoc.10.117

• established. From a stereochemical point of view, these results can be summarized as shown in Scheme 7-v. Other recent studies have reported stereocontrolled AT reactions. Han et al. [33] described the preparation of optically active organophosphorus acid derivatives from menthyl-based H-phosphinates (or

• chiral HPLC or CPG. In a recent study, Montchamp et al. used the AT reaction for the determination of the ee of P-chiral H-phosphinates by the formation of diastereoisomers (Scheme 33) [108]. The ee determined by this method, which can be achieved directly in the NMR tube before recording 31P NMR spectra

Preparation of phosphines through C–P bond formation

• Iris Wauters,
• Wouter Debrouwer and
• Christian V. Stevens

Beilstein J. Org. Chem. 2014, 10, 1064–1096, doi:10.3762/bjoc.10.106

• , phosphonates, phosphinates and phosphate derivatives, etc.) are out of the scope of this review. Review Preparation of alkylphosphines via formation of a C(sp3)–P bond Reaction of organometallic reagents with halophosphines One of the main approaches to synthesize a carbon–phosphorus bond involves the

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

• organophosphorus compounds: the phosphinates R1R2P(O)(OR) [9]. Because the phosphinic acid moiety P(O)OH can mimic carboxylic acids, its incorporation into heterocycles may offer new opportunities for the discovery of biologically active analogs. However, little or no biological data is available at this time

• ,b were prepared in 51% and 62% yields. The same approach was reported earlier by Mioskowski and coworkers [15][16] except the starting phosphinates 3a,b were prepared less efficiently by the sila-Arbuzov reaction of bis(trimethylsiloxy)phosphine (Me3SiO)2PH. Phosphindoles Montchamp and coworkers

• synthesis of chiral bicyclic phosphinates 23a–k by domino hydrophosphinylation/Michael/Michael reaction was realized by Fourgeaud et al. (Scheme 10) [25]. Several 1-oxa-3-aza-6-phosphabicyclo[3.3.0]octanes derivatives 23a–k were obtained in yields around 70% by reacting allenes 21 with imines 22 derived

A novel family of (1-aminoalkyl)(trifluoromethyl)- and -(difluoromethyl)phosphinic acids – analogues of α-amino acids

• Natalia V. Pavlenko,
• Tatiana I. Oos,
• Yurii L. Yagupolskii,
• Igor I. Gerus,
• Uwe Doeller and
• Lothar Willms

Beilstein J. Org. Chem. 2014, 10, 722–731, doi:10.3762/bjoc.10.66

• efforts have established H-phosphinates R(H)P(O)(OR′) or appropriate P(III) acids R(H)P(O)(OH) as appropriate starting materials for the preparation of aminophosphinic acids. The most typical route involves the three-component reaction of an aldehyde, an amine and a P–H substrate in a one-pot Mannich type

• protocol [19][20][21]. An alternative to this approach involves the simple addition of alkyl H-phosphinates or H-phosphinic acids to Schiff bases [5][22]. In this paper we exploit both routes to prepare (1-aminoalkyl)(trifluoromethyl)- and -(difluoromethyl)phosphinic acids using P–H compounds bearing CF3

• conversion yield but after purification over silica gel only the appropriate acid 19a was isolated. In the case of the reaction of ester 5 with imine 16e no adduct was formed. Ethyl phosphinates 18b–d were obtained as a mixture of two diastereoisomers, which were not separated but they are clearly observed

Kinetics and mechanism of the anilinolysis of aryl phenyl isothiocyanophosphates in acetonitrile

• Hasi Rani Barai and
• Hai Whang Lee

Beilstein J. Org. Chem. 2013, 9, 615–620, doi:10.3762/bjoc.9.68

• departing chloride [17][18][19][20][21][22][23]. The authors also suggested TSf-type, in which hydrogen bonding of an amine hydrogen atom occurs to the departing phenoxy oxygen atom for the anilinolyses of aryl dimethyl, methyl and diphenyl phosphinates [24]. Thus, at this point, the authors are in favor of