Cu–Bpin-mediated dimerization of 4,4-dichloro-2-butenoic acid derivatives enables the synthesis of densely functionalized cyclopropanes

• Patricia Gómez-Roibás,
• Andrea Chaves-Pouso and
• Martín Fañanás-Mastral

Beilstein J. Org. Chem. 2025, 21, 877–883, doi:10.3762/bjoc.21.71

• a mixture of Z:E isomers (Table 1, entry 8). Having identified the proper combination of base and solvent, we then screened different copper catalysts. Different NHCs, bisphosphines and phosphines were tested (Table 1, entries 9–14) and excellent chemo- and diastereoselectivity was observed in all

Recent advances in the electrochemical synthesis of organophosphorus compounds

• Babak Kaboudin,
• Milad Behroozi,
• Sepideh Sadighi and
• Fatemeh Asgharzadeh

Beilstein J. Org. Chem. 2025, 21, 770–797, doi:10.3762/bjoc.21.61

• oxidation of phosphines to phosphine oxides, followed by further anodic oxidation to give a phosphine oxide radical. In the subsequent step, treatment of the thiol radical (formed via the deprotonation of thiols with cesium carbonate and anodic oxidation) with the phosphine oxide radical gave the

Dioxazolones as electrophilic amide sources in copper-catalyzed and -mediated transformations

• Seungmin Lee,
• Minsuk Kim,
• Hyewon Han and
• Jongwoo Son

Beilstein J. Org. Chem. 2025, 21, 200–216, doi:10.3762/bjoc.21.12

• -phosphorylation of dioxazolones using organic phosphines and copper catalysts [91]. As shown in Scheme 6, a variety of dioxazolones 14 were explored for the synthesis of N-acyl iminophosphoranes 16. Dioxazolones containing aryl and heteroaryl groups were successfully transformed into the desired products in high

Recent advances in organocatalytic atroposelective reactions

• Henrich Szabados and
• Radovan Šebesta

Beilstein J. Org. Chem. 2025, 21, 55–121, doi:10.3762/bjoc.21.6

• purities, solid yields and very good diastereomeric ratios. The hydroxy group present in products 156 and 158 could be transformed to provide axially chiral phosphines that could be utilized as chiral ligands in transition-metal-catalyzed reactions. Testing both substrates 156 and 158 for conformational

Intramolecular C–H arylation of pyridine derivatives with a palladium catalyst for the synthesis of multiply fused heteroaromatic compounds

• Yuki Nakanishi,
• Shoichi Sugita,
• Kentaro Okano and
• Atsunori Mori

Beilstein J. Org. Chem. 2024, 20, 3256–3262, doi:10.3762/bjoc.20.269

• . The addition of ligand improved the yield of 2a as shown in Table 1, entries 7–10. Among several ligands, including Buchwald-type phosphines L1–L4 [33] examined, it was found that the use CyJohnPhos (L3) afforded the cyclized product in 90% yield and the reaction with PPh3 (L4) as a ligand was also

Recent advances in transition-metal-free arylation reactions involving hypervalent iodine salts

• Ritu Mamgain,
• Kokila Sakthivel and
• Fateh V. Singh

Beilstein J. Org. Chem. 2024, 20, 2891–2920, doi:10.3762/bjoc.20.243

O,S,Se-containing Biginelli products based on cyclic β-ketosulfone and their postfunctionalization

• Kateryna V. Dil and
• Vitalii A. Palchykov

Beilstein J. Org. Chem. 2024, 20, 2143–2151, doi:10.3762/bjoc.20.184

• ). Results and Discussion Reaction optimization Over the past two decades more than 300 various catalytic systems have been proposed for Biginelli chemistry, e.g., simple inorganic and organic acids, metal salts, metal oxides, ionic liquids, phosphines, nanocatalysts, organocatalysts, ion exchange resins [1

Efficacy of radical reactions of isocyanides with heteroatom radicals in organic synthesis

• Akiya Ogawa and
• Yuki Yamamoto

Beilstein J. Org. Chem. 2024, 20, 2114–2128, doi:10.3762/bjoc.20.182

• by ESR measurement [37]. Similar to the thiol addition to isocyanides, disubstituted phosphines (R’2PH) induce radical addition to isocyanides in the presence of AIBN as a radical initiator yielding the corresponding iminoformyl phosphines, R’2P–CH=NR, (12, R = c-C6H11 or n-C6H11, E = Et2P) in good

• thioselenation and catalytic dithiolation of isocyanides. Synthesis of carbacephem framework. Sequential addition of (PhSe)2 to ethyl propiolate and isocyanide. Isocyanide insertion reaction into carbon-tellurium bonds. Radical addition to isocyanides with disubstituted phosphines. Radical addition to phenyl

Towards an asymmetric β-selective addition of azlactones to allenoates

• Behzad Nasiri,
• Ghaffar Pasdar,
• Paul Zebrowski,
• Katharina Röser,
• David Naderer and
• Mario Waser

Beilstein J. Org. Chem. 2024, 20, 1504–1509, doi:10.3762/bjoc.20.134

• studies we also realized that the masked β-AA derivatives 2 undergo enantioselective β-addition to allenoates 3 under chiral ammonium salt catalysis (Scheme 1B) [18]. Interestingly, hereby we also found that the use of alternative catalyst systems (i.e., tertiary phosphines) allows for a γ-selective

Generation of alkyl and acyl radicals by visible-light photoredox catalysis: direct activation of C–O bonds in organic transformations

• Mithu Roy,
• Bitan Sardar,
• Itu Mallick and
• Dipankar Srimani

Beilstein J. Org. Chem. 2024, 20, 1348–1375, doi:10.3762/bjoc.20.119

• product. The photomediated formation of acyl radicals directly from acids mostly employs DMDC or phosphines (e.g., PPh3, PMe2Ph) as additives and [Ir(III)] as photocatalyst. In 2022, Chu and co-workers [32] developed a protocol to form acyl radicals directly from acids utilizing Ph2S as activator and the

• directly activated via photoredox catalysis. In 2018, Doyle and co-workers [54] documented a catalytic method for the deoxygenation of benzylic alcohols to toluenes, utilizing phosphines and photoredox catalyst under visible-light irradiation (Scheme 18). In this method, they were able to synthesize

Ligand effects, solvent cooperation, and large kinetic solvent deuterium isotope effects in gold(I)-catalyzed intramolecular alkene hydroamination

• Ruichen Lan,
• Brock Yager,
• Yoonsun Jee,
• Cynthia S. Day and
• Amanda C. Jones

Beilstein J. Org. Chem. 2024, 20, 479–496, doi:10.3762/bjoc.20.43

• -withdrawing phosphines. A DCM/alcohol cooperative effect was quantified, and a continuum of isotope effects was measured with low KIE’s in the absence of deuterated alcoholic solvent, increasing to large solvent KIE’s when comparing reactions in pure MeOH to those in pure MeOH-d4. The effects are interpreted

• undertaking a 1H NMR spectroscopic kinetic survey of solvent, ligand, and substituent effects on the general reaction 1 → 3 (with a variety of N-protecting groups), to supplement known qualitative observations. We found that, (1) electron-withdrawing phosphines accelerate hydroamination, (2) reactions are

• understood to be especially prone to decomposition [20]. Further enhancement of stability can be achieved by utilizing tris(biphenyl)phosphines, thus enabling efficient intermolecular hydroamination [22]. Our results reveal the optimal ligand demands for alkene hydroamination – phosphines with electron

Using the phospha-Michael reaction for making phosphonium phenolate zwitterions

• Matthias R. Steiner,
• Max Schmallegger,
• Larissa Donner,
• Johann A. Hlina,
• Christoph Marschner,
• Judith Baumgartner and
• Christian Slugovc

Beilstein J. Org. Chem. 2024, 20, 41–51, doi:10.3762/bjoc.20.6

• powerful tool for performing organic reactions [1] and polymerizations [2]. In this context phosphines have proven to be potent Lewis-base catalysts [3][4] for a variety of reactions [5], including but not limited to Rauhut–Currier [6], Morita–Baylis–Hillman [7], and Michael reactions [8][9][10]. In all

• candidates as well. Ortho-hydroxy-substituted phosphines have been mainly used as chelating ligands for metal complexes until recently [16][17][18]. Further, ortho-hydroxy phosphines have been used for the synthesis of probes in metabolic labeling [19], as a photocatalyst in the defluoroalkylation of

• trifluoromethyl groups [20] and the cross-coupling of aryl halides [21]. Like phosphonium salts in general are used as catalysts [22][23], phosphonium salts based on ortho-hydroxy-substituted phosphines received particular attention because of their zwitterionic nature and have been used as catalysts in the

Application of N-heterocyclic carbene–Cu(I) complexes as catalysts in organic synthesis: a review

• Nosheen Beig,
• Varsha Goyal and
• Raj K. Bansal

Beilstein J. Org. Chem. 2023, 19, 1408–1442, doi:10.3762/bjoc.19.102

• ligands in organometallic chemistry. After the first synthesis of stable monomeric NHCs, spectroscopic studies promptly revealed their similarity with phosphines. Indeed, both these classes of ligands are σ-donor ligands with low π-backdonating character [16][17]. In the beginning, the NHCs were perceived

Selective and scalable oxygenation of heteroatoms using the elements of nature: air, water, and light

• Damiano Diprima,
• Hannes Gemoets,
• Stefano Bonciolini and
• Koen Van Aken

Beilstein J. Org. Chem. 2023, 19, 1146–1154, doi:10.3762/bjoc.19.82

• reaction conditions were also applicable to substrates containing other heteroatoms (i.e., P and Se). This allowed us to broaden the scope of the protocol to phosphinoxides (2o, 2p) from phosphines, organophosphates (2q, 2r) from organophosphites, and selenoxide 2s from selenides. Finally, to prove the

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

Aromatic C–H bond functionalization through organocatalyzed asymmetric intermolecular aza-Friedel–Crafts reaction: a recent update

• Anup Biswas

Beilstein J. Org. Chem. 2023, 19, 956–981, doi:10.3762/bjoc.19.72

• the reaction partners in a highly ordered three dimensional transition state through noncovalent interactions (like H-bonding, π–π interactions) thus promoting the stereoselective reaction. Examples of covalent bonding organocatalysts are amines [6][7], N-heterocyclic carbenes [8][9], phosphines [10

NaI/PPh₃-catalyzed visible-light-mediated decarboxylative radical cascade cyclization of N-arylacrylamides for the efficient synthesis of quaternary oxindoles

• Dan Liu,
• Yue Zhao and
• Frederic W. Patureau

Beilstein J. Org. Chem. 2023, 19, 57–65, doi:10.3762/bjoc.19.5

• conditions. Some diverse phosphines were then screened. Aromatic phosphines performed best (Table 1, entries 8 and 9), the cheapest PPh3 remaining however optimal. In contrast, tricyclohexylphosphine PCy3 performed poorly (Table 1, entry 10), and bulky tri-o-tolylphosphine almost shut down the reaction

Comparison of crystal structure and DFT calculations of triferrocenyl trithiophosphite’s conformance

• Ruslan P. Shekurov,
• Mikhail N. Khrizanforov,
• Ilya A. Bezkishko,
• Tatiana P. Gerasimova,
• Almaz A. Zagidullin,
• Daut R. Islamov and
• Vasili A. Miluykov

Beilstein J. Org. Chem. 2022, 18, 1499–1504, doi:10.3762/bjoc.18.157

• phosphines, a relatively small number of trivalent phosphorus derivatives has been used to construct multiferrocene compounds. The use of ferrocene derivatives containing a phosphorus–sulfur bond is a promising direction, since coordination with a metal atom can occur both at the phosphorus and sulfur atoms

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

• objects of growing interest in the fields of coordination chemistry [3][4][5] and asymmetric catalysis [6][7]. Due to the sp2-hybridization of the phosphorus atom, phosphaferrocenes are commonly regarded as phosphorus ligands with weaker σ-donor character than classical tertiary phosphines and stronger π

• mediator in the synthesis of asymmetric phosphines starting from white phosphorus [15]. Moreover, the presence of the lone pair of the P atom opens the route to polynuclear complexes [16][17][18] and coordination polymers [19][20][21] with the mixed σ-/π-coordination mode, which is not typical for

Tri(n-butyl)phosphine-promoted domino reaction for the efficient construction of spiro[cyclohexane-1,3'-indolines] and spiro[indoline-3,2'-furan-3',3''-indolines]

• Hui Zheng,
• Ying Han,
• Jing Sun and
• Chao-Guo Yan

Beilstein J. Org. Chem. 2022, 18, 669–679, doi:10.3762/bjoc.18.68

• reagents to give versatile cyclic compounds with recovery of the tertiary phosphine [25][26][27][28][29][30][31][32][33][34]. The superior catalytic ability of tertiary phosphines was primarily attributed to their excellent nucleophilicity as a nucleophile trigger and decent cleaving ability as a leaving

New advances in asymmetric organocatalysis

• Radovan Šebesta

Beilstein J. Org. Chem. 2022, 18, 240–242, doi:10.3762/bjoc.18.28

• repertoire of chemical transformations that are amenable to organocatalysis [14]. Within the realm of covalent activation, chiral carbenes and phosphines are diverse and structurally rich groups of catalysts. The synthetic scope was greatly expanded by noncovalent activation via a range of proton-mediated

Diametric calix[6]arene-based phosphine gold(I) cavitands

• Gabriele Giovanardi,
• Andrea Secchi,
• Arturo Arduini and
• Gianpiero Cera

Beilstein J. Org. Chem. 2022, 18, 190–196, doi:10.3762/bjoc.18.21

• macrocyclic cavity. Keywords: 1,2,3-alternate conformation; calix[6]arenes; gold(I) catalysis; phosphines; Introduction One of the latest challenges in supramolecular chemistry is the design and development of novel macrocyclic-based entities able to influence the catalytic activities of the metal center [1

• ][2][3]. In this context, phosphines represent the most exploited class of ligands in homogeneous catalysis [4]. Noteworthy, reason of their wide applicability is the possibility of controlling the steric and electronic properties by proper functionalizations, hence tuning the catalytic properties of

Catalyzed and uncatalyzed procedures for the syntheses of isomeric covalent multi-indolyl hetero non-metallides: an account

• Ranadeep Talukdar

Beilstein J. Org. Chem. 2021, 17, 2102–2122, doi:10.3762/bjoc.17.137

• similar mechanism (Scheme 8b) [62][63]. The reduced form of indole, i.e., indoline 50 coordinates with the Lewis acid to form a complex which activates PhSiH3 (frustrated Lewis pair) for silylation (69, Scheme 8b). Phosphines The base-mediated syntheses of bis(indol-2-yl)phosphines 76 and 78 were

• )silanes reported by Han. Base-mediated syntheses of bis and tris(indol-2-yl)phosphines. Synthesis of bis(indol-2-yl)sulfides using SL2-type reagents. Synthesis of 2,3’- and 2,2’-bis(indolyl)sulfides using disulfides as substrates. Synthesis of diindol-2-ylsulfide (84) from 2-iodoindole (92) and thiourea

Electron-rich triarylphosphines as nucleophilic catalysts for oxa-Michael reactions

• Susanne M. Fischer,
• Simon Renner,
• A. Daniel Boese and
• Christian Slugovc

Beilstein J. Org. Chem. 2021, 17, 1689–1697, doi:10.3762/bjoc.17.117

• stability of the phosphines was also evaluated and the most electron-rich TMTPP was found to be only slightly more sensitive to oxidation than TPP. Finally, the catalysts were employed in the oxa-Michael polymerization of 2-hydroxyethyl acrylate. With TMTPP polymers characterized by number average molar

• chemistry; organocatalysis; phosphine; solvent-free synthesis; Introduction Phosphines are potent nucleophiles that are used as catalysts in many reactions, like Rauhut–Currier, Morita–Baylis–Hillman or Michael reactions [1][2][3]. The first step of these reactions is a conjugate addition of the phosphine

• mixture was dissolved in dichloromethane and precipitated from diethyl ether resulting in about 50% polymer yield featuring Mn values of 1500–1800 g/mol [30]. Next, the oxidation stability of the catalysts was tested. For this purpose, the three different phosphines were exposed to air for 14 d in dark

Recent advances in palladium-catalysed asymmetric 1,4–additions of arylboronic acids to conjugated enones and chromones

• Jan Bartáček,
• Jan Svoboda,
• Martin Kocúrik,
• Jaroslav Pochobradský,
• Alexander Čegan,
• Miloš Sedlák and
• Jiří Váňa

Beilstein J. Org. Chem. 2021, 17, 1048–1085, doi:10.3762/bjoc.17.84

• (phosphines, NHC-carbenes, bisoxazolines, pyridine-oxazolines, and miscellaneous) is used. Review Catalytic systems based on phosphine ligands A pioneering work on the enantioselective addition of boron-derived carbon nucleophiles to cyclic enones was published by the group of Miyaura et al. in 2005 [32