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

• arenes via palladium-catalyzed electrooxidation, further showcasing the versatility and potential of this approach in organic synthesis (Scheme 42b) [58]. These methodologies underline the expanding role of palladium catalysis in electrochemical transformations, offering robust strategies for the

Multicomponent syntheses of pyrazoles via (3 + 2)-cyclocondensation and (3 + 2)-cycloaddition key steps

• Ignaz Betcke,
• Alissa C. Götzinger,
• Maryna M. Kornet and
• Thomas J. J. Müller

Beilstein J. Org. Chem. 2024, 20, 2024–2077, doi:10.3762/bjoc.20.178

• process with hydrazine hydrate to give 3,5-substituted pyrazoles 136 (Scheme 47) [150]. Notably, nitro groups are reduced to amines due to the reductive conditions. Furthermore, neither aliphatic hydroxyiminoyl chlorides nor internal alkynes are competent substrates in this transformation. Palladium

• catalysis not only enables the synthesis of alkynones, but also facilitates the introduction of protected alkynal moieties, which can be converted to pyrazoles in a one-pot fashion. Sonogashira coupling is particularly well-suited for this purpose. The alkynylation of propynal diethyl acetal (140) and

Benzylic C(sp³)–H fluorination

• Alexander P. Atkins,
• Alice C. Dean and
• Alastair J. J. Lennox

Beilstein J. Org. Chem. 2024, 20, 1527–1547, doi:10.3762/bjoc.20.137

• monofluorination radiolabelling using [18F]NFSI. Electrophilic fluorination of benzylic C–H bonds has been demonstrated as a powerful approach. However, these techniques can be constrained to defined substrate classes and the requirement of using strong bases. Palladium catalysis Palladium-catalysed chemistry is

Palladium-catalyzed three-component radical-polar crossover carboamination of 1,3-dienes or allenes with diazo esters and amines

• Geng-Xin Liu,
• Xiao-Ting Jie,
• Ge-Jun Niu,
• Li-Sheng Yang,
• Xing-Lin Li,
• Jian Luo and
• Wen-Hao Hu

Beilstein J. Org. Chem. 2024, 20, 661–671, doi:10.3762/bjoc.20.59

• multicomponent reaction protocol. Keywords: carboamination; diazo chemistry; palladium catalysis; radical-polar crossover; three-component reaction; Introduction Since the discovery of the existence of non-canonical amino acids (AAs) in organisms, such structural motifs have attracted considerable attention

• be difficult to achieve using either radical or polar chemistry alone. In recent years, Gevorgyan, Glorius, Huang and their co-workers reported elegant examples of the carboamination of 1,3-dienes with unactivated alkyl halides and amines under photoinduced palladium catalysis via a radical-polar

Mono or double Pd-catalyzed C–H bond functionalization for the annulative π-extension of 1,8-dibromonaphthalene: a one pot access to fluoranthene derivatives

• Nahed Ketata,
• Linhao Liu,
• Ridha Ben Salem and
• Henri Doucet

Beilstein J. Org. Chem. 2024, 20, 427–435, doi:10.3762/bjoc.20.37

Synthetic approach to 2-alkyl-4-quinolones and 2-alkyl-4-quinolone-3-carboxamides based on common β-keto amide precursors

• Yordanka Mollova-Sapundzhieva,
• Plamen Angelov,
• Danail Georgiev and
• Pavel Yanev

Beilstein J. Org. Chem. 2023, 19, 1804–1810, doi:10.3762/bjoc.19.132

• , limiting the reaction time to 60–90 min under these conditions allowed some of the N-hydroxy derivatives 4 to be isolated in good yield (Table 5), even though it did not entirely prevent the formation of products 5. Palladium catalysis was not appropriate for the hydrogenation of compounds 3f and 3g

One-pot nucleophilic substitution–double click reactions of biazides leading to functionalized bis(1,2,3-triazole) derivatives

• Hans-Ulrich Reissig and
• Fei Yu

Beilstein J. Org. Chem. 2023, 19, 1399–1407, doi:10.3762/bjoc.19.101

• reductive ring openings of bis(1,2,3-triazole) derivative 21 to divalent carbohydrate mimetics with hydrogen under palladium catalysis or with samarium diiodide did not proceed cleanly and need further optimization. Earlier approaches to multivalent carbohydrate mimetics B, D or F based on enantiopure

Pyridine C(sp²)–H bond functionalization under transition-metal and rare earth metal catalysis

• Haritha Sindhe,
• Malladi Mounika Reddy,
• Karthikeyan Rajkumar,
• Akshay Kamble,
• Amardeep Singh,
• Anand Kumar and
• Satyasheel Sharma

Beilstein J. Org. Chem. 2023, 19, 820–863, doi:10.3762/bjoc.19.62

• hydrolyzed to get the corresponding ketones. In 2018, Albéniz and group [99] reported the direct C3-arylation of pyridines with the help of bipy-6-OH as coordinating ligand under palladium catalysis (Scheme 29). In most of the cases the arylated pyridines 152 were obtained as mixtures of ortho-/meta-/para

• and 163 through a two-fold C–H activation under palladium catalysis. Silver carbonate and 2,6-lutidine were found to be an effective base and ligand, respectively, for providing the desired products 164 and 165 in good yields (Scheme 31). In 2015, an economic route for copper-catalyzed biaryl coupling

Palladium-catalyzed enantioselective three-component synthesis of α-arylglycine derivatives from glyoxylic acid, sulfonamides and aryltrifluoroborates

• Bastian Jakob,
• Nico Schneider,
• Luca Gengenbach and
• Georg Manolikakes

Beilstein J. Org. Chem. 2023, 19, 719–726, doi:10.3762/bjoc.19.52

• products. Keywords: amino acids; asymmetric catalysis; multicomponent reaction; palladium catalysis; Petasis reaction; sulfonamides; Introduction α-Amino acids play a crucial role in every aspect of our human life [1]. They are important synthetic intermediates in the chemical industry and used for the

Strategies in the synthesis of dibenzo[b,f]heteropines

• David I. H. Maier,
• Barend C. B. Bezuidenhoudt and
• Charlene Marais

Beilstein J. Org. Chem. 2023, 19, 700–718, doi:10.3762/bjoc.19.51

• thioethers from aryl halides and triflates through palladium catalysis [50][51]. Scheme 10 provides a retrosynthesis of amination in the synthesis of dibenzo[b,f]azepine 45 as an example. Arnold et al. [30] reported an excellent method for the convergent synthesis of variable sized dibenzo-fused heterocycles

Transition-metal-catalyzed C–H bond activation as a sustainable strategy for the synthesis of fluorinated molecules: an overview

• Louis Monsigny,
• Floriane Doche and
• Tatiana Besset

Beilstein J. Org. Chem. 2023, 19, 448–473, doi:10.3762/bjoc.19.35

• electron-withdrawing groups were functionalized and the expected products were isolated in moderate to high yields (4a–f, 58–91%). Palladium catalysis: Several works have been reported for the palladium-catalyzed trifluoromethylthiolation reaction of various aromatic compounds 5 by C–H bond activation and

• Several research groups have been interested in the development of strategies for the formation of vinylic C(sp2)–SCF3 bonds, offering an efficient tool towards the synthesis of challenging Z-isomers. Palladium catalysis: In 2018, Bouillon and Besset described the first example of a selective palladium

• palladium catalysis Very recently, the palladium-catalyzed trifluoromethylselenolation of (hetero)aromatic and olefinic derivatives has been investigated by the group of Billard using similar catalytic systems as those depicted for the trifluoromethylthiolation reactions. Indeed, using amides 37 derived

Sequential hydrozirconation/Pd-catalyzed cross coupling of acyl chlorides towards conjugated (2E,4E)-dienones

• Benedikt Kolb,
• Daniela Silva dos Santos,
• Sanja Krause,
• Anna Zens and
• Sabine Laschat

Beilstein J. Org. Chem. 2023, 19, 176–185, doi:10.3762/bjoc.19.17

• ; hydrozirconation; palladium catalysis; Schwartz's reagent; terpenes; Introduction Conjugated dienones are recurring structural motifs in natural products. Several biologically relevant compounds carry (2Ε,4E)-unsaturated ketones or the corresponding esters or amides. Selected examples are clifednamide H (1) which

Synthesis and investigation on optical and electrochemical properties of 2,4-diaryl-9-chloro-5,6,7,8-tetrahydroacridines

• Najeh Tka,
• Mohamed Adnene Hadj Ayed,
• Mourad Ben Braiek,
• Mahjoub Jabli and
• Peter Langer

Beilstein J. Org. Chem. 2021, 17, 2450–2461, doi:10.3762/bjoc.17.162

Methodologies for the synthesis of quaternary carbon centers via hydroalkylation of unactivated olefins: twenty years of advances

• Thiago S. Silva and
• Fernando Coelho

Beilstein J. Org. Chem. 2021, 17, 1565–1590, doi:10.3762/bjoc.17.112

The preparation and properties of 1,1-difluorocyclopropane derivatives

• Kymbat S. Adekenova,
• Peter B. Wyatt and
• Sergazy M. Adekenov

Beilstein J. Org. Chem. 2021, 17, 245–272, doi:10.3762/bjoc.17.25

• reaction of 2-(2,2-difluorocyclopropyl)naphthalene (167) with sodium arylsulfinates 168 under palladium catalysis afforded the 2-fluoroallylic sulfones 166 in moderate to good yields with (Z)-selectivity. This method showed a good compatibility with a broad range of substrates and substituents. As

Novel library synthesis of 3,4-disubstituted pyridin-2(1H)-ones via cleavage of pyridine-2-oxy-7-azabenzotriazole ethers under ionic hydrogenation conditions at room temperature

• Romain Pierre,
• Anne Brethon,
• Sylvain A. Jacques,
• Aurélie Blond,
• Sandrine Chambon,
• Sandrine Talano,
• Catherine Raffin,
• Branislav Musicki,
• Claire Bouix-Peter,
• Loic Tomas,
• Gilles Ouvry,
• Rémy Morgentin,
• Laurent F. Hennequin and
• Craig S. Harris

Beilstein J. Org. Chem. 2021, 17, 156–165, doi:10.3762/bjoc.17.16

• goal of creating a rapid, 3-step route requiring a single preparative LC–MS purification at the end of the sequence (Figure 1). Results and Discussion Exploration of the C-3 amide vector: formation of the pyridine-2-(1H)-one motif by palladium catalysis We decided to validate the route by preparing

Recent developments in enantioselective photocatalysis

• Callum Prentice,
• James Morrisson,
• Andrew D. Smith and
• Eli Zysman-Colman

Beilstein J. Org. Chem. 2020, 16, 2363–2441, doi:10.3762/bjoc.16.197

When metal-catalyzed C–H functionalization meets visible-light photocatalysis

• Lucas Guillemard and
• Joanna Wencel-Delord

Beilstein J. Org. Chem. 2020, 16, 1754–1804, doi:10.3762/bjoc.16.147

Allylic cross-coupling using aromatic aldehydes as α-alkoxyalkyl anions

• Akihiro Yuasa,
• Kazunori Nagao and
• Hirohisa Ohmiya

Beilstein J. Org. Chem. 2020, 16, 185–189, doi:10.3762/bjoc.16.21

• rearrangement and then successfully trapped with aryl bromides under palladium catalysis (Scheme 1). This system was extended to an asymmetric version using the chiral α-silyloxybenzylcopper(I) species having a chiral NHC ligand. In the asymmetric system, one example of allylic carbonate was used as the carbon

Recent advances in transition-metal-catalyzed incorporation of fluorine-containing groups

• Xiaowei Li,
• Xiaolin Shi,
• Xiangqian Li and
• Dayong Shi

Beilstein J. Org. Chem. 2019, 15, 2213–2270, doi:10.3762/bjoc.15.218

• different catalysts, such as palladium, copper, silver, iron, nickel, ruthenium, cobalt, etc. Palladium catalysis Palladium is a member of the nickel triad in the periodic table, and palladium complexes exist in three oxidation states, Pd(0), Pd(II), and Pd(IV). Straightforward interconversion between

Regioselective Pd-catalyzed direct C1- and C2-arylations of lilolidine for the access to 5,6-dihydropyrrolo[3,2,1-ij]quinoline derivatives

• Hai-Yun Huang,
• Haoran Li,
• Thierry Roisnel,
• Jean-François Soulé and
• Henri Doucet

Beilstein J. Org. Chem. 2019, 15, 2069–2075, doi:10.3762/bjoc.15.204

Synthesis of pyrrolo[1,2-a]quinolines by formal 1,3-dipolar cycloaddition reactions of quinolinium salts

• Anthony Choi,
• Rebecca M. Morley and
• Iain Coldham

Beilstein J. Org. Chem. 2019, 15, 1480–1484, doi:10.3762/bjoc.15.149

• the adducts 9 and 10. The bromide 15b was coupled with phenylboronic acid using palladium catalysis to give derivative 16 (the chloride 15a was inert under these conditions). The ability to prepare halogenated derivatives and to undergo palladium coupling demonstrates further versatility of these

Synthesis of dipolar molecular rotors as linkers for metal-organic frameworks

• Sebastian Hamer,
• Fynn Röhricht,
• Marius Jakoby,
• Ian A. Howard,
• Xianghui Zhang,
• Christian Näther and
• Rainer Herges

Beilstein J. Org. Chem. 2019, 15, 1331–1338, doi:10.3762/bjoc.15.132

• higher yields. Starting from commercially available 5,6-dibromo-1,3-benzodioxole (13a) and literature known 6,7-dibromo-1,4-benzodioxane (13b) [55], dicyanation of the dibromo compounds was achieved with zinc(II) cyanide under palladium catalysis [56]. The typical Rosemund–von-Braun reaction using copper

Multicomponent reactions (MCRs): a useful access to the synthesis of benzo-fused γ-lactams

• Edorta Martínez de Marigorta,
• Jesús M. de Los Santos,
• Ana M. Ochoa de Retana,
• Javier Vicario and
• Francisco Palacios

Beilstein J. Org. Chem. 2019, 15, 1065–1085, doi:10.3762/bjoc.15.104

• hydrazine 114 and sulfur dioxide (Scheme 33). Rearrangement of the so-obtained intermediate 119, through radical 120, would provide oxindole 115. The same acrylamide 113 (R1 = H) has been recently used in another multicomponent synthesis along with CO (23) and benzodiazepine derivative 121 under palladium

• catalysis to give a 1:1 mixture of diastereoisomers of oxindole 122 with good yield (Scheme 34) [111]. In this case, the process consists in a palladium-catalysed cyclization followed by a carbonylation and anion capture. Several analogues of (2-oxoindolin-3-yl)methanesulfonohydrazides 115 have been

Recent advances in hypervalent iodine(III)-catalyzed functionalization of alkenes

• Xiang Li,
• Pinhong Chen and
• Guosheng Liu

Beilstein J. Org. Chem. 2018, 14, 1813–1825, doi:10.3762/bjoc.14.154

• . Compared to the diverse reactivity profiles of transition metal-catalyzed functionalization of alkenes, hypervalent iodine (III)-mediated reactions are limited to nucleophilic substitution processes. Recently, Liu and co-workers reported a novel cooperative strategy by combining palladium catalysis and