Advances in radical peroxidation with hydroperoxides

• Oleg V. Bityukov,
• Pavel Yu. Serdyuchenko,
• Andrey S. Kirillov,
• Gennady I. Nikishin,
• Vera A. Vil’ and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2024, 20, 2959–3006, doi:10.3762/bjoc.20.249

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

• benzylic position (Scheme 31). 1.3.2 Co-assisted anodic oxidation. In 2021, Xu and colleagues developed an electrocatalytic approach for the intramolecular oxidative allylic amination and C–H alkylation using cobalt–salen complexes as catalysts [43]. In this reaction, the cobalt catalyst [Co(II)] is first

Advancements in hydrochlorination of alkenes

• Daniel S. Müller

Beilstein J. Org. Chem. 2024, 20, 787–814, doi:10.3762/bjoc.20.72

• the metal-catalyzed hydrochlorination of alkenes based on MH HAT reactions (Scheme 23) [80]. They discovered that a combination of a cobalt catalyst, a silane, and tosyl chloride promoted the hydrochlorination of terminal unactivated alkenes. The scope of the reaction is relatively broad when

Clauson–Kaas pyrrole synthesis using diverse catalysts: a transition from conventional to greener approach

• Dileep Kumar Singh and
• Rajesh Kumar

Beilstein J. Org. Chem. 2023, 19, 928–955, doi:10.3762/bjoc.19.71

• aromatization steps led to product 43 upon catalyst regeneration. Recently, Ryabchuk et al. [74] used the 3d-metal cobalt catalyst Co/NGr-C@SiO2-L under solvent-free conditions to synthesize various N-aryl-substituted pyrroles 45 in 50–88% yields from the corresponding nitroarenes 44 via the Clauson–Kaas

Recent developments and trends in the iron- and cobalt-catalyzed Sonogashira reactions

• Surendran Amrutha,
• Sankaran Radhika and
• Gopinathan Anilkumar

Beilstein J. Org. Chem. 2022, 18, 262–285, doi:10.3762/bjoc.18.31

• recovered and reused, but it could also result in a reduced metal contamination of the products. However, most of the immobilized catalysts suffer from some problems like catalyst deactivation, low turnover numbers, and also leaching of metal. A new heterogeneous cobalt catalyst (Co@imine-porous organic

• without any remarkable decrease in its catalytic activity. A novel cobalt catalyst with cobalt immobilized on nanochitosan fibers (Co-DMM@MNPs/chitosan) was fabricated using dimethyl malonate [36] and its applicability tested in a Sonogashira coupling reaction. The catalyst was found to be highly active

• clearly shown that the complex of Co-N-heterocyclic ligand exhibits a higher activity. Sonogashira cross-coupling reactions were also reported by making use of a heterogeneous, efficient and green cobalt catalyst obtained through complexation of cobalt with methyl salicylate-functionalized chitosan fibres

On the application of 3d metals for C–H activation toward bioactive compounds: The key step for the synthesis of silver bullets

• Renato L. Carvalho,
• Amanda S. de Miranda,
• Mateus P. Nunes,
• Roberto S. Gomes,
• Guilherme A. M. Jardim and
• Eufrânio N. da Silva Júnior

Beilstein J. Org. Chem. 2021, 17, 1849–1938, doi:10.3762/bjoc.17.126

Regioselective cobalt(II)-catalyzed [2 + 3] cycloaddition reaction of fluoroalkylated alkynes with 2-formylphenylboronic acids: easy access to 2-fluoroalkylated indenols

• Tatsuya Kumon,
• Miroku Shimada,
• Jianyan Wu,
• Shigeyuki Yamada and
• Tsutomu Konno

Beilstein J. Org. Chem. 2020, 16, 2193–2200, doi:10.3762/bjoc.16.184

• -fluoroalkylated indenols, together with a very small amount of 3-fluoroalkylated indanones as side products. Keywords: [2 + 3] cycloaddition; cobalt catalyst; fluorine-containing; indenols; regioselective; Introduction 2,3-Disubstituted indenol derivatives are important compounds possessing high potential due

• -fluoroalkylated indanones are shown in Scheme 5 [28][38]. Thus, the reaction presumably proceeds as follows: (1) transmetalation of the cobalt catalyst with 2-formylphenylboronic acids (2) gives the arylcobalt species Int-1, (2) insertion of the alkyne 1 into the [Co]–Ar bond (see Int-2a) [39], (3) migration

Photocatalysis with organic dyes: facile access to reactive intermediates for synthesis

• Stephanie G. E. Amos,
• Marion Garreau,
• Luca Buzzetti and
• Jerome Waser

Beilstein J. Org. Chem. 2020, 16, 1163–1187, doi:10.3762/bjoc.16.103

A systematic review on silica-, carbon-, and magnetic materials-supported copper species as efficient heterogeneous nanocatalysts in “click” reactions

• Pezhman Shiri and
• Jasem Aboonajmi

Beilstein J. Org. Chem. 2020, 16, 551–586, doi:10.3762/bjoc.16.52

• phenol 8 was generated by the reaction of 2-hydroxybenzaldehyde (5) and o‐phenylenediamine (7) at rt using a cobalt catalyst. In the next step, a benzimidazole-containing aldehyde 9 was obtained by the reaction of 6 with benzimidazole-substituted phenol 8. This ligand was immobilized on propylamine

Synthesis of triphenylene-fused phosphole oxides via C–H functionalizations

• Md. Shafiqur Rahman and
• Naohiko Yoshikai

Beilstein J. Org. Chem. 2020, 16, 524–529, doi:10.3762/bjoc.16.48

• catalyst (Scheme 2). This one-pot construction of the benzo[b]phosphole core ensured the preferential phosphole ring closure in proximity of the alkoxy group of the arylzinc reagent 1 (regioselectivity of ≈3:1), presumably due to a secondary interaction between the MOM group and the cobalt catalyst during

Recent developments in photoredox-catalyzed remote ortho and para C–H bond functionalizations

• Rafia Siddiqui and
• Rashid Ali

Beilstein J. Org. Chem. 2020, 16, 248–280, doi:10.3762/bjoc.16.26

• benzothiazoles via oxidant-free C–H thiolation: On the other hand, a novel dual photoredox catalytic system of photoredox catalyst 11 and a cobalt catalyst was designed by Wu and Lei for the construction of benzothiazoles [101]. Because of the properties of the photoredox catalyst 11, the reaction was carried

Combination of multicomponent KA² and Pauson–Khand reactions: short synthesis of spirocyclic pyrrolocyclopentenones

• Riccardo Innocenti,
• Elena Lenci,
• Gloria Menchi and
• Andrea Trabocchi

Beilstein J. Org. Chem. 2020, 16, 200–211, doi:10.3762/bjoc.16.23

• –Khand reaction (Table 1, entry 13), possibly due to a coordinating effect towards the cobalt catalyst. Such an effect was confirmed when the N-tosylpiperidone was used as the ketone component, as also in this case the presence of the tosyl group impaired the acetylated KA2 adduct from reacting under

Hydroarylations by cobalt-catalyzed C–H activation

• Rajagopal Santhoshkumar and
• Chien-Hong Cheng

Beilstein J. Org. Chem. 2018, 14, 2266–2288, doi:10.3762/bjoc.14.202

• temperature (Scheme 7) [48]. These reactions resemble the Ni(0)-catalyzed hydroheteroarylation reaction [49]. In addition, imines 9 and 11 bearing a p-methoxyphenyl (PMP) group were also treated with internal alkynes in the presence of a cobalt catalyst generated from CoBr2, P(3-ClC6H4)3, and t-BuCH2MgBr at

• . Based on the mechanistic studies, a possible reaction mechanism for the hydroarylation reaction was proposed in Scheme 9. The reaction begins with the generation of an ambiguous low-valent cobalt catalyst from the reaction of CoBr2, ligand and Grignard reagent, which gives the alkane and MgX2 as the by

• -products. Then, coordination of the alkyne with the cobalt catalyst afforded B1 and the oxidative addition of C–H gave the cobalt complex B2. Intramolecular insertion of the Co–H bond into the alkyne and subsequent reductive elimination of the less-hindered alkenyl carbon with aryl group in B3 provides the

Cationic cobalt-catalyzed [1,3]-rearrangement of N-alkoxycarbonyloxyanilines

• Itaru Nakamura,
• Mao Owada,
• Takeru Jo and
• Masahiro Terada

Beilstein J. Org. Chem. 2018, 14, 1972–1979, doi:10.3762/bjoc.14.172

• , Aoba-ku, Sendai 980-8578 Japan 10.3762/bjoc.14.172 Abstract A cationic cobalt catalyst efficiently promoted the reaction of N-alkoxycarbonyloxyanilines at 30 °C, affording the corresponding ortho-aminophenols in good to high yields. As reported previously, our mechanistic studies including oxygen-18

• 1,3-bis(diphenylphosphino)propane (dppp), totally diminished the activity of cationic cobalt catalyst (Table 1, entries 6 and 7). Among metal chlorides examined, CoCl2 exhibited the best catalytic activity at 30 °C, affording the corresponding 2a in 68% yield (Table 1, entry 9), as reported previously

• group on the oxygen atom was readily isomerized to the ortho-aminophenol derivative under its preparing conditions in the absence of the cationic cobalt catalyst. In sharp contrast to alkoxycarbonyloxy groups, acyloxy groups, such as the benzoyloxy group, were not migrated to the ortho-position

Thiocarbonyl-enabled ferrocene C–H nitrogenation by cobalt(III) catalysis: thermal and mechanochemical

• Santhivardhana Reddy Yetra,
• Zhigao Shen,
• Hui Wang and
• Lutz Ackermann

Beilstein J. Org. Chem. 2018, 14, 1546–1553, doi:10.3762/bjoc.14.131

• essential nature of the cobalt catalyst (Table 1, entry 13). In contrast to the thiocarbonyl-assisted C–H amidation, the corresponding ketone failed thus far to deliver the desired product, under otherwise identical reaction conditions. With the optimized reaction conditions in hand, we explored the

• robustness of the cobalt-catalyzed ferrocene C–H amidation with a variety of 1,4,2-dioxazol-5-ones 2 (Scheme 1). Hence, the chemoselectivity of the cobalt catalyst was reflected by fully tolerating sensitive electrophilic functional groups, including amido, chloro, bromo and nitro substituents in the para

Three-component coupling of aryl iodides, allenes, and aldehydes catalyzed by a Co/Cr-hybrid catalyst

• Kimihiro Komeyama,
• Shunsuke Sakiyama,
• Kento Iwashita,
• Itaru Osaka and
• Ken Takaki

Beilstein J. Org. Chem. 2018, 14, 1413–1420, doi:10.3762/bjoc.14.118

• iodides, allenes, and aldehydes has been developed to afford multi-substituted homoallylic alcohols in a diastereoselective manner. Control experiments for understanding the reaction mechanism reveal that the cobalt catalyst is involved in the oxidative addition and carbometalation steps in the reaction

• three-component coupling reaction of aryl iodides, allenes, and aldehydes to produce highly substituted homoallylic alcohols in a diastereoselective manner has been demonstrated. In the coupling reaction, two catalysts played individual roles; the cobalt catalyst activated aryl iodides to form

Photocatalytic formation of carbon–sulfur bonds

• Alexander Wimmer and
• Burkhard König

Beilstein J. Org. Chem. 2018, 14, 54–83, doi:10.3762/bjoc.14.4

• generate a carbon-centred radical intermediate. The cobalt-catalyst is involved in two ways: oxidation and deprotonation of the radical species yielding the desired product and oxidation of the Eosin Y radical anion to close the photocatalytic cycle. The H2 evolution was not quantitative, which was

Unpredictable cycloisomerization of 1,11-dien-6-ynes by a common cobalt catalyst

• Abdusalom A. Suleymanov,
• Dmitry V. Vasilyev,
• Valentin V. Novikov,
• Yulia V. Nelyubina and
• Dmitry S. Perekalin

Beilstein J. Org. Chem. 2017, 13, 639–643, doi:10.3762/bjoc.13.62

Selected synthetic strategies to cyclophanes

• Sambasivarao Kotha,
• Mukesh E. Shirbhate and
• Gopalkrushna T. Waghule

Beilstein J. Org. Chem. 2015, 11, 1274–1331, doi:10.3762/bjoc.11.142

• ] have reported the synthesis of various pyridinophanes by a [2 + 2 + 2] cycloaddition reaction mediated by a cobalt catalyst (Scheme 51). To this end, different bisalkynes 271 were reacted with p-toluenenitrile (295, 1 mol equiv) in 1:1 ratio to obtain [2,4]pyridinophane 296 and [2,5]pyridinophane 297

Electrochemical selenium- and iodonium-initiated cyclisation of hydroxy-functionalised 1,4-dienes

• Philipp Röse,
• Steffen Emge,
• Jun-ichi Yoshida and
• Gerhard Hilt

Beilstein J. Org. Chem. 2015, 11, 174–183, doi:10.3762/bjoc.11.18

• ]. The synthesis of the 1,4-dienes was then accomplished utilising the cobalt-catalyst precursor and reducing conditions in the presence of zinc iodide for abstracting the bromide anions at room temperature. The TMS-protected allylic alcohol was applied in the cobalt-catalysed 1,4-hydrovinylation process

Building complex carbon skeletons with ethynyl[2.2]paracyclophanes

• Ina Dix,
• Lidija Bondarenko,
• Peter G. Jones,
• Thomas Oeser and
• Henning Hopf

Beilstein J. Org. Chem. 2014, 10, 2013–2020, doi:10.3762/bjoc.10.209

• triple bonds under the influence of a cobalt catalyst such as CpCo(CO)2 has been observed many times, notably by the Vollhardt group [12]. In our case, however, the process is not complete. Rather than yielding the expected biphenylenophane 27, the reaction stops at the stage of the cyclobutadiene

Recent advances in transition-metal-catalyzed intermolecular carbomagnesiation and carbozincation

• Kei Murakami and
• Hideki Yorimitsu

Beilstein J. Org. Chem. 2013, 9, 278–302, doi:10.3762/bjoc.9.34

• efficiently with good stereoselectivity (Scheme 33). A more versatile arylmetalation of dialkylacetylenes using arylzinc reagents in the presence of a cobalt catalyst was then reported by Yorimitsu and Oshima (Scheme 34, top) [115]. Treatment of dialkylacetylenes with arylzinc reagents in acetonitrile in the

C2-Alkylation of N-pyrimidylindole with vinylsilane via cobalt-catalyzed C–H bond activation

• Zhenhua Ding and
• Naohiko Yoshikai

Beilstein J. Org. Chem. 2012, 8, 1536–1542, doi:10.3762/bjoc.8.174

• with a vinylsilane was achieved by using a cobalt catalyst generated in situ from CoBr2, bathocuproine, and cyclohexylmagnesium bromide. The reaction allows coupling between a series of N-pyrimidylindoles and vinylsilanes at a mild reaction temperature of 60 °C, affording the corresponding alkylated

Miniemulsion polymerization as a versatile tool for the synthesis of functionalized polymers

• Daniel Crespy and
• Katharina Landfester

Beilstein J. Org. Chem. 2010, 6, 1132–1148, doi:10.3762/bjoc.6.130

• polystyrene nanoparticles were synthesized in emulsion and miniemulsion by non-covalently immobilized metallocene catalysts [67]. The catalytic polymerization of butadiene with a cobalt catalyst was found to give highly crystalline 1,2-polybutadiene with a particle size of 150–200 nm [68]. The