Ortho-ester-substituted diaryliodonium salts enabled regioselective arylocyclization of naphthols toward 3,4-benzocoumarins

• Ke Jiang,
• Cheng Pan,
• Limin Wang,
• Hao-Yang Wang and
• Jianwei Han

Beilstein J. Org. Chem. 2024, 20, 841–851, doi:10.3762/bjoc.20.76

• -positions to the ester group were all well-tolerated (Table 3). To gain further insights into the reaction mechanism, we conducted control experiments. Given the utility of diaryliodonium salts in radical chemistry, we introduced 2 equivalents of 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) or 2 equivalents

SOMOphilic alkyne vs radical-polar crossover approaches: The full story of the azido-alkynylation of alkenes

• Julien Borrel and
• Jerome Waser

Beilstein J. Org. Chem. 2024, 20, 701–713, doi:10.3762/bjoc.20.64

• , greatly increasing the molecular complexity of the starting substrate. Using radical chemistry would lead to a regioselective addition of azide radicals to the alkene, forming selectively the most stabilized C-centered radical. A prominent method for the generation of azide radicals relies on hypervalent

• azido-hydration reaction [18]. The homopropargylic azide was obtained in only 28% yield using phenyl vinyl ketone. Based on reported aza-alkynylation reactions [19][20][21][22][23] and modern azidation methods using radical chemistry [17][24][25][26] three approaches could be envisaged. All of them

Mechanisms for radical reactions initiating from N-hydroxyphthalimide esters

• Carlos R. Azpilcueta-Nicolas and
• Jean-Philip Lumb

Beilstein J. Org. Chem. 2024, 20, 346–378, doi:10.3762/bjoc.20.35

Radical chemistry in polymer science: an overview and recent advances

• Zixiao Wang,
• Feichen Cui,
• Yang Sui and
• Jiajun Yan

Beilstein J. Org. Chem. 2023, 19, 1580–1603, doi:10.3762/bjoc.19.116

• Zixiao Wang Feichen Cui Yang Sui Jiajun Yan School of Physical Science and Technology, ShanghaiTech University, 393 Middle Huaxia Rd., Shanghai, 201210, China 10.3762/bjoc.19.116 Abstract Radical chemistry is one of the most important methods used in modern polymer science and industry. Over the

• past century, new knowledge on radical chemistry has both promoted and been generated from the emergence of polymer synthesis and modification techniques. In this review, we discuss radical chemistry in polymer science from four interconnected aspects. We begin with radical polymerization, the most

• constantly acquire new inspirations from organic chemists. Dialogues on radical chemistry between the two communities will deepen the understanding of the two fields and benefit the humanity. Keywords: crosslinking; polymer surface modification; post-polymerization modification; radical chemistry; radical

C–H bond functionalization: recent discoveries and future directions

• Indranil Chatterjee

Beilstein J. Org. Chem. 2023, 19, 1568–1569, doi:10.3762/bjoc.19.114

• the abstraction of intramolecular hydrogen atoms. Radical chemistry is a viable alternative to the two-electron process, involving C–H bond functionalization in the absence of any ligand and using low-cost redox-active metals (Fe, Cu, Mn, etc.) rather than heavy metals (Rh, Ir, etc.). Although radical

Radical ligand transfer: a general strategy for radical functionalization

• David T. Nemoto Jr,
• Kang-Jie Bian,
• Shih-Chieh Kao and
• Julian G. West

Beilstein J. Org. Chem. 2023, 19, 1225–1233, doi:10.3762/bjoc.19.90

• challenging-to-generate “uncontrollable” species prone to side reactions to versatile reactive intermediates enabling construction of myriad C–C and C–X bonds. This maturation of free radical chemistry has been enabled by several advances, including the proliferation of efficient radical generation methods

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

Photoredox catalysis enabling decarboxylative radical cyclization of γ,γ-dimethylallyltryptophan (DMAT) derivatives: formal synthesis of 6,7-secoagroclavine

• Alessio Regni,
• Francesca Bartoccini and
• Giovanni Piersanti

Beilstein J. Org. Chem. 2023, 19, 918–927, doi:10.3762/bjoc.19.70

• generated by reductive decarboxylation, could add in an 8-endo-trig manner (common in radical chemistry) to the alkene and the resulting radical could be oxidized to the cation by the oxidized form of the photocatalyst to close the photocatalytic cycle, followed by formation of the double bond. Even though

Photocatalytic sequential C–H functionalization expediting acetoxymalonylation of imidazo heterocycles

• Deepak Singh,
• Shyamal Pramanik and
• Soumitra Maity

Beilstein J. Org. Chem. 2023, 19, 666–673, doi:10.3762/bjoc.19.48

• acetylating agent. The developed method is heavy-metal free, as shown by the use of inexpensive PTH, as well as a base-free approach, and involves aerial oxygen to generate exciting derivatives, which may prove to be valuable in the field of radical chemistry research in future. Strategies of C-3

Strategies to access the [5-8] bicyclic core encountered in the sesquiterpene, diterpene and sesterterpene series

• Cécile Alleman,
• Charlène Gadais,
• Laurent Legentil and
• François-Hugues Porée

Beilstein J. Org. Chem. 2023, 19, 245–281, doi:10.3762/bjoc.19.23

• -positive and Gram-negative bacteria (Scheme 31B). 4.4 Photocatalyzed oxidative ring expansion: alternative radical chemistry for pleuromutilin scaffold construction Following the advent of photoredox catalysis in ring-opening and ring-expansion chemistry [75], a new route was proposed by Foy and Pronin to

Combining the best of both worlds: radical-based divergent total synthesis

• Kyriaki Gennaiou,
• Antonios Kelesidis,
• Maria Kourgiantaki and
• Alexandros L. Zografos

Beilstein J. Org. Chem. 2023, 19, 1–26, doi:10.3762/bjoc.19.1

• of atom economy and protecting-group-free synthesis dominating the field of total synthesis. In this new era, total synthesis is moving towards natural efficacy by utilizing both the biosynthetic knowledge of divergent synthesis and the latest developments in radical chemistry. This contemporary

• chemical libraries with natural scaffolds for biological screening. The evidenced increase of divergent radical syntheses in the last few years indicates that this approach is here to change the way chemists will practice total synthesis in the future. Evolution of radical chemistry for organic synthesis

Visible-light-mediated copper photocatalysis for organic syntheses

• Yajing Zhang,
• Qian Wang,
• Zongsheng Yan,
• Donglai Ma and
• Yuguang Zheng

Beilstein J. Org. Chem. 2021, 17, 2520–2542, doi:10.3762/bjoc.17.169

• bonds and can be applied to radical chemistry. This review discusses copper-catalyzed reactions including alkene and alkyne, organic halide, and alkyl C–H functionalization. 3. Visible-light-mediated copper-catalyzed alkene and alkyne functionalization 3.1 Olefinic C–H functionalization and allylic

A visible-light-induced, metal-free bis-arylation of 2,5-dichlorobenzoquinone

• Pieterjan Winant and
• Wim Dehaen

Beilstein J. Org. Chem. 2021, 17, 2315–2320, doi:10.3762/bjoc.17.149

• precursor, potentially leading to both regioisomers and unwanted side products, complicating purification. As a result, accounts of bis-arylation using radical chemistry are scarce and report very low yields [29][30][31][32]. While transition-metal catalysis is a viable strategy, it is often based on

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

• , carbanion, and radical chemistry. Furthermore, gem-difluorocyclopropanes readily go through carbonylation, dehalogenation, and annulation, resulting in various useful materials. 2.1 Thermal rearrangements The substitution of hydrogen with fluorine in cyclopropane leads to a significant weakening of the C–C

• . Further applications of free radical chemistry have developed through the use of radical initiators under comparatively mild conditions to form cyclopropylmethyl radicals, which can readily release their strain by opening to give homoallyl radicals. gem-Difluorocyclopropanes, because of their

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

• catalytic system is extremely appealing. In that perspective, the scope of this review aims to present innovative reactions combining C–H activation and visible-light induced photocatalysis. Keywords: C–H activation; C–H functionalization; dual catalysis; photoredox catalysis; radical chemistry

Terpenes

• Jeroen S. Dickschat

Beilstein J. Org. Chem. 2019, 15, 2966–2967, doi:10.3762/bjoc.15.292

• initially formed terpene hydrocarbons can subsequently be modified by enzymatic oxidations that often involve radical chemistry. The non-functionalised hydrocarbons are volatile and often exhibit interesting odour properties [3]. As a consequence, these compounds may act as chemical signals such as

Vicinal difunctionalization of alkenes by four-component radical cascade reaction of xanthogenates, alkenes, CO, and sulfonyl oxime ethers

• Shuhei Sumino,
• Takahide Fukuyama,
• Mika Sasano,
• Ilhyong Ryu,
• Antoine Jacquet,
• Frédéric Robert and
• Yannick Landais

Beilstein J. Org. Chem. 2019, 15, 1822–1828, doi:10.3762/bjoc.15.176

• a single operation [1][2][3][4][5]. Needless to say, the contribution by radical chemistry is not trivial [5][6][7]. While alkenes and alkynes have served as efficient radical donor/acceptor type C2 synthons in multicomponent radical reactions, CO and isonitriles were shown to react as donor

Detection of therapeutic radiation in three-dimensions

• John A. Adamovics

Beilstein J. Org. Chem. 2017, 13, 1325–1331, doi:10.3762/bjoc.13.129

• the polymerization of acrylamide with N,N’-methylenebisacrylamide and various monomers to yield a cloud like precipitate in the aqueous gel [13]. Due to the nature of their radical chemistry, polymer gel dosimeters have several limitations. They are susceptible to atmospheric oxygen inhibiting the

Fates of imine intermediates in radical cyclizations of N-sulfonylindoles and ene-sulfonamides

• Hanmo Zhang,
• E. Ben Hay,
• Stephen J. Geib and
• Dennis P. Curran

Beilstein J. Org. Chem. 2015, 11, 1649–1655, doi:10.3762/bjoc.11.181

• '-formamidoethyl)-2-oxindoles. These transformations add new dimensions to the growing radical chemistry of ene-sulfonamides. (a) Radical reactions of ene-sulfonamides give diverse isolated products; (b) these products are often derived from transient imine intermediates. Isolation of stable imines strengthens the

Synthesis of tripodal catecholates and their immobilization on zinc oxide nanoparticles

• Franziska Klitsche,
• Julian Ramcke,
• Julia Migenda,
• Andreas Hensel,
• Tobias Vossmeyer,
• Horst Weller,
• Silvia Gross and
• Wolfgang Maison

Beilstein J. Org. Chem. 2015, 11, 678–686, doi:10.3762/bjoc.11.77

• ] were converted to the corresponding triscatecholates 11 and 13 by coupling to dopamine (Scheme 2). The resulting triscatecholates 11 and 13 may be used as synthetically flexible platforms for functionalizations of surfaces via either nucleophilic addition (to the Michael acceptor in 11) or radical

• chemistry after immobilization. Immobilization on ZnO NPs Three different catecholates were selected to study the binding properties to ZnO NPs (Figure 2). Monomeric PEG-catecholate 14 [46] and the tripodal homologue 3 were chosen to study the stability of the coatings and the particles in aqueous solution

Visible-light photoredox catalysis enabled bromination of phenols and alkenes

• Yating Zhao,
• Zhe Li,
• Chao Yang,
• Run Lin and
• Wujiong Xia

Beilstein J. Org. Chem. 2014, 10, 622–627, doi:10.3762/bjoc.10.53

• regioselectivity for the bromination of phenols and alkenes. Further development of photoredox catalysis in the context of radical chemistry and its application in other reactions are currently underway in our laboratory. Experimental General procedure for the bromination of phenols and alkenes To a 10 mL round

The renaissance of organic radical chemistry – deja vu all over again

• Corey R. J. Stephenson,
• Armido Studer and
• Dennis P. Curran

Beilstein J. Org. Chem. 2013, 9, 2778–2780, doi:10.3762/bjoc.9.312

• organic radical chemistry dates back over 110 years, and it has been thriving for decades because it continuously reinvents itself. Often this happens when groups of researchers with different interests and expertise immigrate to the field. About 30 years ago there began a flourishing period in the field

• of organic radical chemistry that delivered groundbreaking results, especially in organic synthesis. By the 1990’s, radical reactions (especially cyclizations) were broadly recognized as powerful tools to make molecules. This Renaissance I in organic radical chemistry was built on prior renaissances

• radical chemistry addressing all these major fields can be found in the recently published four-volume “Encyclopedia of Radicals in Chemistry, Biology and Materials” [2]. Over the past few years, the process has again come full circle as research in organic radical chemistry, especially synthetic radical

Damage of polyesters by the atmospheric free radical oxidant NO₃^•: a product study involving model systems

• Catrin Goeschen and
• Uta Wille

Beilstein J. Org. Chem. 2013, 9, 1907–1916, doi:10.3762/bjoc.9.225

• Catrin Goeschen Uta Wille ARC Centre of Excellence for Free Radical Chemistry and Biotechnology, School of Chemistry and Bio21 Institute, The University of Melbourne, 30 Flemington Road, Parkville, VIC 3010, Australia 10.3762/bjoc.9.225 Abstract Manufactured polymer materials are used in

Creating Complexity

• Donald Craig

Beilstein J. Org. Chem. 2013, 9, 1881–1882, doi:10.3762/bjoc.9.220

• of catalysis, radical chemistry, stereoselective synthesis and molecular diversity. I thank them warmly for their high-quality contributions, which demonstrate the central role of organic synthesis in all its guises, in the creation of complexity. Donald Craig London, July 2013

Aerobic radical multifunctionalization of alkenes using tert-butyl nitrite and water

• Daisuke Hirose and
• Tsuyoshi Taniguchi

Beilstein J. Org. Chem. 2013, 9, 1713–1717, doi:10.3762/bjoc.9.196

• the current work has shown that this old methodology still has a large potential. The development of other direct C–H functionalization reactions based on radical chemistry is currently on-going together with further optimization of the presented reaction in our laboratory. The effect of water in