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

• -butylperoxy radical B provides the target product 121. The Fe-catalyzed oxidative functionalization of silylallenes 122 with TBHP with the formation of propargylic peroxides 123 was described (Scheme 42) [100]. The authors proposed that tert-butoxy radical A, formed by the reaction of TBHP with Fe(II

A new oxidatively stable ligand for the chiral functionalization of amino acids in Ni(II)–Schiff base complexes

• Alena V. Dmitrieva,
• Oleg A. Levitskiy,
• Yuri K. Grishin and
• Tatiana V. Magdesieva

Beilstein J. Org. Chem. 2023, 19, 566–574, doi:10.3762/bjoc.19.41

• path yielding the bimetallic Ni(II) complex [36]. Thus, L4 in Scheme 1 was shown to be suitable for the oxidative functionalization of the amino acid fragment [37]. A bulky tert-butyl group can be also proposed as a protecting moiety. One could expect that the t-Bu group will prevent fast oxidative

• . This result is important; it indicates the possibility for further oxidative functionalization of the amino acid fragment using the Ni–Schiff base templates derived from the new ligand L7. One-electron reduction of the complex (GlyNi)L7 is mainly metal centered (with some impact of the π* orbital of

Redox-active molecules as organocatalysts for selective oxidative transformations – an unperceived organocatalysis field

• Elena R. Lopat’eva,
• Igor B. Krylov,
• Dmitry A. Lapshin and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2022, 18, 1672–1695, doi:10.3762/bjoc.18.179

• -organocatalysts. Organocatalysis classification used in the present perspective. Oxidative processes catalyzed by amines. N-Heterocyclic carbene (NHC) catalysis in oxidative functionalization of aldehydes. Examples of asymmetric oxidative processes catalyzed by chiral Brønsted acids. Asymmetric aerobic α

Photoredox catalysis in nickel-catalyzed C–H functionalization

• Lusina Mantry,
• Rajaram Maayuri,
• Vikash Kumar and
• Parthasarathy Gandeepan

Beilstein J. Org. Chem. 2021, 17, 2209–2259, doi:10.3762/bjoc.17.143

• powerful tool in organic synthesis, they generally require prefunctionalized starting materials, which significantly affect the reaction's atom economy and produce inorganic, organometallic salt wastes [23][24][25]. During the last decade, the oxidative functionalization of inert C‒H into carbon–carbon (C

Tandem copper and photoredox catalysis in photocatalytic alkene difunctionalization reactions

• Nicholas L. Reed,
• Madeline I. Herman,
• Vladimir P. Miltchev and
• Tehshik P. Yoon

Beilstein J. Org. Chem. 2019, 15, 351–356, doi:10.3762/bjoc.15.30

• ) salts proved to be unique in their ability to turn over the copper cocatalyst without deleteriously impacting the reactivity of the organoradical intermediates. Keywords: copper; diamination; oxidative functionalization; oxyamination; photoredox catalysis; radical; Introduction Over the past decade, a

• that are not accessible from the native reactivity of the organoradical intermediates by themselves. Our laboratory is interested in the design of photochemical strategies for oxidative functionalization reactions [15][16]. We recently described [17] a new approach to alkene difunctionalization that

Hypervalent iodine compounds for anti-Markovnikov-type iodo-oxyimidation of vinylarenes

• Igor B. Krylov,
• Stanislav A. Paveliev,
• Mikhail A. Syroeshkin,
• Alexander A. Korlyukov,
• Pavel V. Dorovatovskii,
• Yan V. Zubavichus,
• Gennady I. Nikishin and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2018, 14, 2146–2155, doi:10.3762/bjoc.14.188

• . It was shown that the iodine atom in the prepared iodo-oxyimides can be substituted by various nucleophiles. Keywords: free radicals; hypervalent iodine; imide-N-oxyl radicals; iodination; N-hydroxyimides; oxidative functionalization; Introduction The presented work opens a new chapter in the

Selective carboxylation of reactive benzylic C–H bonds by a hypervalent iodine(III)/inorganic bromide oxidation system

• Toshifumi Dohi,
• Shohei Ueda,
• Kosuke Iwasaki,
• Yusuke Tsunoda,
• Koji Morimoto and
• Yasuyuki Kita

Beilstein J. Org. Chem. 2018, 14, 1087–1094, doi:10.3762/bjoc.14.94

• single-electron-transfer (SET) reactivities [33][34][35][36][37] allow selective activation of the benzylic C(sp3)–H bond for oxidative functionalization and coupling reactions. Initially, the SET oxidation ability of pentavalent iodine reagents, especially o-iodoxybenzoic acid (IBX), in benzylic

Functionalization of N-arylglycine esters: electrocatalytic access to C–C bonds mediated by n-Bu₄NI

• Mi-Hai Luo,
• Yang-Ye Jiang,
• Kun Xu,
• Yong-Guo Liu,
• Bao-Guo Sun and
• Cheng-Chu Zeng

Beilstein J. Org. Chem. 2018, 14, 499–505, doi:10.3762/bjoc.14.35

• . In addition, it is demonstrated that the mediated process is superior to the direct electrochemical functionalization. Keywords: C–C formation; electrochemical oxidative functionalization; n-Bu4NI; redox catalyst; Introduction The oxidative cross dehydrogenative coupling (CDC) of two C–H bonds has

Preparation and isolation of isobenzofuran

• Morten K. Peters and
• Rainer Herges

Beilstein J. Org. Chem. 2017, 13, 2659–2662, doi:10.3762/bjoc.13.263

• ) and methylated to DMIBF (7) [8]. However, yields in our hands are quite low. It is known that benzyl ethers are prone to oxidative functionalization [20]. 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) has been used to selectively oxidize benzyl ethers to acetals in the presence of alcohols [21

Unusual reactions of diazocarbonyl compounds with α,β-unsaturated δ-amino esters: Rh(II)-catalyzed Wolff rearrangement and oxidative cleavage of N–H-insertion products

• Valerij A. Nikolaev,
• Jury J. Medvedev,
• Olesia S. Galkina,
• Ksenia V. Azarova and
• Christoph Schneider

Beilstein J. Org. Chem. 2016, 12, 1904–1910, doi:10.3762/bjoc.12.180

• of aroyldiazomethanes 2 and dibenzoyldiazomethane 3c with aminoester 1. Oxidative functionalization of α-СН2-groups in the structure of amines is a rather familiar instrument of organic synthesis, which is widely used for the preparation of amino acids and alkaloids [26][27][28]. Cleavage of σ-С–С

Reaction of allene esters with Selectfluor/TMSX (X = I, Br, Cl) and Selectfluor/NH₄SCN: Competing oxidative/electrophilic dihalogenation and nucleophilic/conjugate addition

• A. Srinivas Reddy and
• Kenneth K. Laali

Beilstein J. Org. Chem. 2015, 11, 1641–1648, doi:10.3762/bjoc.11.180

• catalyst for oxidative functionalization is comparatively less explored [11]. Notable examples of oxidative functionalization by Selectfluor include in situ generation of electrophile equivalents Cl+, Br+, SCN+ and NO2+ and their reactions with aromatics [12], the bromination of representative alkenes with

Novel stereocontrolled syntheses of tashiromine and epitashiromine

• Loránd Kiss,
• Enikő Forró and
• Ferenc Fülöp

Beilstein J. Org. Chem. 2015, 11, 596–603, doi:10.3762/bjoc.11.66

• pyrrole, followed by saturation [37]. The transformation of chiral functionalized pyrrole or pyrrolidine derivatives has served as the basis of the construction of (−)-epitashiromine [38][39] (Figure 4). The oxidative functionalization of cyclic β-amino acid derivatives has been reported to be a

Cross-dehydrogenative coupling for the intermolecular C–O bond formation

• Igor B. Krylov,
• Vera A. Vil’ and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2015, 11, 92–146, doi:10.3762/bjoc.11.13

• compounds [15], the Pd(II)-catalyzed oxidative C–C, C–O, and C–N bond formation [3], the transition metal-catalyzed etherification of unactivated C–H bonds [19], the Pd(II)-catalyzed oxidative functionalization at the allylic position of alkenes [20][21], the oxidative functionalization catalyzed by copper

• salts, were used for the oxidative functionalization at the α-position of carbonyl compounds. N-Hydroxyimides and N-hydroxyamides 204 are involved in the oxidative C–O coupling with 1,3-dicarbonyl compounds and their hetero analogues, such as 2-substituted malononitriles and cyanoacetic esters, 205 in

Heronapyrrole D: A case of co-inspiration of natural product biosynthesis, total synthesis and biodiscovery

• Jens Schmidt,
• Zeinab Khalil,
• Robert J. Capon and
• Christian B. W. Stark

Beilstein J. Org. Chem. 2014, 10, 1228–1232, doi:10.3762/bjoc.10.121

• unprecedented heterocyclic core (2-nitro-4-farnesylpyrrole) with closely related levels of oxidative functionalization of the farnesyl side chain. In 2012 Stark et al. employed a biomimetic strategy to deliver the first asymmetric total synthesis of heronapyrrole C, confirming its constitution and establishing

The chemistry of amine radical cations produced by visible light photoredox catalysis

• Jie Hu,
• Jiang Wang,
• Theresa H. Nguyen and
• Nan Zheng

Beilstein J. Org. Chem. 2013, 9, 1977–2001, doi:10.3762/bjoc.9.234

• . Oxidative functionalization of N-aryltetrahydroisoquinolines using Eosin Y. Synthetic and mechanistic studies of Eosin Y-catalyzed aza-Henry reaction. Oxidative functionalization of N-aryltetrahydroisoquinolines using RB and GO. Merging Ru-based photoredox catalysis and Lewis base catalysis for the Mannich

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

• reactive aryl radical cation intermediate 3•+, whose fate depends strongly on the reaction conditions. In the absence of radical-trapping agents, in particular NO2•, benzylic deprotonation is the exclusive pathway that ultimately leads to oxidative functionalization of the alkyl side chain through

Biocatalytic hydroxylation of n-butane with in situ cofactor regeneration at low temperature and under normal pressure

• Svenja Staudt,
• Christina A. Müller,
• Jan Marienhagen,
• Christian Böing,
• Stefan Buchholz,
• Ulrich Schwaneberg and
• Harald Gröger

Beilstein J. Org. Chem. 2012, 8, 186–191, doi:10.3762/bjoc.8.20

• conditions, was developed. The resulting 2-butanol was obtained as the only regioisomer, at a product concentration of 0.16 g/L. Keywords: biotransformations; cofactor regeneration; green chemistry; hydroxylation; P450-monooxygenase; Introduction The (regioselective) oxidative functionalization of