Three-component N-alkenylation of azoles with alkynes and iodine(III) electrophile: synthesis of multisubstituted N-vinylazoles

• Jun Kikuchi,
• Roi Nakajima and
• Naohiko Yoshikai

Beilstein J. Org. Chem. 2024, 20, 891–897, doi:10.3762/bjoc.20.79

• difunctionalization of alkynes with various heteroatom and carbon nucleophiles [27][28][29][30][31][32][33][34]. Specifically, intermolecular trans-iodo(III)functionalization of alkynes has been achieved using oxygen nucleophiles such as alcohols [28][32], ethers [33], carboxylic acids [31], phosphate esters [31

• other heteroatom nucleophiles is currently underway. Synthesis of N-vinylazoles. Scope of three-component N-alkenylation of azoles. Competition experiments and plausible reaction pathway. Preparative-scale reaction and product transformations. Reaction conditions: (a) Pd(PPh3)4, 4-MeOC6H4B(OH)2, Cs2CO3

Green and sustainable approaches for the Friedel–Crafts reaction between aldehydes and indoles

• Periklis X. Kolagkis,
• Eirini M. Galathri and
• Christoforos G. Kokotos

Beilstein J. Org. Chem. 2024, 20, 379–426, doi:10.3762/bjoc.20.36

• . The difference between the two mechanistic pathways is the nature of activation of the carbonyl group. Protic acids induce the protonation of the carbonyl group of the aldehyde or ketone, enhancing its electrophilic character. Whereas, Lewis acid catalysts bind to the heteroatom of the carbonyl group

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

• absorption spectra of PTH1 was observed, suggesting the formation of a charge transfer complex of the type 88 [68] (Scheme 17A). tert-Butyl radical (64), along with additional 2° and 3° alkyl radicals, resulting from these EDA complexes were harnessed in C(sp3)-heteroatom bond forming reactions [69], and in

• the three-component alkylacylation of olefins [108]. Alternatively, NHC catalysts can mediate the generation of radical intermediates from NHPI esters via the stabilization of a photoactive EDA complex. In 2020, Wang and Chen reported a photochemical C(sp3)-heteroatom coupling reaction of NHPI esters

Synthesis of π-conjugated polycyclic compounds by late-stage extrusion of chalcogen fragments

• Aissam Okba,
• Pablo Simón Marqués,
• Kyohei Matsuo,
• Naoki Aratani,
• Hiroko Yamada,
• Gwénaël Rapenne and
• Claire Kammerer

Beilstein J. Org. Chem. 2024, 20, 287–305, doi:10.3762/bjoc.20.30

• heteroatom-based counterparts, have attracted the attention of the scientific community for two centuries already. Initially, major interest resulted from their structural, optical and electronic properties at the molecular level, but the last decades witnessed the rise of molecular materials and π

• , this class of compounds is prone to valence isomerization via 6π-electrocyclization leading to the formation of heteroatom-containing norcaradiene, and oxepine has been shown to exist in equilibrium with its valence isomer benzene oxide [37]. In contrast with the parent oxepine, which is isolable at

• the synthesis of a series of HBC precursors incorporating a group-16 heteroatom embedded in a seven-membered ring. In the case of oxygen, the fully cyclized HBC 26a containing an oxepine ring and exhibiting a saddle-shape tridimensional structure was successfully prepared (Scheme 8, top). Conversely

Facile access to pyridinium-based bent aromatic amphiphiles: nonionic surface modification of nanocarbons in water

• Lorenzo Catti,
• Shinji Aoyama and
• Michito Yoshizawa

Beilstein J. Org. Chem. 2024, 20, 32–40, doi:10.3762/bjoc.20.5

• PA-OCH3 to solubilize not only conventional nanocarbons but also heteroatom-containing ones. To obtain direct structural information of the encircled (g-C3N4)m, dry-state AFM measurements (on mica) were conducted using an aqueous solution of (PA-OCH3)n·(g-C3N4)m. The obtained AFM images showed large

Recent advancements in iodide/phosphine-mediated photoredox radical reactions

• Tinglan Liu,
• Yu Zhou,
• Junhong Tang and
• Chengming Wang

Beilstein J. Org. Chem. 2023, 19, 1785–1803, doi:10.3762/bjoc.19.131

• emphasized their significance in facilitating the synthesis of diverse compounds and paving the way for further advancements in the field of photocatalysis. The highly efficient construction of carbon–heteroatom (C–X) bonds is of significant importance in the fields of natural products, pharmaceuticals, and

• facilitated by the process of photoexcited radical decarboxylation. On the other hand, the copper catalytic cycle involved the capture of alkyl radicals by the copper complex B, the activation of heteroatom-containing substrates 30 by a base-mediated proton transfer, and the subsequent reductive elimination

N-Sulfenylsuccinimide/phthalimide: an alternative sulfenylating reagent in organic transformations

• Fatemeh Doraghi,
• Seyedeh Pegah Aledavoud,
• Mehdi Ghanbarlou,
• Bagher Larijani and
• Mohammad Mahdavi

Beilstein J. Org. Chem. 2023, 19, 1471–1502, doi:10.3762/bjoc.19.106

• azlactone 146 skeletons. The presence of two heteroatom-bearing tetrasubstituted chiral carbon centers in a one-step fashion, avoiding the use of the heavy metal catalysts, and the performance of the reaction at ambient temperature are the prominent features of the protocol. Sahoo and co-workers found that

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

• atom(s) or another heteroatom into the vacant p-orbital (LUMO) at the carbene carbon atom (Figure 2). In fact, the donation of lone pair electrons to the carbenic center leads to an ylidic structure which induces a “push–pull” effect thereby enhancing the stability of the NHC. The cyclic structure of

• ), bear only a single flanking heteroatom and exist as a zwitterionic structure with no neutral canonical resonance form (Figure 3). In this case, binding takes place via the C4 or C5 position. These NHCs have been found to be stronger electron-donors due to the reduced σ-withdrawal from the carbene carbon

• or carbon–heteroatom double bond, resulting in the formation of a new carbon–silicon (C–Si) or heteroatom–Si (X–Si) bond (Scheme 34). This reaction is widely used in the synthesis of organosilicon compounds and in the modification of surfaces with silicon-containing molecules. NHC–Cu complexes have

Synthesis of ether lipids: natural compounds and analogues

• Marco Antônio G. B. Gomes,
• Alicia Bauduin,
• Chloé Le Roux,
• Romain Fouinneteau,
• Wilfried Berthe,
• Mathieu Berchel,
• Hélène Couthon and
• Paul-Alain Jaffrès

Beilstein J. Org. Chem. 2023, 19, 1299–1369, doi:10.3762/bjoc.19.96

Non-noble metal-catalyzed cross-dehydrogenation coupling (CDC) involving ether α-C(sp³)–H to construct C–C bonds

• Hui Yu and
• Feng Xu

Beilstein J. Org. Chem. 2023, 19, 1259–1288, doi:10.3762/bjoc.19.94

• ) process, the carbocation intermediate B is generated, which is attacked by a nucleophile to afford the target product. Further, C–H bonds in the ortho-position of a heteroatom are activated through a SET pathway generating a radical cation C, which is easily deprotonated by an oxidant to generate a

• source played a key role, with lower yields or no product obtained when the reaction was performed without water or under other light source conditions such as 19 W CFL or irradiation with blue or green LEDs. This method is applicable to various heteroatom-containing compounds such as quinolines

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

• paradigm by Groves and Kochi, many groups have adopted and characterized new ways of using RLT to form valuable carbon–heteroatom bonds from a diverse pool of simple starting materials. RLT has been especially present in modern catalysis, where complexes of earth abundant iron and manganese have been

• simplified manganese salen complex I, allowing for the identity of the carbon–heteroatom bond to be controlled based on added nucleophile and enabling C–Cl, C–N, and C–S bonds to be formed directly while completely suppressing traditional ATRA products [9]. In mechanistic studies, rearrangement products

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

• lone pair of electrons of the imine nitrogen to a suitable vacant orbital of the metal center, thus enhancing the electrophilicity of the imine carbon atom by imparting a positive character on the adjacent heteroatom [22][23]. With the advent of different types of organocatalysts, the aza-Friedel

Intermediates and shunt products of massiliachelin biosynthesis in Massilia sp. NR 4-1

• Till Steinmetz,
• Blaise Kimbadi Lombe and
• Markus Nett

Beilstein J. Org. Chem. 2023, 19, 909–917, doi:10.3762/bjoc.19.69

• formula of 1 was assigned to be C15H19NO3S by high-resolution (HR) ESIMS (m/z 294.1180 [M + H]+; calcd. 294.1169 for C15H20NO3S), which indicated the presence of seven double bond equivalents (DBEs). Upon analyzing the 13C NMR spectrum, the DBEs were assigned to two ring structures, two carbon–heteroatom

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

• . Review C–H Alkylation of pyridine The C–H bond is the backbone of an organic molecule and the conversion of a C–H bond to a C–X bond (X = carbon or heteroatom) forms the basis in organic synthesis. The functionalization of C–H bonds is challenging due to a large kinetic barrier for C–H bond cleavage and

Construction of hexabenzocoronene-based chiral nanographenes

• Ranran Li,
• Di Wang,
• Shengtao Li and
• Peng An

Beilstein J. Org. Chem. 2023, 19, 736–751, doi:10.3762/bjoc.19.54

• ], and nanoribbons [19]. Meanwhile, to modulate the properties of synthetic hydrocarbon NGs, a variety of heteroatom-doped NGs have been constructed [8]. Chirality is a fundamental phenomenon in nature and plays an important role in science, especially in living systems. The chirality in chemistry refers

• exploit three-dimensional aesthetic structures. The continuously developed novel structures contented our interests and curiosity. To further tune the optoelectronic or photophysical properties of nanographenes for real applications, heteroatom doping was found to be an effective strategy. 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

• 10,11-dihydrodibenzo[b,f]heteropines (2). The following section will briefly touch on functionalisation of the scaffold. While some reports are limited to the introduction of a single heteroatom, e.g., nitrogen in the case of azepines 1a or oxygen in the case of oxepines 1b, some approaches allow for

• from 2-bromostyrene (116) via halogen–lithium exchange and quenching with the appropriate heteroatom source (SiR2Cl2, SnMe2Cl2, GeR2Cl2, BBr3). P-Tethered dienes were synthesised via quenching of a 2-vinylphenyl Grignard reagent with phenylphosphonic dichloride (PhPOCl2). O-Tethered dienes were

• etherification entails the palladium or copper-catalysed formation of a carbon–heteroatom bond. Despite significant successes and facile access to the core tricyclic motif, access to dibenzo[b,f]heteropines with disparately substituted aromatic rings fused to the heterocyclic ring and varied substitution

Nucleophile-induced ring contraction in pyrrolo[2,1-c][1,4]benzothiazines: access to pyrrolo[2,1-b][1,3]benzothiazoles

• Ekaterina A. Lystsova,
• Maksim V. Dmitriev,
• Andrey N. Maslivets and
• Ekaterina E. Khramtsova

Beilstein J. Org. Chem. 2023, 19, 646–657, doi:10.3762/bjoc.19.46

• dramatically depends on the nature of the heteroatom X in FPDs I, II, 1 [33][34]. It should be noted that the reactions of 5-aza- and 5-oxa-FPDs I and II with nucleophiles are studied rather well [33][34], and their reactivity did not give us any insights for the development of new approaches to PBTAs. However

Direct C2–H alkylation of indoles driven by the photochemical activity of halogen-bonded complexes

• Martina Mamone,
• Giuseppe Gentile,
• Jacopo Dosso,
• Maurizio Prato and
• Giacomo Filippini

Beilstein J. Org. Chem. 2023, 19, 575–581, doi:10.3762/bjoc.19.42

• ) and carbon–heteroatom (C–X) bonds has been and still is a central topic in organic synthesis [1][2]. Historically, organic chemists have extensively relied on the use of noble-metal-based catalysts (e.g., Pd, Rh, Ir, among others) to achieve such type of functionalization [3][4][5]. However, reliance

Transition-metal-catalyzed domino reactions of strained bicyclic alkenes

• Austin Pounder,
• Eric Neufeld,
• Peter Myler and
• William Tam

Beilstein J. Org. Chem. 2023, 19, 487–540, doi:10.3762/bjoc.19.38

• years [2][3][4][5][6]. Broadly speaking, bicyclic alkenes can be classified into two groups: homobicyclic and heterobicyclic alkenes. Homobicyclic alkenes are hydrocarbons, like norbornadiene, while heterobicyclic alkenes contain at least one heteroatom in the bicyclic framework. Typically, reactions

• bridging heteroatom increases the ring-strain energy of the system, conceptualized by the decrease in bond distances. Typically, there are two modes for ring-strain release. First, functionalization of the double bond mildly alleviates the ring strain by relieving nonoptimal bond angles enforced by the

• in the case of heterobicyclic alkenes, the heteroatom. This preferential exo coordination is not always the case, as norbornadiene derivatives are known to preferentially form chelated endo complexes which can change the stereochemical outcome of the reaction. Nevertheless, the predisposition of

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

• 14 shares the common [5-8-5] tricyclic framework emblematic of the fusicoccan series, albeit cycloaraneosene (14) does not have any heteroatom (Scheme 1) [16]. Focusing on the B–C bicyclic fragment, they used diene 10, readily available from cyclopentane-1,3-dione (9), as the precursor for installing

1,4-Dithianes: attractive C2-building blocks for the synthesis of complex molecular architectures

• Bram Ryckaert,
• Ellen Demeyere,
• Frederick Degroote,
• Hilde Janssens and
• Johan M. Winne

Beilstein J. Org. Chem. 2023, 19, 115–132, doi:10.3762/bjoc.19.12

• intermolecular allyl cation-type cycloadditions (Scheme 14b–d) [103]. At first, this was investigated for its use in typical (4 + 3) cycloadditions with dienes, but mixed results were obtained (Scheme 14b). Whereas other heteroatom-stabilized allyl cations, such as oxathiins developed by Harmata, or furans

• nature can be appreciated in the resonance structures of vinylthionium species 125, wherein the positive charge is relegated to the gold center (Scheme 19). The reactions of dithiolane 116 also work with unactivated (viz 120) and heteroatom-substituted olefins (viz 122) and were found to generally favor

Two-step continuous-flow synthesis of 6-membered cyclic iodonium salts via anodic oxidation

• Julian Spils,
• Thomas Wirth and
• Boris J. Nachtsheim

Beilstein J. Org. Chem. 2023, 19, 27–32, doi:10.3762/bjoc.19.2

• nucleophilic arenes under oxidative acidic conditions.The synthesis of CDIS is more challenging since the arene moiety must be covalently connected to the iodoarene prior to cyclization. Recently, we published two new methods that describe the generation of carbon- and heteroatom-bridged CDIS [28][29]. Herein

Modular synthesis of 2-furyl carbinols from 3-benzyldimethylsilylfurfural platforms relying on oxygen-assisted C–Si bond functionalization

• Sebastien Curpanen,
• Per Reichert,
• Gabriele Lupidi,
• Giovanni Poli,
• Julie Oble and
• Alejandro Perez-Luna

Beilstein J. Org. Chem. 2022, 18, 1256–1263, doi:10.3762/bjoc.18.131

• on the SiMe(OSiMe3)2 unit, which were readily converted through Pd- or Cu-catalyzed electrophilic substitution reactions into an array of furfurals decorated at C3 with carbon- or heteroatom-containing substituents (Scheme 1). Conversely, all of our subsequent efforts to achieve cross-coupling

Mechanochemical bottom-up synthesis of phosphorus-linked, heptazine-based carbon nitrides using sodium phosphide

• Blaine G. Fiss,
• Georgia Douglas,
• Michael Ferguson,
• Jorge Becerra,
• Jesus Valdez,
• Trong-On Do,
• Tomislav Friščić and
• Audrey Moores

Beilstein J. Org. Chem. 2022, 18, 1203–1209, doi:10.3762/bjoc.18.125

• ; Introduction The development of heteroatom-doped graphitic carbon nitrides (g-CN) has been a rapidly growing area of research since their first report towards water splitting in 2009 [1]. Since that time, the addition of elements such as boron [2], phosphorus [3][4][5], sulfur and oxygen [6] have shown to help

• heptazine subunits. The introduction of phosphorus linkages reduced photoluminescent recombination and improved exciton lifetimes, when compared to nitrogen-linked g-CN. Overall, this supports future investigations of the room-temperature mechanochemical synthesis of heteroatom containing carbons as well as

Lewis acid-catalyzed Pudovik reaction–phospha-Brook rearrangement sequence to access phosphoric esters

• Jin Yang,
• Dang-Wei Qian and
• Shang-Dong Yang

Beilstein J. Org. Chem. 2022, 18, 1188–1194, doi:10.3762/bjoc.18.123

• , all of the above transformations were carried out under basic conditions, and thus impose barriers for substrates that bear base-sensitive functional groups. More importantly, heteroatom-containing ketones and aldehydes have been proven to be challenging substrates for all of these existing systems