Ligand effects, solvent cooperation, and large kinetic solvent deuterium isotope effects in gold(I)-catalyzed intramolecular alkene hydroamination

• Ruichen Lan,
• Brock Yager,
• Yoonsun Jee,
• Cynthia S. Day and
• Amanda C. Jones

Beilstein J. Org. Chem. 2024, 20, 479–496, doi:10.3762/bjoc.20.43

• substrate is the most active. In 2012, Kojima and Mikami utilized bimetallic tropos BIPHEP [bis(phosphino)biphenyl]–digold complexes for enantioselective intramolecular hydroamination of N-alkenylureas [9], and they hypothesized that N-alkenylureas could be activated through bimetallic coordination not only

• with alkene but also the urea carbonyl. The Bronsted acidity of the urea would be increased by coordination to gold, and if such coordination is key to enabling reactivity, this would confirm the higher reactivity of urea 1a. The divergent behavior of sulfonamide 1d does not find an easy explanation

• -centered while being C-centered in analogous anions alpha to sulfonamides [51]. Sulfonamides are known to protonate at nitrogen [31]. Gold coordination to carbonyls would be predicted to retain N-centered nucleophilicity, while gold coordination to the sulfonamide nitrogen would not. Sulfonamides are less

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 cation species 89 and the radical anion 90 with the corresponding charges balanced by the LiBF4 additive. Notably, it was suggested that LiBF4 could also facilitate the reduction of the NHPI ester substrate, potentially by the coordination of Li cation to the phthalimide moiety. Next

Elucidating the glycan-binding specificity and structure of Cucumis melo agglutinin, a new R-type lectin

• Jon Lundstrøm,
• Emilie Gillon,
• Valérie Chazalet,
• Nicole Kerekes,
• Antonio Di Maio,
• Ten Feizi,
• Yan Liu,
• Annabelle Varrot and
• Daniel Bojar

Beilstein J. Org. Chem. 2024, 20, 306–320, doi:10.3762/bjoc.20.31

• with a carbohydrate here. It is found in a shallow groove, supporting our data on the lack of a distinct distal binding specificity. We report a tight coordination of the O3 and O4 hydroxy groups of the galactose residue involving Asp21, Asn43, and Gln41 side chains, as well as the Gly24 main chain

• coordination with the Trp36 ring nitrogen (alpha anomer) or the Gly24 main chain oxygen (beta anomer). Conclusion Our work presents a substantial exploration of the binding specificity and mechanism of the hitherto uncharacterized lectin CMA1 from melons. The binding specificity of CMA1, C2-substituted

Substitution reactions in the acenaphthene analog of quino[7,8-h]quinoline and an unusual synthesis of the corresponding acenaphthylenes by tele-elimination

• Ekaterina V. Kolupaeva,
• Narek A. Dzhangiryan,
• Alexander F. Pozharskii,
• Oleg P. Demidov and
• Valery A. Ozeryanskii

Beilstein J. Org. Chem. 2024, 20, 243–253, doi:10.3762/bjoc.20.24

• of quinoquinolines, their planar structure, and very easy coordination to acidic and electrophilic sites (including water [15][22] or the C–H bond of chloroform [11]) almost always lead to co-crystallization. For example, there is no such crystallographic information for quinoquinoline 3 itself. In

Perspectives on push–pull chromophores derived from click-type [2 + 2] cycloaddition–retroelectrocyclization reactions of electron-rich alkynes and electron-deficient alkenes

• Michio Yamada

Beilstein J. Org. Chem. 2024, 20, 125–154, doi:10.3762/bjoc.20.13

• addition of B(C6H5)3, which may be due to the enhancement of the dienophilic nature of the cyano group due to coordination with borane. Rotaxane synthesis Push–pull chromophores with nonplanar configurations have been reported as effective stoppering motifs for rotaxane synthesis. A rational approach

Electron-beam-promoted fullerene dimerization in nanotubes: insights from DFT computations

• Laura Abella,
• Gerard Novell-Leruth,
• Josep M. Ricart,
• Josep M. Poblet and
• Antonio Rodríguez-Fortea

Beilstein J. Org. Chem. 2024, 20, 92–100, doi:10.3762/bjoc.20.10

• methods for more details). It is not the goal of the present work to explain all the steps up to the formation of fullertube C120, but the steps that follow the formation of dimers 1-Cs•+ and 1-D2h•+. We first run a metadynamics simulation for dimer 1-Cs•+ using as CV the coordination number of nine

• CV the coordination number of ten carbon atoms of one C60 molecule (two contiguous hexagons) with respect to ten carbon atoms in the other C60, analogous to the first run. After 7 ps, we also observed the sequential formation of C–C bonds between the two cages in structures now called dimer 3B-D2h

• 20 Å) and a time step of 0.144 fs. We used the metadynamics technique to analyze the dimerization reaction mechanism [28][29][30]. The collective variable (CV) considered for the exploration of the free-energy surface was the coordination number of nine C atoms of one C60 (those that are involved in

1-Butyl-3-methylimidazolium tetrafluoroborate as suitable solvent for BF₃: the case of alkyne hydration. Chemistry vs electrochemistry

• Marta David,
• Elisa Galli,
• Richard C. D. Brown,
• Marta Feroci,
• Fabrizio Vetica and
• Martina Bortolami

Beilstein J. Org. Chem. 2023, 19, 1966–1981, doi:10.3762/bjoc.19.147

• of additional DBU to this solution did not show the signal of DBU in the 13C NMR spectrum (161 ppm), but increased the 166 ppm peak intensity (due to the DBU adduct) (see Supporting Information File 1, Figure S5e). We have no explanation for this behaviour, but the possibility of the coordination of

Aldiminium and 1,2,3-triazolium dithiocarboxylate zwitterions derived from cyclic (alkyl)(amino) and mesoionic carbenes

• Nedra Touj,
• François Mazars,
• Guillermo Zaragoza and
• Lionel Delaude

Beilstein J. Org. Chem. 2023, 19, 1947–1956, doi:10.3762/bjoc.19.145

• -dithiocarboxylate zwitterions (Figure 2) [30][31][32][33][34][35][36][37][38][39][40][41][42][43]. These 1,1-dithiolate inner salts strongly bind main group elements and transition metals through various coordination modes. Indeed, we and others have already reported the synthesis of diverse metallic complexes

• featuring monodentate [44][45], chelating bidentate [46][47][48][49][50][51][52][53][54][55], or bridging bidentate NHC·CS2 ligands [45][51][52]. Small bimetallic clusters [51][52][56], coordination polymers [57], self-assembled monolayers [58], and nanoparticles [45] based on these zwitterions were also

• center that may act as a source of chirality. Thus, the novel compounds reported in this study represent a valuable addition to the family of neutral dithiolate ligands derived from stable nucleophilic carbenes, and we are currently investigating their coordination chemistry toward various transition

Substituent-controlled construction of A₄B₂-hexaphyrins and A₃B-porphyrins: a mechanistic evaluation

• Seda Cinar,
• Dilek Isik Tasgin and
• Canan Unaleroglu

Beilstein J. Org. Chem. 2023, 19, 1832–1840, doi:10.3762/bjoc.19.135

• selective synthesis of expanded porphyrins and their chemistry with regard to their aromaticity and coordination properties. They used meso-aryl-substituted dipyrromethanes and aldehydes in the synthesis of A3B3-type hexaphyrins [13] and 5,10-diaryl-substituted tripyrranes in A4B2-hexaphyrin synthesis [6

Active-metal template clipping synthesis of novel [2]rotaxanes

• Cătălin C. Anghel,
• Teodor A. Cucuiet,
• Niculina D. Hădade and
• Ion Grosu

Beilstein J. Org. Chem. 2023, 19, 1776–1784, doi:10.3762/bjoc.19.130

• ) [30][31], metal-ion template (coordination bonds [22][32], ion-dipol [16], donor–acceptor (charge transfer, π–π stacking) [30][33], and oligoamide macrocycle-hydrogen acceptors (hydrogen bonding) [20][34]. In active-metal template methods (Figure 1) the metal ion acts both as template and catalyst for

Selectivity control towards CO versus H₂ for photo-driven CO₂ reduction with a novel Co(II) catalyst

• Lisa-Lou Gracia,
• Philip Henkel,
• Olaf Fuhr and
• Claudia Bizzarri

Beilstein J. Org. Chem. 2023, 19, 1766–1775, doi:10.3762/bjoc.19.129

• (26.6 ppm) in the Earth crust [26]. Although it should not be considered a cost-effective option at present, as several social and environmental concerns are associated with its extraction, the high stability of the Co(II) ion and the versatility of the ligands used for coordination offer some

• ·) and after the addition of two protons, CO and H2O are produced. The cycle could be closed by the coordination of thiocyanate to the cationic Co(II) species, which is left after the generation of the products, or maybe the reduction of the above-mentioned species occurs with another PS cycle. This

Effects of the aldehyde-derived ring substituent on the properties of two new bioinspired trimethoxybenzoylhydrazones: methyl vs nitro groups

• Dayanne Martins,
• Roberta Lamosa,
• Talis Uelisson da Silva,
• Carolina B. P. Ligiero,
• Sérgio de Paula Machado,
• Daphne S. Cukierman and
• Nicolás A. Rey

Beilstein J. Org. Chem. 2023, 19, 1713–1727, doi:10.3762/bjoc.19.125

• ]. The study also found that those coordination compounds were selective towards abnormal cells, exhibiting lower toxicity for healthy human hepatocytes. On the other hand, an important development in cancer research is the use of physiological metal ion complexes, which afford more biocompatibility and

Tying a knot between crown ethers and porphyrins

• Maksym Matviyishyn and
• Bartosz Szyszko

Beilstein J. Org. Chem. 2023, 19, 1630–1650, doi:10.3762/bjoc.19.120

• the possible future directions. Keywords: crown ethers; porphyrinoids; self-assembly; sensors; supramolecular chemistry; Introduction Many areas of modern supramolecular chemistry, organic, inorganic, materials and coordination chemistry, are based upon macrocyclic compounds of specifically-designed

• synthesis of three-dimensional cryptands by Lehn [5], and spherands by Cram [6]. Later on, various classes of macrocyclic compounds were designed, demonstrating remarkable features in areas spreading from simple coordination chemistry [7], through host–guest chemistry, sensing [8], biomedicine [9], and

• other two have imine character [11][12]. They are rigid, planar molecules which feature macrocyclic aromaticity due to the cyclic delocalisation of π electrons [13]. The well-defined macrocyclic cavity termed the coordination core, can encompass one, two, or more central ions (typically metal/metalloid

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

• and the quinones react with unoxidized catechols to form o-semiquinone radicals afterwards [12]. The semiquinone radicals can help DOPA adhere onto organic surfaces. At a basic pH, the system is cured and mechanically stabilized through the formation of DOPA-metal coordination bonds. The cohesion of

• (OMRP) is also a commonly used polymerization method, which uses transition-metal complexes such as titanium and vanadium for coordination polymerization [69]. However, due to the high cost of these complexes and their post-processing, OMRP is not widely used. The chain termination reaction of OMRP is

Morpholine-mediated defluorinative cycloaddition of gem-difluoroalkenes and organic azides

• Tzu-Yu Huang,
• Mario Djugovski,
• Sweta Adhikari,
• Destinee L. Manning and
• Sudeshna Roy

Beilstein J. Org. Chem. 2023, 19, 1545–1554, doi:10.3762/bjoc.19.111

• defluorinative processes in gem-difluoroalkenes. NiCl2(PCy3)2 and NiCl2(dppp)2 were chosen for our initial investigations since they have been used in both the defluorination of gem-difluoroalkenes and the coordination with the azides to promote [3 + 2] cycloaddition reactions [2][31][32]. Based on our

• did not improve the yields when a cyano group was present on the azide handle. In fact, the use of CuSO4 with the cyano group lowered the yield (31%, see entry 12 in Table 1) which might be due to a coordination of the copper catalyst with the cyano group hindering the triazole formation [37]. The

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

• efficient Lewis acid catalyst (Scheme 10) [50]. In the procedure, oxidative cleavage of one S–N bond and 1,2-sulfur migration afforded π-conjugated 6-substituted 2,3-diarylbenzo[b]thiophenes 16. A plausible mechanism is shown in Scheme 11. The coordination of AlCl3 with the phthalimide/succinimide unit of 1

• -(arylsulfenyl)succinimide 1 (Scheme 27) [62]. The reaction involves the formation of active cobalt species I from the interaction of KOAc with the cobalt pre-catalyst. Treatment of I with 63 resulted in the five-membered cobaltocycle complex II. Next, coordination of 1 to II gave III, followed by intramolecular

• reductive elimination to yield ketone 78. In the acylthiolation cycle, the azaphilic ZnCl2 activated NTSE 1’’’ via N–Zn coordination to facilitate the leaving ability of succinimide. Then, nucleophilic substitution of arylmagnesium bromide 75 to intermediate IV provided thioester 79. In 2022, Gao and co

Cyclization of 1-aryl-4,4,4-trichlorobut-2-en-1-ones into 3-trichloromethylindan-1-ones in triflic acid

• Vladislav A. Sokolov,
• Andrei A. Golushko,
• Irina A. Boyarskaya and
• Aleksander V. Vasilyev

Beilstein J. Org. Chem. 2023, 19, 1460–1470, doi:10.3762/bjoc.19.105

• ][4][5][6][7][8][9][10]). Protonation (or coordination) of basic centers (carbons of unsaturated bonds and heteroatoms) of organic molecules in Brønsted (or Lewis) acids gives rise to not only monocations, but also to highly reactive dicationic (and even higher charged) species. Thus, different

α-(Aminomethyl)acrylates as acceptors in radical–polar crossover 1,4-additions of dialkylzincs: insights into enolate formation and trapping

• Angel Palillero-Cisneros,
• Paola G. Gordillo-Guerra,
• Fernando García-Alvarez,
• Olivier Jackowski,
• Franck Ferreira,
• Fabrice Chemla,
• Joel L. Terán and
• Alejandro Perez-Luna

Beilstein J. Org. Chem. 2023, 19, 1443–1451, doi:10.3762/bjoc.19.103

• that α-(aminomethyl)acrylates are suitable acceptors for 1,4-additions of dialkylzincs in aerobic conditions. The air-promoted radical–polar crossover process involves the 1,4-addition of an alkyl radical followed by homolytic substitution at the zinc atom of dialkylzinc. Coordination of the nitrogen

• with the starting acrylate for 1 h prior to the addition of air had a significant impact on the stereoselectivity. When air was introduced directly after Et2Zn (Table 3, entry 3) a much lower 59:41 dr was observed. This behavior was suggestive of the need for coordination of diethylzinc both to the

• -addition and SH2 of the formed enoxyl radical facilitated by coordination of nitrogen to zinc. The zinc enolate thus formed evolves following different pathways according to the type of substrate and reaction conditions. In the absence of a carbonyl electrophile, enolates of substrates with trisubstituted

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

• . A number of excellent reviews on different aspects of NHC chemistry has been published during this period [12][13][14]. NHCs have been widely employed in homogeneous catalysis [12] and as ligands for the preparation of coordination compounds of different metals [13]. The M–NHC bond is relatively

• anionic hybrid NHC, “IMes-acac” consisting of fused diaminocarbene and acetylacetonato units. The latter afforded a series of representative Cu(I) complexes through bidentate coordination (Scheme 16) [30]. 1.2 Deprotonation of NHC-precursors with Cu2O Another important and facile method involves heating

• respectively, incorporating NHC–Cu(I) bromide and Cu(II) phenoxymine coordination. These complexes could be independently prepared through transmetallation by reacting NHC–AgBr 74 with copper(II) precursors Cu(SO3CF3)2 or CuCl2·2H2O (Scheme 26) [32]. Oro and co-workers synthesized new NHC–CuX complexes 78a,b

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

• copper is mainly to activate the C(sp2)–H bond by coordination or activating the oxidant to achieve the reaction cycle. Subsequently, Li and Ahmad et al. reported a Cu(I)-catalyzed C(sp2)–H activation and ether formation of C(sp2)–C(sp3) bonds via CDC, respectively (Scheme 14) [65][66]. The isotope

• )–H and C(sp3)–H bonds by the ortho-alkylation reaction of aromatic carboxamides containing (pyridin-2-yl)isopropylamine (PIP–NH2) as an N,N-bidentate directing group (Scheme 32) [97]. The mechanism study showed that these reactions were a Co(III/IV/II) catalytic cycle, and the coordination of Co with

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

• center. Subsequent reoxidation of the metal with coordination of a new equivalent of anionic ligand allows for the RLT complex to be regenerated, making this strategy inherently compatible with catalysis. Building on this, one of the most important examples of catalytic RLT can be found in the human

• captured via RLT from an in-situ generated iron–azide complex, resulting in net reduction of iron. The competent RLT species can then be regenerated through oxidation by the iodinane species and coordination of another equivalent of azide. This reaction was particularly notable for the wide alkene scope

Exploring the role of halogen bonding in iodonium ylides: insights into unexpected reactivity and reaction control

• Carlee A. Montgomery and
• Graham K. Murphy

Beilstein J. Org. Chem. 2023, 19, 1171–1190, doi:10.3762/bjoc.19.86

• contributing factors. 2.2 Halogen bond-initiated reactions: early discoveries Iodonium ylides have long been employed as metallocarbene precursors, and Müller et al. contributed significant evidence that their reactions with olefins took place within the coordination sphere of the metal [103][104][105][106

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

• excited state lifetimes [95][96], most reactions employing such photocatalysts require special reaction design (e.g., coordination of substrates as ligands to enable intramolecular metal to ligand charge transfer (MLCT)). Only recently have a few examples been reported that observed bimolecular quenching

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

• presence of 4 mol % ZrOCl2∙8H2O as a catalyst in water at 60 °C (Scheme 11a). Among many catalysts used for the synthesis of N-substituted pyrroles, Zr(IV) compounds, especially ZrOCl2∙8H2O have received more attention because of its high coordination ability, low toxicity, low cost and high activity. In

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

• chelate environmental Fe3+. Ligand groups, such as hydroxamate, phenolate, catecholate, carboxylate, or oxazoline/thiazoline residues, confer siderophores their high affinity for the binding of Fe3+ [3][4][5]. Following the coordination of the metal, the Fe3+-loaded siderophore complex is transported back