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

• -stage transition metals have contributed immensely to synthetic organic and organometallic chemistry, increasing societal awareness in terms of sustainable developments and resource management has prompted chemists to explore the use of environmentally benign, inexpensive, and earth-abundant metals [18

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

Total synthesis of insect sex pheromones: recent improvements based on iron-mediated cross-coupling chemistry

• Eric Gayon,
• Guillaume Lefèvre,
• Olivier Guerret,
• Adrien Tintar and
• Pablo Chourreu

Beilstein J. Org. Chem. 2023, 19, 158–166, doi:10.3762/bjoc.19.15

• groups can act as stabilizing additives to on-cycle organometallic intermediates in cross-coupling procedures. Given that the quantity of free anionic leaving groups, released at each turnover cycle, increases upon completion of the coupling process, it means that the catalyst resting state strongly

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

• °C and 0 °C, temperatures at which these organometallic reagents are also reported to be quite stable. The zincated dithiins can also be prepared by transmetalation of the magnesiated dithiins at −30 °C, and these organozinc reagents can then be used in room temperature Pd-catalyzed cross-coupling

Preparation of an advanced intermediate for the synthesis of leustroducsins and phoslactomycins by heterocycloaddition

• Anaïs Rousseau,
• Guillaume Vincent and
• Cyrille Kouklovsky

Beilstein J. Org. Chem. 2022, 18, 1385–1395, doi:10.3762/bjoc.18.143

• obtained when using equimolar amounts of both 19 and 11b (Table 1, entries 1 and 2). These disappointing results with alkyne 19 prompted us to investigate the coupling with an organometallic reagent derived from vinyl iodide 20. This reagent was already synthesized and coupled with acyclic ketones in

• previous syntheses of leustroducsins or phoslactomycins [7][8][9][10][11][12][13][14][15][16][17]. Thus, treatment of 20 with n-butyllithium in THF gave the organometallic intermediate which was condensed onto ketone 11b (Scheme 8, Table 2). Since no product was obtained under these standard conditions, we

Ferrocenoyl-adenines: substituent effects on regioselective acylation

• Mateja Toma,
• Gabrijel Zubčić,
• Jasmina Lapić,
• Senka Djaković,
• Davor Šakić and
• Valerije Vrček

Beilstein J. Org. Chem. 2022, 18, 1270–1277, doi:10.3762/bjoc.18.133

• the acylation of purines from a regioselective to a regiospecific mode. Keywords: DFT; ferrocene; nucleophilicity; purine; steric effect; Introduction Nucleosides in which the sugar part is replaced with an organometallic moiety have attracted remarkable interest [1][2][3]. One important class are

• organometallic (metallocene) and heterocyclic (purine) parts. Specifically, adenine and its N6-derivatives, most of which are pharmaceutically attractive and/or biologically relevant [20][21][22], have been selected to study the mechanism underlying the synthesis of the ferrocene–nucleobase conjugates. Several

Enantioselective total synthesis of putative dihydrorosefuran, a monoterpene with an unique 2,5-dihydrofuran structure

• Irene Torres-García,
• Josefa L. López-Martínez,
• Rocío López-Domene,
• Manuel Muñoz-Dorado,
• Ignacio Rodríguez-García and
• Miriam Álvarez-Corral

Beilstein J. Org. Chem. 2022, 18, 1264–1269, doi:10.3762/bjoc.18.132

• 4 mediated by the organometallic half-sandwich complex [CpTiIIICl2] [11][12]. Following this retrosynthetic proposal, our route starts from ethyl 4-oxobutanoate (4) [13] which was prepared by ozonolysis of commercially available ethyl pent-4-enoate (Scheme 2). Coupling of the aldehyde 4 with 1

Vicinal ketoesters – key intermediates in the total synthesis of natural products

• Marc Paul Beller and
• Ulrich Koert

Beilstein J. Org. Chem. 2022, 18, 1236–1248, doi:10.3762/bjoc.18.129

• intermediates in the total synthesis of natural products utilizing their electrophilic keto group as reactive site. Suitable key reactions are, e.g., aldol additions, carbonyl ene reactions, Mannich reactions, and additions of organometallic reagents. The vicinal arrangement of carbonyl groups allows the

• bearing an electrophilic keto group as reactive site. The vicinal arrangement of carbonyl groups allows the stabilization of reactive conformations by chelation or dipole control. Suitable key reactions are e.g., aldol additions, carbonyl ene reactions, Mannich reactions, and additions of organometallic

Polymer and small molecule mechanochemistry: closer than ever

• José G. Hernández

Beilstein J. Org. Chem. 2022, 18, 1225–1235, doi:10.3762/bjoc.18.128

• molecules (but also inorganic precursors, organometallic complexes, enzymes, monomeric units, or even polymers) in bulk and to provide the energy required for the system to react (Figure 1b and Figure 1c) [7][8][9][10][11][12]. At times, the methodological differences between both approaches seem to have

• , force-sensitive molecular mechanophores are now complemented by organometallic-based force-responsive mechanophores that are not purely organic molecular fragments [16][17][18]. In fact, the concept of a mechanophore is now broader and may include any force-reactive functional unit, whether it possesses

Scope of tetrazolo[1,5-a]quinoxalines in CuAAC reactions for the synthesis of triazoloquinoxalines, imidazoloquinoxalines, and rhenium complexes thereof

• Laura Holzhauer,
• Chloé Liagre,
• Olaf Fuhr,
• Nicole Jung and
• Stefan Bräse

Beilstein J. Org. Chem. 2022, 18, 1088–1099, doi:10.3762/bjoc.18.111

• confirmed via single crystal X-ray crystallography. Several other byproducts, such as the bistriazolo product were isolated (see Supporting Information File 1). The obtained triazoloquinoxaline and TIQ products are promising ligands for complexation with different metals. The formation of organometallic

First example of organocatalysis by cathodic N-heterocyclic carbene generation and accumulation using a divided electrochemical flow cell

• Daniele Rocco,
• Ana A. Folgueiras-Amador,
• Richard C. D. Brown and
• Marta Feroci

Beilstein J. Org. Chem. 2022, 18, 979–990, doi:10.3762/bjoc.18.98

• as ligands in organometallic catalysts [9] and as versatile organocatalysts [10] in a very wide range of organic reactions such as classical benzoin condensation, transesterification, acylation, Knoevenagel reaction, Claisen condensation etc. The electrochemical generation of carbenes from ILs avoids

Cathodic generation of reactive (phenylthio)difluoromethyl species and its reactions: mechanistic aspects and synthetic applications

• Sadanobu Iwase,
• Shinsuke Inagi and
• Toshio Fuchigami

Beilstein J. Org. Chem. 2022, 18, 872–880, doi:10.3762/bjoc.18.88

• , these methods require various metal and organometallic reagents. On the other hand, electrochemical organic synthesis is a metal-free process and does not require any hazardous reagents and it produces less waste than conventional chemical syntheses. Therefore, electrochemical synthesis is desirable

Synthesis of α-(perfluoroalkylsulfonyl)propiophenones: a new set of reagents for the light-mediated perfluoroalkylation of aromatics

• Durbis J. Castillo-Pazos,
• Juan D. Lasso and
• Chao-Jun Li

Beilstein J. Org. Chem. 2022, 18, 788–795, doi:10.3762/bjoc.18.79

• perfluorinated chains into aromatic rings have been developed since the first reports of such transformation by George Tiers in 1960, and McLoughlin and Thrower in 1969 [2][3]. Most approaches have made extensive use of organometallic chemistry, radical initiators, photocatalysis, electrochemistry, and more

Inductive heating and flow chemistry – a perfect synergy of emerging enabling technologies

• Conrad Kuhwald,
• Sibel Türkhan and
• Andreas Kirschning

Beilstein J. Org. Chem. 2022, 18, 688–706, doi:10.3762/bjoc.18.70

• 400 °C exposed to an air flow. The importance of this study is the fact that no activating agents are required and water is the only byproduct. Organometallic chemistry and heating are not among the most intuitively sensible combinations. However, prior to the formation of an organometallic species

Menadione: a platform and a target to valuable compounds synthesis

• Acácio S. de Souza,
• Ruan Carlos B. Ribeiro,
• Dora C. S. Costa,
• Fernanda P. Pauli,
• David R. Pinho,
• Matheus G. de Moraes,
• Fernando de C. da Silva,
• Luana da S. M. Forezi and
• Vitor F. Ferreira

Beilstein J. Org. Chem. 2022, 18, 381–419, doi:10.3762/bjoc.18.43

Diametric calix[6]arene-based phosphine gold(I) cavitands

• Gabriele Giovanardi,
• Andrea Secchi,
• Arturo Arduini and
• Gianpiero Cera

Beilstein J. Org. Chem. 2022, 18, 190–196, doi:10.3762/bjoc.18.21

• via conventional protocols using (Me2S)AuCl. Notably, the organometallic macrocycles A,B,C(AuCl)2 could be isolated via column chromatography separation. Gold(I) catalysts were subsequently fully characterized by NMR analysis and high-resolution mass spectrometry. The conformation of the catalysts, in

DABCO-promoted photocatalytic C–H functionalization of aldehydes

• Bruno Maia da Silva Santos,
• Mariana dos Santos Dupim,
• Cauê Paula de Souza,
• Thiago Messias Cardozo and
• Fernanda Gadini Finelli

Beilstein J. Org. Chem. 2021, 17, 2959–2967, doi:10.3762/bjoc.17.205

• is reduced by the photocatalyst (PC−) after coordination to aryl bromide, promoting the turnover of organometallic and photoredox cycles. DABCO is regenerated via deprotonation by an inorganic base. We also investigated the mechanism operating when the reaction is performed in the absence of bicyclic

Iron-catalyzed domino coupling reactions of π-systems

• Austin Pounder and
• William Tam

Beilstein J. Org. Chem. 2021, 17, 2848–2893, doi:10.3762/bjoc.17.196

• ], nickel [20][21][22][23], and iridium [24][25][26][27] have taken center stage when it comes to the development of synthetic methodology. Although these late TMs have contributed enormously to the various fields of organic, inorganic, and organometallic chemistry, growing concerns regarding their economic

• compared to the more studied late TMs [39][40][41][42][43]. Besides the more recognized concept of TM cross-coupling reactions revolving around an organic electrophile bearing a leaving group and an organometallic nucleophile, there is another large area of cross-coupling reactions that have been under

Biological properties and conformational studies of amphiphilic Pd(II) and Ni(II) complexes bearing functionalized aroylaminocarbo-N-thioylpyrrolinate units

• Samet Poyraz,
• Samet Belveren,
• Sabriye Aydınoğlu,
• Mahmut Ulger,
• Abel de Cózar,
• Maria de Gracia Retamosa,
• Jose M. Sansano and
• H. Ali Döndaş

Beilstein J. Org. Chem. 2021, 17, 2812–2821, doi:10.3762/bjoc.17.192

• , antitumoral, antimalarial, antifungal, or antiviral activities [14]. In this study, as a continuation of our work related to organometallic compounds with very low/modest amphiphilic character [15][16][17], we propose the incorporation of a 3-indolylmethyl group in the ligand and compare the bioactivity

• organometallic compounds were screened for their antibacterial activity against a range of Gram-positive (Staphylococcus aureus, Bacillus subtilis) and Gram-negative (Aeromonas hydrophila, Escherichia coli, Acinetobacter baumannii) bacteria and antimycobacterial activity against M. tuberculosis H37Rv strains

• anti(myco)bacterial and antifungal activity of newly prepared organometallic compounds were investigated against some Gram-positive, Gram-negative bacteria, M. tuberculosis H37Rv strains and C. albicans, C. tropicalis, C. glabrata fungi. The screened novel complexes showed different degrees of

Recent advances in the asymmetric phosphoric acid-catalyzed synthesis of axially chiral compounds

• Alemayehu Gashaw Woldegiorgis and
• Xufeng Lin

Beilstein J. Org. Chem. 2021, 17, 2729–2764, doi:10.3762/bjoc.17.185

• ., fredericamycin A and acutumine [99]), SPINOL-based ligands and catalysts [100], and organometallic complexes with important applications. The use of chiral catalysts for spirocyclization reactions brings asymmetry at the site of the spirocyclic center while tolerating different electronic and steric functional

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

Transition-metal-free intramolecular Friedel–Crafts reaction by alkene activation: A method for the synthesis of some novel xanthene derivatives

• Tülay Yıldız,
• İrem Baştaş and
• Hatice Başpınar Küçük

Beilstein J. Org. Chem. 2021, 17, 2203–2208, doi:10.3762/bjoc.17.142

• organometallic chemistry and using transition metal catalysts, which need expensive and toxic chemicals. With the increasing interest in these methods, new organocatalysts and reagents that are less toxic, easier to use, readily accessible, and cheap have been developed [37]. In particular, the synthesis of

Chemical syntheses and salient features of azulene-containing homo- and copolymers

• Vijayendra S. Shetti

Beilstein J. Org. Chem. 2021, 17, 2164–2185, doi:10.3762/bjoc.17.139

• aqueous acid solution. Further, the coordination of polymers 37 and 39 to a multinuclear Ru cluster was investigated by the same group [32]. The organometallic complexes 40–43 were synthesized by treating polymers 37 and 39 with Ru3(CO)12 in refluxing xylene (Scheme 9). The ruthenium content in these

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

• organometallic chemistry and catalysis [128]. The first example of a stoichiometric manganese-mediated C–H activation, reported by Stone, Bruce, and co-workers (1970) [129], was an ortho-metalation in azobenzenes. In recent years, with the expansion of the C–H activation field, manganese catalysts have been

Fritsch–Buttenberg–Wiechell rearrangement of magnesium alkylidene carbenoids leading to the formation of alkynes

• Tsutomu Kimura,
• Koto Sekiguchi,
• Akane Ando and
• Aki Imafuji

Beilstein J. Org. Chem. 2021, 17, 1352–1359, doi:10.3762/bjoc.17.94

• treated with organometallic reagents to evaluate which combination of sulfoxides and organometallic reagents yielded alkynes the most efficiently. The use of 1-chlorovinyl p-tolyl sulfoxide and isopropylmagnesium chloride was optimal for this purpose. A variety of 1-chlorovinyl p-tolyl sulfoxides were

• series of 1-heteroatom-substituted vinyl p-tolyl sulfoxides 2a, 5–7, and 1-unsubstituted sulfoxide 8 were treated with organometallic reagents with the aim of finding the optimal combination of the metal and heteroatom substituent for the FBW rearrangement (Table 1). The 2,2-bis(4-methoxyphenyl

• chloride and 1-chlorovinyl p-tolyl sulfoxide 2a was the optimal combination of organometallic reagent and carbenoid precursor. The substrate scope was explored with a variety of sulfoxides 2b–g (Table 2). The 2,2-diphenyl-substituted sulfoxide 2b was converted into alkyne 4b by treatment with