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

• field of organic synthesis. These compounds are readily accessible, safe, and more stable than toxic, unstable, and foul-smelling thiols. These electrophilic sulfur sources have deserved particular interest for the C–S bond formation via the reaction with various nucleophiles. Their preparation is

• according to the different positions of the OMe group. The preparation of α,α-bisthiofunctionalized butenolides through a bis-sulfenylation methodology was reported by Zhou and Yuan et al. [49]. For this purpose, they applied N-(alkyl(aryl)sulfanyl)succinimides or N-(phenylsulfanyl)phthalimides using a

• that is enhanced due to the Lewis basic character of the final product. Reddy and co-workers developed a simple method for the preparation of 1,2-thiosulfonylethenes 71 and 1,1-dithioethenes 69 in the presence of a nickel catalyst (Scheme 30) [64]. Various alkynyl bromides 68 as starting materials

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

• , which are subsequently cyclized into indanones 3. From a synthetic point of view, the use of hydroxy ketones 1 as starting compounds for the cyclization without additional preparation and isolation of the corresponding enones 2 is more economical as it reduces the number of steps in the synthesis. Other

Functions of enzyme domains in 2-methylisoborneol biosynthesis and enzymatic synthesis of non-natural analogs

• Binbin Gu,
• Lin-Fu Liang and
• Jeroen S. Dickschat

Beilstein J. Org. Chem. 2023, 19, 1452–1459, doi:10.3762/bjoc.19.104

• -methylisoborneol For the enzymatic preparation of non-natural analogs of 1 different combinations of DMAPP and IPP derivatives were used (Table 1). The synthesis of the DMAPP analogs DA-1, DA-2 and DA-6 and of the IPP analogs IA-1, IA-2 and IA-3 was reported previously [26][33][34], and DA-3, DA-4 and DA-5 were

• coupling of DMAPP and 2-Me-IPP to 2-Me-GPP, and 2MIBS for the conversion into 1. Enzymatic synthesis of analogs of 1. A) Preparation of 2 from DA-4 and IA-1, B) preparation of 3 and the inseparable mixture of 4 and 5 from DA-5 and IA-1, C) structures of 2MIBS side products 6 and 7, and D) the

• stereochemical course for the geminal methyl groups in GPP investigated by feeding of (1-13C)-1-desoxyxylulose. Black dots represent 13C-labelled carbons. Enzymatic synthesis of analogs of 1a. Supporting Information Supporting Information File 88: Biosynthesis and enzymatic preparation of the non-natural

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

• , thereby precluding its synthetic exploitation. Results and Discussion Preparation of α-(aminomethyl)acrylates We commenced our study by preparing a selection of α-(aminomethyl)acrylates with variations of the nitrogen protecting group and the ester substituent. Towards this end, the direct allylation of

• . Furthermore, our protocol provides a complement to existing literature, as none of the previously reported methods to convert α-(aminomethyl)acrylates into enantioenriched β-amino acids is applicable for the preparation of β2,2-amino acids [27][28][29][30][31]. Experimental 1. Procedure for the monoallylation

• of primary amines and tert-butylsulfinamide (preparation of compounds 5–7 and 8a–c). In a round-bottomed flask under argon, n-BuLi (1.0 equiv, soln. in heptane) was added dropwise to a THF (0.2 mol·L−1) solution of the appropriate primary amine or tert-butylsulfinamide (1.0 equiv) at −55 °C. The

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

• the metal to the π* orbital of the NHC. Over the last two decades, NHC–metal complexes have been extensively used as efficient catalysts in different types of organic reactions. Of these, NHC–Cu(I) complexes found prominence for various reasons, such as ease of preparation, possibility of structural

• carboxylation, C(sp2)–H alkenylation and allylation, C(sp2)–H arylation, C(sp2)–H amidation, and C(sp2)–H thiolation. Preceding the section of applications, a brief description of the structure of NHCs, nature of NHC–metal bond, and methods of preparation of NHC–Cu complexes is provided. Keywords: conjugate

• generation of the first NHC can be credited to Öfele [1] who could prepare an imidazolylidene–Cr(VI) complex in 1968 (Scheme 1). Likewise, in the same year, Wanzlick [2] obtained imidazolylidene–Hg(II) complex 4 (Scheme 2). The preparation of an isolable and bottlable NHC, imidazolylidene 6 (Scheme 3

One-pot nucleophilic substitution–double click reactions of biazides leading to functionalized bis(1,2,3-triazole) derivatives

• Hans-Ulrich Reissig and
• Fei Yu

Beilstein J. Org. Chem. 2023, 19, 1399–1407, doi:10.3762/bjoc.19.101

• . Supporting Information Supporting Information File 86: Experimental procedures, spectroscopic and analytical characterization data of new compounds as well as copies of the NMR spectra. Acknowledgements We thank Dr. Reinhold Zimmer for his valuable assistance during preparation of the manuscript. Funding We

Consecutive four-component synthesis of trisubstituted 3-iodoindoles by an alkynylation–cyclization–iodination–alkylation sequence

• Nadia Ledermann,
• Alae-Eddine Moubsit and
• Thomas J. J. Müller

Beilstein J. Org. Chem. 2023, 19, 1379–1385, doi:10.3762/bjoc.19.99

• [9][10][11] and their preparation is an evergreen in organic synthesis [12][13][14][15]. Although the classical Fischer indole synthesis provides a very reliable and broadly applicable access to indole derivatives [16][17][18], striving for new indole syntheses is ongoing. In particular, metal

Visible-light-induced nickel-catalyzed α-hydroxytrifluoroethylation of alkyl carboxylic acids: Access to trifluoromethyl alkyl acyloins

• Feng Chen,
• Xiu-Hua Xu,
• Zeng-Hao Chen,
• Yue Chen and
• Feng-Ling Qing

Beilstein J. Org. Chem. 2023, 19, 1372–1378, doi:10.3762/bjoc.19.98

• challenging, and to the best of our knowledge, only Kawase's group [26] reported the preparation of such compounds starting from α-hydroxy acids or α-amino acids in the presence of trifluoroacetic anhydride and pyridine with very limited substrate scope (Scheme 1c). Therefore, the development of a more

• of readily available alkyl carboxylic acids with N-trifluoroethoxyphthalimide. The present study provides a mild and efficient method for the preparation of trifluoromethyl alkyl acyloins in moderate to high yields and with good functional group compatibility. Further studies on expansion of the

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

• properties via an original mechanism of action. The increasing interest in studying ether lipids for fundamental and applied researches invited to review the methodologies developed to prepare ether lipids. In this review we focus on the synthetic method used for the preparation of alkyl ether lipids either

• community working on the analysis of EL that require the preparation of standards for analytical purposes. The analysis and quantification of ether lipids is a very important field of research and development that was previously reviewed [47][48]. In this review, we focus on synthesis methodologies applied

• to prepare alkyl ether lipids. The synthesis methods specifically designed for the preparation of alkenyl ether lipids (plasmalogen) are not reviewed herein. For each compound, their synthesis is reported jointly, when appropriate, with some elements relative to their biological activity. The next

Metal catalyst-free N-allylation/alkylation of imidazole and benzimidazole with Morita–Baylis–Hillman (MBH) alcohols and acetates

• Olfa Mhasni,
• Jalloul Bouajila and
• Farhat Rezgui

Beilstein J. Org. Chem. 2023, 19, 1251–1258, doi:10.3762/bjoc.19.93

• bifonazole have become well-established drugs for the treatment of numerous mycotic infections (Figure 1) [9][10]. Therefore, the development of new methods for the preparation of such compounds is highly required. The MBH acetates, instead of the corresponding alcohols, have been extensively used as

• . Typical procedure for the preparation of imidazole derivatives 8 A mixture of acyclic MBH alcohol 1 (1 mmol), imidazole (2a, 2 mmol) and DABCO (1 mmol), was stirred at reflux temperature of methanol or toluene. After completion of the reaction, the solvent was removed by rotary evaporation and CH2Cl2 (10

Acetaldehyde in the Enders triple cascade reaction via acetaldehyde dimethyl acetal

• Alessandro Brusa,
• Debora Iapadre,
• Maria Edith Casacchia,
• Alessio Carioscia,
• Giuliana Giorgianni,
• Giandomenico Magagnano,
• Fabio Pesciaioli and
• Armando Carlone

Beilstein J. Org. Chem. 2023, 19, 1243–1250, doi:10.3762/bjoc.19.92

• single operation and from readily available substrates. Their combination with asymmetric aminocatalysis [4][6][7][8] has recently led to innovative approaches for the one-step enantioselective preparation of stereochemically dense molecules. Nowadays, organocatalytic cascade processes provide a powerful

Selective construction of dispiro[indoline-3,2'-quinoline-3',3''-indoline] and dispiro[indoline-3,2'-pyrrole-3',3''-indoline] via three-component reaction

• Ziying Xiao,
• Fengshun Xu,
• Jing Sun and
• Chao-Guo Yan

Beilstein J. Org. Chem. 2023, 19, 1234–1242, doi:10.3762/bjoc.19.91

• procedure for the preparation of compounds 3a–m To a round flask was added 3-isatyl-1,4-dicarbonyl compound 1 (0.20 mmol), isatin 2 (0.20 mmol), ammonium acetate (0.80 mmol), piperidine (0.30 mmol), toluene (2.0 mL) and methanol (2.0 mL). The mixture was heated at 50 °C for seven hours. After removing the

• . for C42H37Cl2N3O5, 756.2002; found, 756.1989. General procedure for the preparation of compounds 4a–p To a round flask was added 3-isatyl-1,4-dicarbonyl compound 1 (0.20 mmol), isatin 2 (0.20 mmol), ammonium acetate (0.80 mmol), piperidine (0.30 mmol), toluene (2.0 mL) and methanol (2.0 mL). The

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

• in linear internal alkenes. Building on this key iron catalysis result, our group and that of Shi contemporaneously reported the photochemical diazidation of alkenes using stoichiometric iron and no external oxidant or ancillary ligand, providing a simple protocol for the preparation of vicinal

Two new lanostanoid glycosides isolated from a Kenyan polypore Fomitopsis carnea

• Winnie Chemutai Sum,
• Sherif S. Ebada,
• Didsanutda Gonkhom,
• Cony Decock,
• Rémy Bertrand Teponno,
• Josphat Clement Matasyoh and
• Marc Stadler

Beilstein J. Org. Chem. 2023, 19, 1161–1169, doi:10.3762/bjoc.19.84

• , Germany), and Avantor Performance Materials (Deventer, Netherlands). An in-house Purelab® flex water purification system (Veolia Water Technologies, Celle, Germany), was used in the preparation of deionized water. Fungal material examined The current study specimen was collected by one of the authors C.D

• comparison of its morphological traits to close relatives. Fermentation and metabolites extraction Mycelial cultures of F. carnea were fermented on solid and liquid-state media based on previously established methodologies [37]. Essentially, the preparation of solid-state media was as follows: 90 mg of rice

New one-pot synthesis of 4-arylpyrazolo[3,4-b]pyridin-6-ones based on 5-aminopyrazoles and azlactones

• Vladislav Yu. Shuvalov,
• Ekaterina Yu. Vlasova,
• Tatyana Yu. Zheleznova and
• Alexander S. Fisyuk

Beilstein J. Org. Chem. 2023, 19, 1155–1160, doi:10.3762/bjoc.19.83

• aldehyde with thioglycolic acid and aminopyrazole, followed by the extrusion of sulfur from the resulting thiazepine [20] (method C). The three-stage synthesis of 4-arylpyrazolo[3,4-b]pyridin-6-ones, involving the preparation of 3-aryl-N-(1H-pyrazol-5-yl)propiolamides (method D), also leads to the

• formation of the target products with low yields [21]. Therefore, the development of a new effective method for the preparation of 4-arylpyrazolo[3,4-b]pyridin-6-ones is an urgent task. Results and Discussion One of the rational approaches to the synthesis of fused pyridine derivatives is based on the

• temperatures from 90 to 150 °C for 1.5, 3.5 and 6 h in the presence of KOH or t-BuOK (Table 1). The best yield of 4-phenylpyrazolo[3,4-b]pyridin-6-one 4а (81%) was achieved at 150 °C in DMSO containing 1.5 equiv of t-BuOK for 1.5 h. Obviously, the preparation of 4-phenylpyrazolo[3,4-b]pyridin-6-one 4а could be

Synthesis of imidazo[4,5-e][1,3]thiazino[2,3-c][1,2,4]triazines via a base-induced rearrangement of functionalized imidazo[4,5-e]thiazolo[2,3-c][1,2,4]triazines

• Dmitry B. Vinogradov,
• Alexei N. Izmest’ev,
• Angelina N. Kravchenko,
• Yuri A. Strelenko and
• Galina A. Gazieva

Beilstein J. Org. Chem. 2023, 19, 1047–1054, doi:10.3762/bjoc.19.80

• ][1,2,4]triazine or imidazo[4,5-e]thiazolo[2,3-c][1,2,4]triazine and the expansion of the thiazolidine ring to a thiazine core. The methodology proved to be effective for the preparation of a series of target compounds with different substituents in the tricyclic fragment. Examples of natural and

Copper-catalyzed N-arylation of amines with aryliodonium ylides in water

• Kasturi U. Nabar,
• Bhalchandra M. Bhanage and
• Sudam G. Dawande

Beilstein J. Org. Chem. 2023, 19, 1008–1014, doi:10.3762/bjoc.19.76

• in oxidation, C–C, C–X bond formation, rearrangements, and halogenation reactions [23][24][25]. Due to the nontoxic nature, easier preparation, and handling of the hypervalent iodine reagents, many researchers are attracted to unravel the chemistry and reactivity of these reagents. Amongst different

The unique reactivity of 5,6-unsubstituted 1,4-dihydropyridine in the Huisgen 1,4-diploar cycloaddition and formal [2 + 2] cycloaddition

• Xiu-Yu Chen,
• Hui Zheng,
• Ying Han,
• Jing Sun and
• Chao-Guo Yan

Beilstein J. Org. Chem. 2023, 19, 982–990, doi:10.3762/bjoc.19.73

• act as activated alkene to take part in various cycloaddition reactions [35][36][37][38][39][40]. For example, Lavilla and co-workers developed a Sc(OTf)3-catalyzed three-component reaction of 5,6-unsubstituted 1,4-dihydropyridines, arylamines and ethyl glyoxylate for the preparation of various pyrido

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

• temeperatures. In 2000, the application of the Clauson–Kaas reaction was nicely explored by Sonnet et al. [56] for the preparation of diverse pyrrolizinones. The pyrrole derivatives 5 and 7 were synthesized by the classical Clauson–Kaas reaction by refluxing amines 4 or 6 with 2,5-dimethoxytetrahydrofuran (2

• synthesis of arylpyrrolo- and pyrazolopyrrolizinones, in which the Clauson–Kaas reaction was used as key step for the preparation of pyrrole derivatives 13. The condensation of amines 12 with 2,5-DMTHF (2) was carried out in the presence of p-chloropyridine hydrochloride as catalyst and dioxane as reaction

• 2013, Zhang and co-workers [67] reported the preparation of a new recyclable magnetic nanoparticle-supported antimony catalyst (γ-Fe2O3@SiO2-Sb-IL) and its application in the filtration-free, Clauson–Kaas synthesis of N-substituted pyrroles. This catalyst is fairly easy to make, air stable, and

First synthesis of acylated nitrocyclopropanes

• Kento Iwai,
• Rikiya Kamidate,
• Khimiya Wada,
• Haruyasu Asahara and
• Nagatoshi Nishiwaki

Beilstein J. Org. Chem. 2023, 19, 892–900, doi:10.3762/bjoc.19.67

• mass spectrometers. All measurements were made on a Rigaku AFC7R diffractometer with graphite monochromatized Mo Kα radiation. Melting points were recorded on an SRS-Optimelt automated melting point system and were uncorrected. Preparation of nitrostyrenes 2 Nitrostyrenes 2 were prepared according to

Light-responsive rotaxane-based materials: inducing motion in the solid state

• Adrian Saura-Sanmartin

Beilstein J. Org. Chem. 2023, 19, 873–880, doi:10.3762/bjoc.19.64

• molecular materials, the development of a wide variety of suitable compounds is essential. The use of stimuli-responsive molecules has paved the way for the preparation of advanced functional materials [6][7][8][9][10]. In this scenario, mechanically interlocked molecules (MIMs) have postulated as ideal

• the interlocked arrangement. As an illustrative example, cucurbit[8]uril-based pseudorotaxanes having a pair of styrylpyridinium threads bearing carboxylic acid groups were employed in the preparation of the uranium-organic framework U-CB[8]-MPyVB (Figure 4a) [63]. The solid structure of the MOFs

• deformation paves the way to the development of photoactuator devices leading to envision advanced applications in optomechanics and microrobotics. Outlook The employment of light-responsive rotaxanes and pseudorotaxanes in the preparation of functional advanced materials leads to envision a promising future

A fluorescent probe for detection of Hg²⁺ ions constructed by tetramethyl cucurbit[6]uril and 1,2-bis(4-pyridyl)ethene

• Xiaoqian Chen,
• Naqin Yang,
• Yue Ma,
• Xinan Yang and
• Peihua Ma

Beilstein J. Org. Chem. 2023, 19, 864–872, doi:10.3762/bjoc.19.63

• ) was purchased from Aladdin, and the other reagents were analytical grade and ready for use. TMeQ[6] was synthesized and purified in our laboratory. Preparation of complex 1 TMeQ[6] (15 mg, 14.26 µmol), ZnCl2 (5 mg, 36.7 μmol) and 1,2-bis(4-pyridyl)ethene (3 mg, 16.48 µmol), were dissolved in 5 mL of 3

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

Facile access to 3-sulfonylquinolines via Knoevenagel condensation/aza-Wittig reaction cascade involving ortho-azidobenzaldehydes and β-ketosulfonamides and sulfones

• Ksenia Malkova,
• Andrey Bubyrev,
• Stanislav Kalinin and
• Dmitry Dar’in

Beilstein J. Org. Chem. 2023, 19, 800–807, doi:10.3762/bjoc.19.60

• synthesis of quinoline-3-sulfonyl chlorides which are the most common reagents for their preparation. As a possible solution, the approach to the heterocyclic core construction from a sulfonamide-containing building block may be considered. In turn, diversely substituted quinoline-3-sulfones are available

• was predominantly applied for the preparation of the corresponding esters. Inspired by this study, we became interested to utilize o-azidobenzaldehydes 1 in combination with ketosulfonamides/ketosulfones 2 as precursors in a new convenient synthetic procedure leading towards 3-sulfonyl-substituted

• quinolines (sulfonamides and sulfones) (Figure 2b). Herein, we report the successful implementation of this approach. Results and Discussion The Knoevenagel condensation/aza-Wittig reaction cascade was used for the preparation of 3-sulfonyl-substituted quinolines. The process proceeds in a domino fashion

Synthesis of substituted 8H-benzo[h]pyrano[2,3-f]quinazolin-8-ones via photochemical 6π-electrocyclization of pyrimidines containing an allomaltol fragment

• Constantine V. Milyutin,
• Andrey N. Komogortsev,
• Boris V. Lichitsky,
• Mikhail E. Minyaev and
• Valeriya G. Melekhina

Beilstein J. Org. Chem. 2023, 19, 778–788, doi:10.3762/bjoc.19.58

• applications in various areas of science and technology [3][4][5]. For example, the use of photoreactions for the preparation of complex natural products allows reducing the number of synthetic steps [6][7][8][9]. Moreover, in some cases photochemical processes can open access to complicated multifunctional

• were not optimal and the process could be significantly improved. In order to employ the aforementioned approach for the preparation of pyrimidines containing an allomaltol moiety we initially selected the interaction of enaminone 13a with cyanamide as a model reaction. We varied time and temperature

• photochemical side processes involving the thiophene ring. Conclusion In summary we have developed an approach for the preparation of pyrimidines with an allomaltol fragment. The suggested method started with the synthesis of pyrimidines from the reaction of 2-(1-(dimethylamino)-3-oxo-3-arylprop-1-en-2-yl)-3