Unveiling the regioselectivity of rhodium(I)-catalyzed [2 + 2 + 2] cycloaddition reactions for open-cage C₇₀ production

• Cristina Castanyer,
• Anna Pla-Quintana,
• Anna Roglans,
• Albert Artigas and
• Miquel Solà

Beilstein J. Org. Chem. 2024, 20, 272–279, doi:10.3762/bjoc.20.28

• medical applications) and improving their stability, among other desirable properties. The most common reactions used to functionalize fullerenes are Diels–Alder and 1,3-dipolar cycloadditions and Bingel–Hirsch cyclopropanations [19][20]. In most cases, functionalization occurs while preserving the carbon

Trifluoromethylated hydrazones and acylhydrazones as potent nitrogen-containing fluorinated building blocks

• Zhang Dongxu

Beilstein J. Org. Chem. 2023, 19, 1741–1754, doi:10.3762/bjoc.19.127

• under basic conditions, and expanded the synthetic method to N-substituted acylhydrazones [106][107] (Scheme 18). In the early development of 1,3-dipolar cycloadditions of azomethine imines, the acyclic azomethine imines were unstable and their in situ preparation required Brønsted acid or thermal

Decarboxylative 1,3-dipolar cycloaddition of amino acids for the synthesis of heterocyclic compounds

• Xiaofeng Zhang,
• Xiaoming Ma and
• Wei Zhang

Beilstein J. Org. Chem. 2023, 19, 1677–1693, doi:10.3762/bjoc.19.123

• products 3c and 3d can be used for a second cycloaddition to form products 4a and 4b. The non-stabilized AMYs C1 and C2 have neither an EWG nor an Ar group to localize the negative charge. The 1,3-dipolar cycloadditions of C-type AMYs lead to the formation of [3 + 2] adducts 5 or 6 with low regio- and

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

• -benzothiazol-2-yl(diazo)acetates (Scheme 1, entry 3) [12], dearomative [3 + 2] cycloaddition reactions of benzothiazoles with cyclopropanes (Scheme 1, entry 4) [13][14][15], multicomponent reactions (MCRs) of benzothiazoles, isocyanides and 2-methylidenemalonates (Scheme 1, entry 5) [16], 1,3-dipolar

• cycloadditions of N-alkylbenzothiazolium salts (Scheme 1, entry 6) [17][18][19][20][21][22], MCRs of 2-methylbenzothiazole, acetylenedicarboxylates and active methylene compounds (Scheme 1, entry 7) [23][24][25], MCRs of (1,3-benzothiazol-2-yl)acetonitrile, aldehydes and acylcyanides (Scheme 1, enry 8) [3][26

Selective sulfonylation and isonitrilation of para-quinone methides employing TosMIC as a source of sulfonyl group or isonitrile group

• Chuanhua Qu,
• Run Huang,
• Yong Li,
• Tong Liu,
• Yuan Chen and
• Guiting Song

Beilstein J. Org. Chem. 2021, 17, 2822–2831, doi:10.3762/bjoc.17.193

• combination of acidic α-carbon atoms, isocyano groups, and sulfonyl moieties [18]. In general, TosMIC undergoes base-mediated 1,3-dipolar cycloadditions with activated alkenes to provide pyrroles as products [18] (Scheme 1A). Recently, alternative functionalizations using TosMIC as a tosyl source of

Synthesis of new bile acid-fused tetrazoles using the Schmidt reaction

• Dušan Đ. Škorić,
• Olivera R. Klisurić,
• Dimitar S. Jakimov,
• Marija N. Sakač and
• János J. Csanádi

Beilstein J. Org. Chem. 2021, 17, 2611–2620, doi:10.3762/bjoc.17.174

• hazardous [26][27]. Some recent studies employ this reagent in the Schmidt synthesis of tetrazoles from ketones that are smaller in size and simpler than the steroidal ketones in this work [28][29]. For the synthesis of steroidal tetrazoles, most often 1,3-dipolar cycloadditions are being used. In this way

A comprehensive review of flow chemistry techniques tailored to the flavours and fragrances industries

• Guido Gambacorta,
• James S. Sharley and
• Ian R. Baxendale

Beilstein J. Org. Chem. 2021, 17, 1181–1312, doi:10.3762/bjoc.17.90

Selective and reversible 1,3-dipolar cycloaddition of 6-aryl-1,5-diazabicyclo[3.1.0]hexanes with 1,3-diphenylprop-2-en-1-ones under microwave irradiation

• Alexander P. Molchanov,
• Mariia M. Efremova,
• Mariya A. Kryukova and
• Mikhail A. Kuznetsov

Beilstein J. Org. Chem. 2020, 16, 2679–2686, doi:10.3762/bjoc.16.218

• AMIs can be generated in situ by thermal opening of any C–N bond of the diaziridine ring in 6-aryl-substituted 1,5-diazabicyclo[3.1.0]hexanes or 7-aryl-substituted 1,6-diazabicyclo[4.1.0]heptanes, respectively [16][17]. For the thermal generation conditions, the 1,3-dipolar cycloadditions of AMIs were

• -dipolar cycloadditions under thermal or catalytic conditions [1][2]. In general, cyclic azomethine imines are classified into two types, depending on their structure: N,N'-cyclic AMIs with both nitrogen atoms included in the cyclic system and C,N-cyclic AMIs having the C=N motif in the cycle (Scheme 1) [3

• reaction undergo cycloreversion under the reaction conditions. Keywords: azomethine imines; cycloaddition; diazabicyclohexanes; diaziridines; regioselectivity; Introduction Cyclic azomethine imines (AMIs) are very useful synthetic blocks for the preparation of diverse dinitrogenated heterocycles by 1,3

Highly selective Diels–Alder and Heck arylation reactions in a divergent synthesis of isoindolo- and pyrrolo-fused polycyclic indoles from 2-formylpyrrole

• Carlos H. Escalante,
• Eder I. Martínez-Mora,
• Carlos Espinoza-Hicks,
• Alejandro A. Camacho-Dávila,
• Fernando R. Ramos-Morales,
• Francisco Delgado and
• Joaquín Tamariz

Beilstein J. Org. Chem. 2020, 16, 1320–1334, doi:10.3762/bjoc.16.113

• ][64][65][66][67][68][69][70], and pericyclic reactions (Diels–Alder and 1,3-dipolar cycloadditions) [71][72][73][74][75]. To account for the endo selectivity of all the tested dienes, the geometry of cycloaddends at the TSs was carefully analyzed (Figure 4 and Supporting Information File 1, Appendix 6

Ferrocenyl-substituted tetrahydrothiophenes via formal [3 + 2]-cycloaddition reactions of ferrocenyl thioketones with donor–acceptor cyclopropanes

• Grzegorz Mlostoń,
• Mateusz Kowalczyk,
• André U. Augustin,
• Peter G. Jones and
• Daniel B. Werz

Beilstein J. Org. Chem. 2020, 16, 1288–1295, doi:10.3762/bjoc.16.109

• practical importance [1][2]. The development of chemo- and diastereoselective syntheses for these compounds is thus a challenging problem. An elegant and highly efficient method for the construction of the tetrahydrothiophene ring is based on 1,3-dipolar cycloadditions of in-situ-generated thiocarbonyl S

Synthesis of pyrrolidinedione-fused hexahydropyrrolo[2,1-a]isoquinolines via three-component [3 + 2] cycloaddition followed by one-pot N-allylation and intramolecular Heck reactions

• Xiaoming Ma,
• Suzhi Meng,
• Xiaofeng Zhang,
• Qiang Zhang,
• Shenghu Yan,
• Yue Zhang and
• Wei Zhang

Beilstein J. Org. Chem. 2020, 16, 1225–1233, doi:10.3762/bjoc.16.106

• related to natural products [18][19][20]. Among the well-established MCRs, three-component 1,3-dipolar cycloadditions of benzaldehydes, maleimides, and amino esters have been developed for making N-containing 5-membered heterocycles (Scheme 1) [21][22]. The [3 + 2] cycloadditions of maleimides with

A systematic review on silica-, carbon-, and magnetic materials-supported copper species as efficient heterogeneous nanocatalysts in “click” reactions

• Pezhman Shiri and
• Jasem Aboonajmi

Beilstein J. Org. Chem. 2020, 16, 551–586, doi:10.3762/bjoc.16.52

• , copper nanoparticles-decorated three-dimensional graphene (3D graphene/Cu nanocomposite 87) was reported as a catalyst to perform Huisgen 1,3‐dipolar cycloadditions. Therein, the GO material was mixed with EDA to produce a stable suspension that was transferred to a teflon‐lined autoclave. After heating

• laponite® discs was to prevent their aggregation. Moreover, the catalytic activity of the nanocomposite 136 was explored in 1,3-dipolar cycloadditions of alkynes with in situ-generated organic azides. The reactions proceeded well in an aqueous medium at 70 °C with 0.004 g of the catalyst (Scheme 30). In

Diaminoterephthalate–α-lipoic acid conjugates with fluorinated residues

• Leon Buschbeck,
• Aleksandra Markovic,
• Gunther Wittstock and
• Jens Christoffers

Beilstein J. Org. Chem. 2019, 15, 981–991, doi:10.3762/bjoc.15.96

• example for an application in biochemistry, Figure 1 shows a compound with cyclooctyne and maleimide as functional units. It was used as a "turn-on" fluorescence probe for cross-linking proteins [13]. The highly reactive cyclooctyne residue undergoes 1,3-dipolar cycloadditions with organoazides (copper

Synthesis and fluorescent properties of N(9)-alkylated 2-amino-6-triazolylpurines and 7-deazapurines

• Andrejs Šišuļins,
• Jonas Bucevičius,
• Yu-Ting Tseng,
• Irina Novosjolova,
• Kaspars Traskovskis,
• Ērika Bizdēna,
• Huan-Tsung Chang,
• Sigitas Tumkevičius and
• Māris Turks

Beilstein J. Org. Chem. 2019, 15, 474–489, doi:10.3762/bjoc.15.41

• synthesis of a novel library of 9-alkyl-2-amino-6-triazolylpurine derivatives. Thus, copper-catalyzed azide–alkyne 1,3-dipolar cycloaddition reaction of compounds 6a–c with different para-substituted phenylacetylenes produced the expected compounds 7a–f, 8a–f and 9 (Scheme 1). The yields of 1,3-dipolar

• cycloadditions varied from 51% to 76% in the case of pyrrolidinyl purines 7a–f and from 53% to 86% for piperidinyl purines 8a–f (Table 1 and Table 2). To gain an insight into the structure–photophysical properties relationship of the newly obtained structures, various EDG and EWG at the para-position of the

Synthesis of nonracemic hydroxyglutamic acids

• Dorota G. Piotrowska,
• Iwona E. Głowacka,
• Andrzej E. Wróblewski and
• Liwia Lubowiecka

Beilstein J. Org. Chem. 2019, 15, 236–255, doi:10.3762/bjoc.15.22

• diastereoselectivities of 1,3-dipolar cycloadditions which allow to control stereochemistries at C3 and C5 [79][80]. To illustrate this concept the E/Z mixture of nitrone 70 was reacted with acrylamide 71 prepared from (2S)-bornane-10,2-sultam to afford mainly (20:1) the isoxazolidine (3S,5S)-72 easily separable from

• obtained after cleavage of 84 under basic conditions. From pyroglutamic acid In case of low availability of selected stereoisomers of 4-hydroxyprolines asymmetric syntheses of enantiomeric 4-hydroxypyroglutamates have been elaborated employing 1,3-dipolar cycloadditions of homochiral nitrones and acrylates

An efficient and facile access to highly functionalized pyrrole derivatives

• Meng Gao,
• Wenting Zhao,
• Hongyi Zhao,
• Ziyun Lin,
• Dongfeng Zhang and
• Haihong Huang

Beilstein J. Org. Chem. 2018, 14, 884–890, doi:10.3762/bjoc.14.75

• , azomethine ylide) as the key substrate for 1,3-dipolar cycloadditions, the reaction conditions were very different exemplified by the wide range of reaction times from 0.3 h to 120 h, and the variable yields from 68% to 100% in different solvents. In order to establish the optimal experimental conditions

• yield (64%, Table 2, entry 1). The annulation process did not occur without the catalyst (Table 2, entry 2). Since most of the 1,3-dipolar cycloadditions are known to work best in nonpolar solvents, toluene instead of CH2Cl2 was selected as the reaction solvent. Unfortunately, toluene was not a good

Syn-selective silicon Mukaiyama-type aldol reactions of (pentafluoro-λ⁶-sulfanyl)acetic acid esters with aldehydes

• Anna-Lena Dreier,
• Andrej V. Matsnev,
• Joseph S. Thrasher and
• Günter Haufe

Beilstein J. Org. Chem. 2018, 14, 373–380, doi:10.3762/bjoc.14.25

• [22]. There are not many transformations of aliphatic SF5 compounds described in the literature. Among them are the preparation and derivatization of SF5-aldehydes [23], Diels–Alder reactions [24][25][26], the “click reaction” of SF5-acetylenes with azides to form triazoles [27], and 1,3-dipolar

• cycloadditions of azomethine ylides with pentafluoro-λ6-sulfanyl-substituted acrylic esters and amides [28]. A couple of years ago, we became interested in SF5-substituted ester enolates as reaction intermediates. Thus, in 2016 we reported a highly anti-selective aldol addition of SF5-substituted acetic ester

Dialkyl dicyanofumarates and dicyanomaleates as versatile building blocks for synthetic organic chemistry and mechanistic studies

• Grzegorz Mlostoń and
• Heinz Heimgartner

Beilstein J. Org. Chem. 2017, 13, 2235–2251, doi:10.3762/bjoc.13.221

• isomeric homo-Diels–Alder adducts were found in the mixture. [3 + 2]-Cycloadditions (1,3-dipolar cycloadditions) Electron-rich 1,3-dipoles such as thiocarbonyl S-methanides and azomethine ylides react with dipolarophiles E-1 and Z-1 to give five-membered cycloadducts through stepwise zwitterionic reaction

A novel application of 2-silylated 1,3-dithiolanes for the synthesis of aryl/hetaryl-substituted ethenes and dibenzofulvenes

• Grzegorz Mlostoń,
• Paulina Pipiak,
• Róża Hamera-Fałdyga and
• Heinz Heimgartner

Beilstein J. Org. Chem. 2017, 13, 1900–1906, doi:10.3762/bjoc.13.185

• presented protocol offers a new, highly efficient approach to tetrasubstituted ethenes and dibenzofulvenes bearing aryl and/or hetaryl substituents. Keywords: diazomethanes; 1,3-dipolar cycloadditions; olefination reactions; reaction mechanisms; thioketones; Introduction Aryl and hetaryl-substituted

Synthesis and metal binding properties of N-alkylcarboxyspiropyrans

• Alexis Perry and
• Christina J. Kousseff

Beilstein J. Org. Chem. 2017, 13, 1542–1550, doi:10.3762/bjoc.13.154

• previously reported [28]. Presumably, this reaction proceeds via azomethine ylid 6 (Scheme 3); analogous indolium ylids have been used synthetically in 1,3-dipolar cycloadditions [29] and mechanistic studies have been published on the related decarboxylation of pyridinium 2-carboxylates [30]. Fortunately, α

Ultrasound-promoted organocatalytic enamine–azide [3 + 2] cycloaddition reactions for the synthesis of ((arylselanyl)phenyl-1H-1,2,3-triazol-4-yl)ketones

• Gabriel P. Costa,
• Natália Seus,
• Juliano A. Roehrs,
• Raquel G. Jacob,
• Ricardo F. Schumacher,
• Thiago Barcellos,
• Rafael Luque and
• Diego Alves

Beilstein J. Org. Chem. 2017, 13, 694–702, doi:10.3762/bjoc.13.68

• carbonyl compounds could successfully generate an enamine or an enolate, and these species react as dipolarophiles with organic azides in organocatalyzed 1,3-dipolar cycloadditions. Our research group has demonstrated β-enamine–azide cycloaddition reactions for the synthesis of selenium-functionalized

Dimerization reactions of aryl selenophen-2-yl-substituted thiocarbonyl S-methanides as diradical processes: a computational study

• Michael L. McKee,
• Grzegorz Mlostoń,
• Katarzyna Urbaniak and
• Heinz Heimgartner

Beilstein J. Org. Chem. 2017, 13, 410–416, doi:10.3762/bjoc.13.44

• intermediate, delocalized diradical species. The influence of selenium as a ‘heavy atom’ for stabilization of this intermediate has been emphasized. Keywords: 1,3-dipolar cycloadditions; reaction mechanisms; reactive intermediates; thiocarbonyl S-methanides; thioketones; Introduction Thiocarbonyl S

Development of a continuous process for α-thio-β-chloroacrylamide synthesis with enhanced control of a cascade transformation

• Olga C. Dennehy,
• Valérie M. Y. Cacheux,
• Benjamin J. Deadman,
• Denis Lynch,
• Stuart G. Collins,
• Humphrey A. Moynihan and
• Anita R. Maguire

Beilstein J. Org. Chem. 2016, 12, 2511–2522, doi:10.3762/bjoc.12.246

• ] and 1,3-dipolar cycloadditions [6][7][8][9], and oxidation of the sulfide group [10][11][12] are among a wide array of transformations which have been successfully applied to these compounds (Scheme 1). In order to fully exploit the synthetic potential of these β-chloroacrylamides, however, a means of

Combined experimental and theoretical studies of regio- and stereoselectivity in reactions of β-isoxazolyl- and β-imidazolyl enamines with nitrile oxides

• Ilya V. Efimov,
• Marsel Z. Shafikov,
• Nikolai A. Beliaev,
• Natalia N. Volkova,
• Tetyana V. Beryozkina,
• Wim Dehaen,
• Zhijin Fan,
• Viktoria V. Grishko,
• Gert Lubec,
• Pavel A. Slepukhin and
• Vasiliy A. Bakulev

Beilstein J. Org. Chem. 2016, 12, 2390–2401, doi:10.3762/bjoc.12.233

• 4i), respectively. The regio- and stereospecificity and the apparent reaction rate increase by the introduction of electron-withdrawing substituents into the benzonitrile oxide structure, allow to presume that the reaction of enamines with nitrile oxides can be described as 1,3-dipolar cycloadditions

Diradical reaction mechanisms in [3 + 2]-cycloadditions of hetaryl thioketones with alkyl- or trimethylsilyl-substituted diazomethanes

• Grzegorz Mlostoń,
• Paulina Pipiak and
• Heinz Heimgartner

Beilstein J. Org. Chem. 2016, 12, 716–724, doi:10.3762/bjoc.12.71

• important classes of organic reactions, and [3 + 2]- cycloadditions, also known as 1,3-dipolar cycloadditions or Huisgen reactions, offer a universal tool for the preparation of five-membered heterocycles with a variable number of heteroatoms in the ring [1][2]. In addition to their practical importance