Recent advances in transition-metal-catalyzed incorporation of fluorine-containing groups

• Xiaowei Li,
• Xiaolin Shi,
• Xiangqian Li and
• Dayong Shi

Beilstein J. Org. Chem. 2019, 15, 2213–2270, doi:10.3762/bjoc.15.218

Recent advances on the transition-metal-catalyzed synthesis of imidazopyridines: an updated coverage

• Gagandeep Kour Reen,
• Ashok Kumar and
• Pratibha Sharma

Beilstein J. Org. Chem. 2019, 15, 1612–1704, doi:10.3762/bjoc.15.165

Synthesis of dipolar molecular rotors as linkers for metal-organic frameworks

• Sebastian Hamer,
• Fynn Röhricht,
• Marius Jakoby,
• Ian A. Howard,
• Xianghui Zhang,
• Christian Näther and
• Rainer Herges

Beilstein J. Org. Chem. 2019, 15, 1331–1338, doi:10.3762/bjoc.15.132

• subsequent direct conversion of the TMS-protected acetylenes to the dicarboxylic acids using a method of Kondo and co-workers [42]. Following this procedure, purification of TMS-protected compounds was more convenient as compared to the tedious work-up with carboxylic acid derivatives directly obtained from

Synthesis and selected transformations of 2-unsubstituted 1-(adamantyloxy)imidazole 3-oxides: straightforward access to non-symmetric 1,3-dialkoxyimidazolium salts

• Grzegorz Mlostoń,
• Małgorzata Celeda,
• Katarzyna Urbaniak,
• Marcin Jasiński,
• Vladyslav Bakhonsky,
• Peter R. Schreiner and
• Heinz Heimgartner

Beilstein J. Org. Chem. 2019, 15, 497–505, doi:10.3762/bjoc.15.43

• reactivity analogous to aldonitrones, which enables their conversion via [3 + 2]-cycloadditions with dipolarophiles such as activated ethylenes [8][9], activated acetylenes [10][11] or isocyanates [11][12]. The initially formed [3 + 2]-cycloadducts undergo spontaneous secondary conversions leading to re

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

• the synthetic intermediates obtained in the SNAr reaction (e.g., 6-azido-9-heptyl-2-(piperidin-1-yl)purine (6b)) exists in both tetrazolo- and azido-tautomeric forms in CD3CN solution. The presence of the latter permits the CuAAC reaction with terminal acetylenes and gave a rise to the title compounds

Ring-closing-metathesis-based synthesis of annellated coumarins from 8-allylcoumarins

• Christiane Schultze and
• Bernd Schmidt

Beilstein J. Org. Chem. 2018, 14, 2991–2998, doi:10.3762/bjoc.14.278

• [62] of furanyl carbene complexes and acetylenes [63]. Angelicin (3a) was also obtained via RCM of 8-(1-propenyl)-7-vinyloxycoumarin, but the synthesis of this precursor required four steps, starting from umbelliferone, and proceeded only with moderate regioselectivity for the second step [47]. Next

Generation of 1,2-oxathiolium ions from (arysulfonyl)- and (arylsulfinyl)allenes in Brønsted acids. NMR and DFT study of these cations and their reactions

• Stanislav V. Lozovskiy,
• Alexander Yu. Ivanov,
• Olesya V. Khoroshilova and
• Aleksander V. Vasilyev

Beilstein J. Org. Chem. 2018, 14, 2897–2906, doi:10.3762/bjoc.14.268

• explored in organic synthesis for the construction of various molecules [1][2][3][4][5][6][7]. In particular, arylsulfonyl (ArSO2) allenes are usefull building blocks in miscellaneous transformations. For instance, addition of such allenes to Michael acceptors leading to terminal acetylenes has been

Transition metal-free oxidative and deoxygenative C–H/C–Li cross-couplings of 2H-imidazole 1-oxides with carboranyl lithium as an efficient synthetic approach to azaheterocyclic carboranes

• Lidia A. Smyshliaeva,
• Mikhail V. Varaksin,
• Pavel A. Slepukhin,
• Oleg N. Chupakhin and
• Valery N. Charushin

Beilstein J. Org. Chem. 2018, 14, 2618–2626, doi:10.3762/bjoc.14.240

• of promising heterocyclic carboranes: (i) condensation of decaborane (B10H14) with substituted acetylenes [27][28][29][30], (ii) carboryne-based cycloaddition reactions [31][32][33], and (iii) C–X/C–M cross coupling of halogenated azaheterocycles (X = Br, Cl, F) with carborane organometallic

[3 + 2]-Cycloaddition reaction of sydnones with alkynes

• Veronika Hladíková,
• Jiří Váňa and
• Jiří Hanusek

Beilstein J. Org. Chem. 2018, 14, 1317–1348, doi:10.3762/bjoc.14.113

• )sydnones with DMAD for which positive Hammett ρ-values were observed [54][55]. On the other hand Huisgen and Gotthardt [54] measured bimolecular rate constants for the above-mentioned reaction of 4-methyl-3-phenylsydnone and various acetylenes in p-cymene at 140 °C (Table 2) and found a reactivity sequence

• constants (k, L·mol–1·s–1) measured for the reaction of 4-methyl-3-phenylsydnone and various acetylenes in p-cymene at 140 °C [54]. Photochemical cycloaddition of N-phenylsydnones with DMAD. Thermal cycloaddition of sydnones with terminal alkynes. Thermal cycloaddition of sydnones with internal non

Atom-economical group-transfer reactions with hypervalent iodine compounds

• Andreas Boelke,
• Peter Finkbeiner and
• Boris J. Nachtsheim

Beilstein J. Org. Chem. 2018, 14, 1263–1280, doi:10.3762/bjoc.14.108

• coupled with the alkyne under palladium catalysis. A broad range of TMS-substituted acetylenes 29 was converted efficiently under the optimized reaction conditions, forming the desired arylacetylenes 30 in good yields with high stereoselectivity. The applicable substrate scope is rather broad including

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

Progress in copper-catalyzed trifluoromethylation

• Guan-bao Li,
• Chao Zhang,
• Chun Song and
• Yu-dao Ma

Beilstein J. Org. Chem. 2018, 14, 155–181, doi:10.3762/bjoc.14.11

• Trifluoromethylated acetylenes were widely used in medicinal, agrochemical, and material science. In 2010, Qing and coworkers [60] firstly reported a copper-mediated trifluoromethylation of terminal alkynes using TMSCF3 as a trifluoromethyl source. (Scheme 39). At the beginning of the experiment, undesired diyne

Synthesis and application of trifluoroethoxy-substituted phthalocyanines and subphthalocyanines

• Satoru Mori and
• Norio Shibata

Beilstein J. Org. Chem. 2017, 13, 2273–2296, doi:10.3762/bjoc.13.224

• modification and purification are easy. For example, the synthesis of unsymmetrical TFEO-Pcs, which are also referred to as A3B type phthalocyanines, and their cross-coupling reaction catalyzed by palladium between A3B type TFEO-Pcs and acetylenes have been reported (Scheme 3) [66][67]. A3B type

Mechanochemical synthesis of small organic molecules

• Tapas Kumar Achar,
• Anima Bose and
• Prasenjit Mal

Beilstein J. Org. Chem. 2017, 13, 1907–1931, doi:10.3762/bjoc.13.186

• palladium salts (Pd(OAc)2 or Pd(PPh3)4) and DABCO (1,4-diazabicyclo[2.2.2]octane) various acetylenes and aryl halides were coupled to obtain the Sonogashira coupling products in excellent yields (near quantitative, Scheme 10a). The reactions were reported for aliphatic alkynes as well. In Scheme 10b, an

• triazole moiety (Scheme 37a) using benzyl halides, sodium azide and a terminal alkyne via an alumina-supported copper catalyst. Using 10 mol % of Cu/Al2O3, differently substituted phenyl acetylenes and aliphatic alkynes led to 70–96% yield of triazoles [152]. Phenyl boronic acids were also used to

Transition-metal-free one-pot synthesis of alkynyl selenides from terminal alkynes under aerobic and sustainable conditions

• Adrián A. Heredia and
• Alicia B. Peñéñory

Beilstein J. Org. Chem. 2017, 13, 910–918, doi:10.3762/bjoc.13.92

• acetylenes. Keywords: alkynyl selenide; electrophilic cyclization; nucleophilic substitution; potassium selenocyanate; terminal alkynes; Introduction Alkynyl selenides, as many other selenium compounds, have potential anti-oxidant activities, and may play a role in certain diseases such as cancer, heart

Nucleophilic and electrophilic cyclization of N-alkyne-substituted pyrrole derivatives: Synthesis of pyrrolopyrazinone, pyrrolotriazinone, and pyrrolooxazinone moieties

• Işıl Yenice,
• Sinan Basceken and
• Metin Balci

Beilstein J. Org. Chem. 2017, 13, 825–834, doi:10.3762/bjoc.13.83

• presence of silver nitrate. The synthesized acetylenes 10a,b and commercially available acetylenes 10c,d were converted into bromoalkyne derivatives 11a–d according to the literature procedure (Scheme 1) [29][30]. After the successful generation of alkynyl bromides 11a–d, the next step was the synthesis of

New approach toward the synthesis of deuterated pyrazolo[1,5-a]pyridines and 1,2,4-triazolo[1,5-a]pyridines

• Aleksey Yu. Vorob’ev,
• Vyacheslav I. Supranovich,
• Gennady I. Borodkin and
• Vyacheslav G. Shubin

Beilstein J. Org. Chem. 2017, 13, 800–805, doi:10.3762/bjoc.13.80

• An efficient and operationally simple synthesis of 7-deuteropyrazolo[1,5-a]pyridine and 7-deutero-1,2,4-triazolo[1,5-a]pyridine derivatives using α-H/D exchange of 1-aminopyridinium cations in basic D2O followed by a 1,3-cycloaddition of acetylenes and nitriles is presented. A high regioselectivity

• -1,2,4-triazolo[1,5-a]pyridine derivatives by H/D exchange of 1-aminopyridinium cations followed by the reaction with acetylenes and nitriles. Results and Discussion N-Aminopyridinium salts are easily available via direct N-amination of parent pyridines. Salt 1a was prepared by N-amination of pyridine

• from N-aminopyridium salts through an H/D exchange in basic D2O solution followed by the cycloaddition reaction with acetylenes (Scheme 1). In the first step, the H/D exchange in 1a has been performed with a 0.67 M solution of K2CO3 in D2O at 80 °C for 5 min. After D2O evaporation and the reaction with

Isoxazole derivatives as new nitric oxide elicitors in plants

• Anca Oancea,
• Emilian Georgescu,
• Florentina Georgescu,
• Alina Nicolescu,
• Elena Iulia Oprita,
• Catalina Tudora,
• Lucian Vladulescu,
• Marius-Constantin Vladulescu,
• Florin Oancea and
• Calin Deleanu

Beilstein J. Org. Chem. 2017, 13, 659–664, doi:10.3762/bjoc.13.65

• -deficient alkene led to the intermediate bromoisoxazoline from which, by loss of HBr, a 3,5-disubstituted isoxazole derivative is formed as major regioisomer [34]. Based on the copper(I)-catalyzed click reactions of organic azides with terminal acetylenes [35], different copper(I)-catalyzed synthetic

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

• mechanisms in [3 + 2]-cycloadditions have intensively been studied [16] and recently, a computational study on their appearance in reactions of substituted acetylenes with nitrile oxides has been published [17]. Experimental The Gaussian 09 program system was used for all calculations [18]. The M06-2X

Sydnone C-4 heteroarylation with an indolizine ring via Chichibabin indolizine synthesis

• Florin Albota,
• Mino R. Caira,
• Constantin Draghici,
• Florea Dumitrascu and
• Denisa E. Dumitrescu

Beilstein J. Org. Chem. 2016, 12, 2503–2510, doi:10.3762/bjoc.12.245

• activated acetylenes, the hybrid structures 1 containing a pyrroloazine (pyrroloisoquinoline or pyrrolophthalazine) connected to the sydnone ring through a keto group [5]. As a result, it was of interest to prepare analogous compounds containing a pyrroloazine directly attached to the C-4 position of a

Practical synthetic strategies towards lipophilic 6-iodotetrahydroquinolines and -dihydroquinolines

• David R. Chisholm,
• Garr-Layy Zhou,
• Ehmke Pohl,
• Roy Valentine and
• Andrew Whiting

Beilstein J. Org. Chem. 2016, 12, 1851–1862, doi:10.3762/bjoc.12.174

• , phosphine additives and strong heating or microwave conditions in order to effect coupling with most acetylenes. Accordingly, it was anticipated that the aryl iodides would be more versatile due to their greater propensity to undergo oxidative additions. Therefore, in this paper we report herein the

Multicomponent reactions: A simple and efficient route to heterocyclic phosphonates

• Mohammad Haji

Beilstein J. Org. Chem. 2016, 12, 1269–1301, doi:10.3762/bjoc.12.121

• aldehydes 224 generated terminal acetylenes 226 which cyclized with the second molecule of phosphonate 225 in the presence of Cu(I) to afford (5-methyl-1H-pyrazol-3-yl)phosphonates 230 in 46–81% yields (Scheme 46) [84]. Also, a domino reaction based on the dual reactivity of BOR as a homologation reagent as

• 1,2-dihydropyridine-3-phosphonate 259. Yavari et al. have described the phosphorylation of benzothiazole (263) and isoquinoline (246) through a one-pot three-component reaction with activated acetylenes 260 and diphenyl phosphonate (261) under solvent-free conditions at room temperature (Scheme 54

Enantioselective additions of copper acetylides to cyclic iminium and oxocarbenium ions

• Jixin Liu,
• Srimoyee Dasgupta and
• Mary P. Watson

Beilstein J. Org. Chem. 2015, 11, 2696–2706, doi:10.3762/bjoc.11.290

• solvent also affect the enantioselectivity, with iPr2N(n-Pr) and CH2Cl2 proving best. Notably, only 1,2-addition was observed. With respect to the alkyne, activated terminal acetylenes, such as ynones and propriolates, are best for this reaction. Unactivated alkynes give products in reasonable yields (63

• –77%), but poor enantioselectivities (1–11% ee). However, the use of activated acetylenes provides a functional group handle for elaboration, which the authors demonstrate in the preparation of indolizidine 223AB. Building on their initial discovery of a non-asymmetric, copper-catalyzed, three

Hetero-Diels–Alder reactions of hetaryl and aryl thioketones with acetylenic dienophiles

• Grzegorz Mlostoń,
• Paulina Grzelak,
• Maciej Mikina,
• Anthony Linden and
• Heinz Heimgartner

Beilstein J. Org. Chem. 2015, 11, 576–582, doi:10.3762/bjoc.11.63

• acetylenic dienophiles, other easily available acetylenes were used in the reaction with 1a. In all reactions attempted with phenylacetylene, (pyridin-2-yl)acetylene, and (tert-butyl)acetylene, no conversion of 1a was observed as evidenced by the blue color of the reaction mixture even after 24 h

Synthesis and chemosensing properties of cinnoline-containing poly(arylene ethynylene)s

• Natalia A. Danilkina,
• Petr S. Vlasov,
• Semen M. Vodianik,
• Andrey A. Kruchinin,
• Yuri G. Vlasov and
• Irina A. Balova

Beilstein J. Org. Chem. 2015, 11, 373–384, doi:10.3762/bjoc.11.43

• significantly. We chose the Sonogashira coupling of diethynylcinnolines and alkylated diiodohydroquinone as a method for the formation of PAE’s backbone. It also should be mentioned that despite the fact that sila-Sonogashira coupling have been widely applied for the synthesis of different acetylenes with aryl