Asymmetric organocatalyzed synthesis of coumarin derivatives

• Natália M. Moreira,
• Lorena S. R. Martelli and
• Arlene G. Corrêa

Beilstein J. Org. Chem. 2021, 17, 1952–1980, doi:10.3762/bjoc.17.128

• , provides coumarin derivatives 3 with good to excellent yields and moderate to good enantiomeric excesses (Scheme 5). The authors highlighted that the employed organocatalyst 18 is an alternative to those of squaramide and thiourea commonly used with coumarins. In 2013, Lee et al. reported the

• Scheme 30. An asymmetric Michael addition of 4-hydroxycoumarin (1) to α,β-unsaturated ketones 2 promoted by chiral primary amine thiourea bifunctional catalyst 97 was reported by Mei et al. [66]. Using the optimized conditions, a series of Michael adducts 3 were obtained in excellent yields (up to 97

• %) and enantioselectivities (up to 95% ee) (Scheme 31). As a highlight, optically pure (S)-warfarin (3a) was obtained in 99% ee after simple and single recrystallization. Wang’s group developed a bifunctional thiourea and abietic acid catalyst for enantioselective synthesis. In this context, they applied

Synthesis of 1-indolyl-3,5,8-substituted γ-carbolines: one-pot solvent-free protocol and biological evaluation

• Premansh Dudhe,
• Mena Asha Krishnan,
• Kratika Yadav,
• Diptendu Roy,
• Krishnan Venkatasubbaiah,
• Biswarup Pathak and
• Venkatesh Chelvam

Beilstein J. Org. Chem. 2021, 17, 1453–1463, doi:10.3762/bjoc.17.101

• alkaloid ingenine B [20]. The iodine-catalyzed [3 + 3] cycloaddition of indolyl alcohol to enaminones [21] and the thiourea-catalyzed iso-Pictet–Spengler reaction of isotryptamine with aldehydes [22], are some noteworthy contributions to the field. A cascade or domino reaction is an interesting approach

Organocatalytic asymmetric Michael/acyl transfer reaction between α-nitroketones and 4-arylidenepyrrolidine-2,3-diones

• Chandrakanta Parida and
• Subhas Chandra Pan

Beilstein J. Org. Chem. 2021, 17, 1447–1452, doi:10.3762/bjoc.17.100

• reported. A bifunctional thiourea catalyst was found to be effective for this reaction. With 10 mol % of the catalyst, good results were attained for a variety of 1,5-dihydro-2H-pyrrol-2-ones under mild reaction conditions. Keywords: acyl transfer; enantioselectivity; Michael reaction; organocatalysis

• benzoyl-transfer reaction. However, only 20% enantiomeric excess was achieved. Then, the tert-leucine-derived squaramide catalyst II was employed and here both yield and ee slightly improved. Next, we turned our attention to bifunctional thiourea catalysts [26][27] that proved to be fruitful. Thus, the

• quinine and cinchonidine-derived bifunctional thiourea catalysts III and IV were employed in the reaction and moderate enantiomeric excesses were achieved. The yield and enantioselectivity further improved when using the tert-leucine-derived thiourea catalyst V. Also, Takemoto’s catalyst VI [28] was

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

Synthesis of functionalized imidazo[4,5-e]thiazolo[3,2-b]triazines by condensation of imidazo[4,5-e]triazinethiones with DMAD or DEAD and rearrangement to imidazo[4,5-e]thiazolo[2,3-c]triazines

• Alexei N. Izmest’ev,
• Dmitry B. Vinogradov,
• Natalya G. Kolotyrkina,
• Angelina N. Kravchenko and
• Galina A. Gazieva

Beilstein J. Org. Chem. 2021, 17, 1141–1148, doi:10.3762/bjoc.17.87

• derivatives consists in the condensation of acetylenedicarboxylic acid esters with heterocyclic compounds containing a thiourea fragment, e.g., pyrimidinethiones [18][19], 1,2,4-triazolethiols [20], and 1,2,4-triazinethiones [21][22]. An important feature of the reactions of dialkyl acetylenedicarboxylates

Synthetic accesses to biguanide compounds

• Oleksandr Grytsai,
• Cyril Ronco and
• Rachid Benhida

Beilstein J. Org. Chem. 2021, 17, 1001–1040, doi:10.3762/bjoc.17.82

Stereoselective synthesis and transformation of pinane-based 2-amino-1,3-diols

• Ákos Bajtel,
• Mounir Raji,
• Matti Haukka,
• Ferenc Fülöp and
• Zsolt Szakonyi

Beilstein J. Org. Chem. 2021, 17, 983–990, doi:10.3762/bjoc.17.80

• ). The LAH reduction of oxazolidine 17 gave N-benzyl-N-methyl analogue 18 which, alternatively, was prepared directly from 2-oxazolidinone 9 via N-benzylation followed by LAH reduction in 2 steps. When compound 13 was reacted with phenylisothiocyanate, thiourea 20 was obtained, which underwent a

Microwave-assisted multicomponent reactions in heterocyclic chemistry and mechanistic aspects

• Shivani Gulati,
• Stephy Elza John and
• Nagula Shankaraiah

Beilstein J. Org. Chem. 2021, 17, 819–865, doi:10.3762/bjoc.17.71

• construction of dihydropyrimidinones 78 utilizing a three-component reaction of acyclic 1,3-diketones 54, urea/thiourea (77) and aldehyde 5 exploring La2O3 as catalyst under microwave irradiation under solvent-free conditions with good functional group tolerance and excellent yields (Scheme 28). The reaction

The synthesis of chiral β-naphthyl-β-sulfanyl ketones via enantioselective sulfa-Michael reaction in the presence of a bifunctional cinchona/sulfonamide organocatalyst

• Deniz Tözendemir and
• Cihangir Tanyeli

Beilstein J. Org. Chem. 2021, 17, 494–503, doi:10.3762/bjoc.17.43

• building blocks for the construction of more elaborate structures [7][8][9][10][11]. An outstanding class of quinine derived organocatalysts exhibits a bifunctional mode of activation by the incorporation of an acidic unit, such as urea, thiourea, squaramide or sulfonamide moieties, giving rise to the

• and thiourea–quinine organocatalysts both gave the target compound with only 41% ee, which was well below satisfactory (Table 1, entries 10 and 11). The best catalyst in terms of enantioselectivity proved to be the newly designed catalyst 5, which gave the desired product with 63% ee in 1 hour (Table

Chiral anion recognition using calix[4]arene-based ureido receptors in a 1,3-alternate conformation

• Tereza Horáčková,
• Jan Budka,
• Vaclav Eigner,
• Wen-Sheng Chung,
• Petra Cuřínová and
• Pavel Lhoták

Beilstein J. Org. Chem. 2020, 16, 2999–3007, doi:10.3762/bjoc.16.249

• . The shapes and geometries of anions are widely different, and therefore the design of corresponding tailor-made receptors is based mostly on more directional interactions, such as hydrogen bonds. Indeed, an incredible number of neutral receptors bearing amide, sulfonamide, urea, thiourea, pyrrole, or

• highly sophisticated molecules, including anionic receptors [27][28][29][30][31][32][33][34][35][36][37][38][39]. During our ongoing research on anion complexation, we have reported various calix[4]arene receptors based mainly on amide, urea, or thiourea groups [40][41], some of which are available in

Recent developments in enantioselective photocatalysis

• Callum Prentice,
• James Morrisson,
• Andrew D. Smith and
• Eli Zysman-Colman

Beilstein J. Org. Chem. 2020, 16, 2363–2441, doi:10.3762/bjoc.16.197

• enantioselectivity via triplet state intermediate 200, rather than proceeding via an enantioselective rearrangement. Bifunctional hydrogen bonding photocatalysts have been developed by other groups as well. Sivaguru developed an atropisomeric thiourea-based catalyst 201 and used it for the intramolecular

Access to highly substituted oxazoles by the reaction of α-azidochalcone with potassium thiocyanate

• Mysore Bhyrappa Harisha,
• Pandi Dhanalakshmi,
• Rajendran Suresh,
• Raju Ranjith Kumar and
• Shanmugam Muthusubramanian

Beilstein J. Org. Chem. 2020, 16, 2108–2118, doi:10.3762/bjoc.16.178

• existing alkaloids and a number of pharmaceutically active compounds [51][52][53]. 2-Aminothiazole has a thiourea-like character with a tendency to modulate promiscuously multiple biological targets. Thiazole derivatives also exhibit a broad spectrum of biological activities including antiviral, antiprion

Natural dolomitic limestone-catalyzed synthesis of benzimidazoles, dihydropyrimidinones, and highly substituted pyridines under ultrasound irradiation

• Kumar Godugu,
• Venkata Divya Sri Yadala,
• Mohammad Khaja Mohinuddin Pinjari,
• Trivikram Reddy Gundala,
• Lakshmi Reddy Sanapareddy and
• Chinna Gangi Reddy Nallagondu

Beilstein J. Org. Chem. 2020, 16, 1881–1900, doi:10.3762/bjoc.16.156

• heteroaromatic aldehydes. To expand the scope of this method, thiourea (6) was also investigated (Table 6, entries 13–17). Benzaldehyde (2a) reacted with ethyl acetoacetate (4) and thiourea (6) to give the product 7m in an excellent isolated yield (96%, Table 6, entry 13). Benzaldehyde derivatives bearing

• electron-donating groups, such as 4-Me (2b) and 4-OMe (2c) exhibited a good reactivity with ethyl acetoacetate (4) and thiourea (6) to produce the products 7n (95%) and 7o (95%) in excellent yields, respectively (Table 6, entries 14 and 15). Benzaldehyde with electron-withdrawing groups, such as 4-NO2 (2f

• ) and 4-Cl (2i) at the para position reacted well with ethyl acetoacetate (4) and thiourea (6) to afford the corresponding products 7p and 7q in good isolated yields (94 and 95%) (Table 6, entries 16 and 17). Most of the synthesized compounds are known and were identified easily by comparison of the

Stereoselective Biginelli-like reaction catalyzed by a chiral phosphoric acid bearing two hydroxy groups

• Xiaoyun Hu,
• Jianxin Guo,
• Cui Wang,
• Rui Zhang and
• Victor Borovkov

Beilstein J. Org. Chem. 2020, 16, 1875–1880, doi:10.3762/bjoc.16.155

• DHPMs becomes an urgent and paramount task. In connection with this, multicomponent Biginelli and Biginelli-like reactions of aldehydes, urea/thiourea, and enolizable carbonyls revealed as very efficient tools to prepare DHPMs [3]. Although the Biginelli reaction was firstly discovered over a century

One-pot synthesis of 1,3,5-triazine-2,4-dithione derivatives via three-component reactions

• Gui-Feng Kang and
• Gang Zhang

Beilstein J. Org. Chem. 2020, 16, 1447–1455, doi:10.3762/bjoc.16.120

• 100050, China 10.3762/bjoc.16.120 Abstract A catalyst-free one-pot synthetic methodology was developed for the preparation of 1,3,5-triazine-2,4-dithione derivatives through three-component reactions of arylaldehydes, thiourea, and orthoformates. The procedure tolerated a diverse range of arylaldehydes

• and orthoformates and provided a rapid entry to a variety of 4-aryl-6-(alkylthio)-3,4-dihydro-1,3,5-triazine-2(1H)-thiones (29 examples). The synthetic strategy relies on the dual role of thiourea in the cyclization with the aldehydes and the alkylation via an intermediate imidate formation. The

• structures of 1,3,5-triazine-2,4-dithione derivatives were characterized by spectroscopic techniques as well as by single crystal X-ray diffraction. Keywords: aldehydes; multicomponent reactions; nitrogen heterocycles; thiourea; triazinethiones; Introduction The construction of nitrogen-containing

Recent synthesis of thietanes

• Jiaxi Xu

Beilstein J. Org. Chem. 2020, 16, 1357–1410, doi:10.3762/bjoc.16.116

• displacements of 1,3-dihaloalkanes with different sulfide salts, thiourea was also used as a nucleophile in the double displacements, actually following the preparation procedure of thiols, affording thietane derivatives. Thiourea reacted with 3,3-bis(chloromethyl)oxetane (76) in the presence of HClO4 to yield

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

Regio- and stereoselective synthesis of new ensembles of diversely functionalized 1,3-thiaselenol-2-ylmethyl selenides by a double rearrangement reaction

• Svetlana V. Amosova,
• Andrey A. Filippov,
• Nataliya A. Makhaeva,
• Alexander I. Albanov and
• Vladimir A. Potapov

Beilstein J. Org. Chem. 2020, 16, 515–523, doi:10.3762/bjoc.16.47

• proceeding at the C2 carbon atom of the seleniranium cation 2 with dithiocarbomates [31], thiourea [32], alcohols [42], functionalized organic acids [43][44], functionalized pyridines [45], ammonium thiocyanate [46], and mercapto benzazoles [40] were developed (Scheme 4). The new methodology of a

The use of isoxazoline and isoxazole scaffolding in the design of novel thiourea and amide liquid-crystalline compounds

• Itamar L. Gonçalves,
• Rafaela R. da Rosa,
• Vera L. Eifler-Lima and
• Aloir A. Merlo

Beilstein J. Org. Chem. 2020, 16, 175–184, doi:10.3762/bjoc.16.20

• Ciências e Tecnologia, Universidade NOVA de Lisboa, 2829-516 Caparica, Portugal Institute of Chemistry, Universidade Federal do Rio Grande do Sul, Porto Alegre, RS, Brazil 10.3762/bjoc.16.20 Abstract A series of novel thiourea and amide liquid crystals containing 5-membered isoxazoline and isoxazole rings

• . Thiourea and amide derivatives were predominantly SmA mesophase inductors. A nematic mesophase was observed only for thioureas and amides containing an isoxazole ring. Additionaly, the liquid crystal behavior was also dependent on the relative position of nitrogen and oxygen atoms on the 5-membered

• heterocycle. Keywords: amides; isoxazole; isoxazoline; liquid crystal; thiourea; Introduction Thioureas are a structurally diversified group of organic compounds, with technological applications in different areas. The structural diversity of the thiourea moiety is linked to possibly one or both nitrogen

The reaction of arylmethyl isocyanides and arylmethylamines with xanthate esters: a facile and unexpected synthesis of carbamothioates

• Narasimhamurthy Rajeev,
• Toreshettahally R. Swaroop,
• Ahmad I. Alrawashdeh,
• Shofiur Rahman,
• Abdullah Alodhayb,
• Seegehalli M. Anil,
• Kuppalli R. Kiran,
• Chandra,
• Paris E. Georghiou,
• Kanchugarakoppal S. Rangappa and
• Maralinganadoddi P. Sadashiva

Beilstein J. Org. Chem. 2020, 16, 159–167, doi:10.3762/bjoc.16.18

• ], iron nanoparticle-catalyzed reactions of 2-naphthol with benzaldehyde and some of its derivatives with thiourea [22], isothiocyanato oxindoles with ketones [23], ammonium isothiocyanates with chalcones [24], and α-isothiocyanato esters with α-keto amides [25]. Among the synthetic methods available for

Why do thioureas and squaramides slow down the Ireland–Claisen rearrangement?

• Dominika Krištofíková,
• Juraj Filo,
• Mária Mečiarová and
• Radovan Šebesta

Beilstein J. Org. Chem. 2019, 15, 2948–2957, doi:10.3762/bjoc.15.290

• rearrangement, we tried to optimize its reaction course under mild conditions using various bases, solvents, and hydrogen-bond-donating catalysts. We also present a computational explanation and NMR kinetic study for the inefficient Ireland–Claisen rearrangement under thiourea and squaramide catalysis. Results

• . For this, we have compared the uncatalyzed Ireland–Claisen rearrangement with three hydrogen-bond-catalyzed reactions. As model H-bonding catalysts, we selected diphenylthiourea, Schreiner thiourea, and the corresponding squaramide with bis(trifluoromethyl)phenyl groups. We have evaluated both the (E

• Schreiner thiourea (C12) had higher activation barriers for both isomers (111.9 kJ·mol−1 for (E) and 95.6 kJ·mol−1 for (Z)). These results suggest that Schreiner thiourea binds stronger to starting silyl ketene acetal than to the corresponding transition state. Therefore, it stabilizes more the starting

Facile regiodivergent synthesis of spiro pyrrole-substituted pseudothiohydantoins and thiohydantoins via reaction of [e]-fused 1H-pyrrole-2,3-diones with thiourea

• Aleksandr I. Kobelev,
• Nikita A. Tretyakov,
• Ekaterina E. Stepanova,
• Maksim V. Dmitriev,
• Michael Rubin and
• Andrey N. Maslivets

Beilstein J. Org. Chem. 2019, 15, 2864–2871, doi:10.3762/bjoc.15.280

• good yields, and the products were isolated without applying preparative chromatography methods. Keywords: diversity-oriented synthesis; hydantoin; nitrogen heterocycles; rearrangement; thiourea; Introduction Hydantoin (imidazolidine-2,4-dione) derivatives are omnipresent among biologically active

• preparation of the target spiro-fused pseudothiohydantoins and thiohydantoins, we examined the reaction of FPD 1a with thiourea by heating equimolar amounts of the reagents in toluene for 5 min (until the disappearance of the dark violet color of FPD 1a). The reaction mixture was examined by UPLC–MS. Two

• major products with m/z = 396 ([M + H]+, ESI+) were observed in a ratio of ≈1:1, which corresponded to adducts of thiourea with FPD 1a. The adducts were isolated, and their structures were elucidated as the desired spiro-fused thiohydantoin 2a and pseudothiohydantoin 3a (Scheme 4). It should be pointed

Diversity-oriented synthesis of spirothiazolidinediones and their biological evaluation

• Sambasivarao Kotha,
• Gaddamedi Sreevani,
• Lilya U. Dzhemileva,
• Milyausha M. Yunusbaeva,
• Usein M. Dzhemilev and
• Vladimir A. D’yakonov

Beilstein J. Org. Chem. 2019, 15, 2774–2781, doi:10.3762/bjoc.15.269

• synthesis of thiazolidinedione derivatives is refluxing chloroacetic acid (2) with thiourea (1), followed by a Knoevenagel condensation with an aldehyde (Scheme 1) [25]. Results and Discussion Limited reports are available dealing with the synthesis of spiro derivatives of thiazolidine-2,4-diones [26][27

A novel three-component reaction between isocyanides, alcohols or thiols and elemental sulfur: a mild, catalyst-free approach towards O-thiocarbamates and dithiocarbamates

• András György Németh,
• György Miklós Keserű and
• Péter Ábrányi-Balogh

Beilstein J. Org. Chem. 2019, 15, 1523–1533, doi:10.3762/bjoc.15.155

• -diimidazole or di-2-pyridyl thionocarbonate [57][58]. Decomposition of dithiocarbamate salts or thiocarbamates with various reagents offers a good alternative [59][60][61][62] as well, however, this approach first requires the synthesis of the appropriate precursor. Nitrile oxides react with thiourea to

Selenophene-containing heterotriacenes by a C–Se coupling/cyclization reaction

• Pierre-Olivier Schwartz,
• Sebastian Förtsch,
• Astrid Vogt,
• Elena Mena-Osteritz and
• Peter Bäuerle

Beilstein J. Org. Chem. 2019, 15, 1379–1393, doi:10.3762/bjoc.15.138

• reagents as aforementioned or DTT 1 with thiourea or thioacetate in a Pd-catalyzed reaction [33] led in both cases to substantially lower yields. For the synthesis of selenolotriacenes (DST) 3 and (DSS) 4 we followed the same strategies and applied the above described Cu-catalyzed C–S and C–Se cross