Harnessing the versatility of hydrazones through electrosynthetic oxidative transformations

• Aurélie Claraz

Beilstein J. Org. Chem. 2024, 20, 1988–2004, doi:10.3762/bjoc.20.175

• generation of electrophilic thiocyanogen as the initial step. Further reaction with the hydrazone 95 and deprotonation led to hydrazonoyl thiocyanate intermediate 99, which isomerized to the thermodynamically more stable isothiocyanate derivatives 100 through 1,3-shift. The latter underwent spontaneous ring

Selectivity control towards CO versus H₂ for photo-driven CO₂ reduction with a novel Co(II) catalyst

• Lisa-Lou Gracia,
• Philip Henkel,
• Olaf Fuhr and
• Claudia Bizzarri

Beilstein J. Org. Chem. 2023, 19, 1766–1775, doi:10.3762/bjoc.19.129

• high-resolution mass spectrometry (ESI), where it was shown the fragment corresponding to complex 1 that lost one isothiocyanate, [M − NCS]+, as the primary signal. Elemental analysis matched the calculated values, incorporating an additional MeOH molecule. Recrystallization was afforded by re

• ). Efforts to selectively achieve one polymorph, through differentiated crystallization processes, were unsuccessful. When analyzing the molecular structure in both crystals, the cobalt core is hexacoordinated, as expected. The two isothiocyanate ions are oriented cis to each other and trans to the

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

• trifluoroacetonitrile imine, are highly versatile in that they react with olefins, acetylenes, dimethyl fumarate, dimethyl maleate, β-diketones, β-keto esters, bicyclic olefins, and potassium isothiocyanate and isocyanate affording the corresponding trifluoromethyl-containing compounds, generally with good yields [51

Sulfur-containing spiroketals from Breynia disticha and evaluations of their anti-inflammatory effect

• Ken-ichi Nakashima,
• Naohito Abe,
• Masayoshi Oyama,
• Hiroko Murata and
• Makoto Inoue

Beilstein J. Org. Chem. 2023, 19, 1604–1614, doi:10.3762/bjoc.19.117

• electrospray ionization HRESIMS analysis, and quantum chemical electronic CD calculations. Furthermore, the absolute configurations of sugar residues were determined by derivatization of the hydrolysates with ʟ-cysteine methyl ester and o-tolyl isothiocyanate followed by HPLC analysis. The anti-inflammatory

• by acid hydrolysis of 1 using the method developed by Tanaka et al. [16], in which the hydrolysates are derivatized with ʟ-cysteine methyl ester and o-tolyl isothiocyanate followed by HPLC analysis. For compound 1, peaks were observed at retention times of 13.96, 20.83, and 22.16 min. The peaks at

• residue was added a solution of ʟ-cysteine methyl ester hydrochloride (2 mg) in pyridine (200 μL), and the mixture was stirred at 65 °C for 1 h. Then, a solution of o-tolyl isothiocyanate (2.2 μL) in pyridine (200 μL) was added and the resulting mixture was stirred at 65 °C for 1 h. The final mixture was

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

• the para-position to the amino group, and when the para-position of aniline was occupied by another group, ortho-substituted products were identified. Fu′s research group established an isothiocyanatoalkylthiation of styrenes 9 in the presence of isothiocyanate 154 and N-(organothio)succinimides 1

Terpenoids from Glechoma hederacea var. longituba and their biological activities

• Dong Hyun Kim,
• Song Lim Ham,
• Zahra Khan,
• Sun Yeou Kim,
• Sang Un Choi,
• Chung Sub Kim and
• Kang Ro Lee

Beilstein J. Org. Chem. 2022, 18, 555–566, doi:10.3762/bjoc.18.58

• hydrolysis, was dissolved in pyridine (0.5 mL), then ʟ-cysteine methyl ester hydrochloride (2 mg) was added. The reaction mixture was stirred at 60 °C for 1 h. Then O-tolyl isothiocyanate (30 μL) was added and stirred at 60 °C for 1 h. The reaction mixture was analyzed without purification by LC–MS analysis

Glycosylated coumarins, flavonoids, lignans and phenylpropanoids from Wikstroemia nutans and their biological activities

• Meifang Wu,
• Xiangdong Su,
• Yichuang Wu,
• Yuanjing Luo,
• Ying Guo and
• Yongbo Xue

Beilstein J. Org. Chem. 2022, 18, 200–207, doi:10.3762/bjoc.18.23

• heated at 60 °C for 1 h, and then 2-methylphenyl isothiocyanate (10 μL) was added to each reaction mixture and heated further for 1 h. The reaction mixture (0.5 mL) was then analyzed by HPLC and detected at 250 nm. Analytical HPLC was performed on a Welch Ultimate XB-C18 column (4.6 mm × 250 mm, 5 microm

Bifunctional thiourea-catalyzed asymmetric [3 + 2] annulation reactions of 2-isothiocyanato-1-indanones with barbiturate-based olefins

• Jiang-Song Zhai and
• Da-Ming Du

Beilstein J. Org. Chem. 2022, 18, 25–36, doi:10.3762/bjoc.18.3

• under the action of catalyst C4. Simultaneously, deprotonated 1a attacks the double bond of 2a from the Si face via intermediate A, resulting in a Michael addition reaction. Then the electron-deficient isothiocyanate moiety is attacked by newly generated α-carbon center from barbiturate-based olefins 2a

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

• -dipolar cycloaddition [16][21][22], were submitted to the reaction with benzoyl isothiocyanate in refluxing acetonitrile to obtain compounds L1, L2 and L3 in good yields [16][21]. Due to the very low biological activity of these ligands by themselves, the chelation with nickel(II) and palladium(II) was

N-Sulfinylpyrrolidine-containing ureas and thioureas as bifunctional organocatalysts

• Viera Poláčková,
• Dominika Krištofíková,
• Boglárka Némethová,
• Renata Górová,
• Mária Mečiarová and
• Radovan Šebesta

Beilstein J. Org. Chem. 2021, 17, 2629–2641, doi:10.3762/bjoc.17.176

• after each step prompted us to apply a Mitsunobu and Staudinger reaction for the preparation of amine 2 (Scheme 1) [33]. This one-pot reaction gave the desired amine 2 in 56% yield. Then, the corresponding isothiocyanate 3a was prepared by reaction of amine 2 with CS2 and DCC according to the reported

• procedure. However, this method gave product 3a in only 44% yield. Therefore, we decided to prepare isothiocyanate 3a using thiophosgene in dry THF with Et3N. This procedure afforded the corresponding isothiocyanate 3a in 86% yield (Scheme 1). Isocyanate 3b was also synthesized from amine 2. The reaction

• nitroalkene 9 using catalyst (S,R)-C2. Synthesis of isothiocyanate 3a and isocyanate 3b. Synthesis of sulfinylthioureas C1 and ureas C2. Synthesis of adducts 8a,d,f in solution. Michael additions of aldehydes 6b–d with nitroalkene 9. Michael addition of 3-phenylpropanal (6c) to nitroalkene 11. Optimization of

Photoinduced post-modification of graphitic carbon nitride-embedded hydrogels: synthesis of 'hydrophobic hydrogels' and pore substructuring

• Cansu Esen and
• Baris Kumru

Beilstein J. Org. Chem. 2021, 17, 1323–1334, doi:10.3762/bjoc.17.92

• –fluorescein isothiocyanate and fluorescein isothiocyanate–dextran fluorescent probes were subjected to HGCM and HGCM-vTA samples with a comparatively shorter releasing experiment than the one performed for RhB dye (Supporting Information File 1, Figure S4a). The static experiment principally relies on

• isothiocyanate conjugate (FITC-Albumin, Sigma-Aldrich), calcium chloride (CaCl2, 97%, Alfa Aesar), cyanuric acid (98%, Sigma-Aldrich), fluoresceinisothiocyanat-dextran (FITC–Dextran, 10.000 Mw), hydrochloric acid (HCl, 37%, Sigma-Aldrich), hydrochloric acid (1 M solution, Sigma-Aldrich), hydrogen peroxide (30

Chemical constituents of Chaenomeles sinensis twigs and their biological activity

• Joon Min Cha,
• Dong Hyun Kim,
• Lalita Subedi,
• Zahra Khan,
• Sang Un Choi,
• Sun Yeou Kim and
• Chung Sub Kim

Beilstein J. Org. Chem. 2020, 16, 3078–3085, doi:10.3762/bjoc.16.257

• 1a (1 mg). To the dried water-soluble phase were added pyridine (0.5 mL) and ʟ-cysteine methyl ester hydrochloride (0.5 mg), and the reaction mixture was stirred at 60 °C for 1 h. Then, o-tolyl isothiocyanate (0.1 mL) was added and the mixture stirred at 60 °C for another 1 h. The reaction mixture

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

• assumption, we decided to study alternative methods for the generation of azomethine imines from adducts 3. For this purpose, pyrazolopyrazole 3g was heated in toluene at 110 °C for 3 hours under microwave irradiation in the presence of dipolarophiles such as maleimide 5, isocyanate 7, and isothiocyanate 9

Recent synthesis of thietanes

• Jiaxi Xu

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

• Synthesis via formal [2 + 2] cycloadditions The [2 + 2] cycloaddition of alkenimines (R2C=C=NAr, 388) and 4-methylbenzenesulfonyl isothiocyanate (4-MeC6H4SO2NCS, 389) gave 2,4-diiminothietanes 390 in 48–54% yields. This is a general method to prepare 2,4-diiminothietane derivatives [102] (Scheme 81

• ). Phosphonium ylides, Ph3P+-C−=C=NR (391) reacted with isothiocyanate in a [2 + 2] cycloaddition to form the four-membered ring phosphonium ylides 392, which further reacted with aromatic aldehydes to afford the corresponding arylidene-2,4-diiminothietanes 393 [103] (Scheme 82). Thietan-2-ylideneacetates 397

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

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

• in the reaction of thiourea with primary amines [6]. Another important synthetic route for substituted thioureas is a two-step approach: (i) the addition/elimination reaction of benzoyl chloride, with a thiocyanate salt, generating in situ, benzoyl isothiocyanate, and (ii) an appropriate amine

• reaction with benzoyl isothiocyanate, yielding the acylthiourea which may be the final product or may be hydrolyzed to obtain the monosubstituted thiourea [7][8]. An alternative and versatile route for generating isothiocyanate for the use in the preparation of disubstituted symmetrical and unsymmetrical

• (14) to its chloride 15, which was submitted to an acyl nucleophile substitution reaction using ammonium thiocyanate as the nucleophile. This yielded the corresponding acyl isothiocyanate 16. The solid residue formed was used directly without further isolation and purification. The additional reaction

α,ß-Didehydrosuberoylanilide hydroxamic acid (DDSAHA) as precursor and possible analogue of the anticancer drug SAHA

• Shital K. Chattopadhyay,
• Subhankar Ghosh,
• Sarita Sarkar and
• Kakali Bhadra

Beilstein J. Org. Chem. 2019, 15, 2524–2533, doi:10.3762/bjoc.15.245

• 11b has been studied since it was the most cytotoxic among all. FITC (fluorescein-5-isothiocyanate)–annexin V/PI flow cytometry of HepG2 cells On HeLa cells, the efficacy of 11b was measured through the application of other apoptotic parameters like phosphatidylserine (PS) externalization, a known

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

• been developed between isocyanides, sulfur and alcohols or thiols under mild reaction conditions to afford O-thiocarbamates and dithiocarbamates in moderate to good yields. The one-pot reaction cascade involves the formation of an isothiocyanate intermediate, thus a catalyst-free synthesis of

• isothiocyanate [48][49][50][51][52] showing better atom economy. Nonetheless, only a few examples can be found in the literature starting from thiocyanates, and regarding the isothiocyanates the preparation of the reagent is required as an additional reaction step before. The synthesis of isothiocyanates

• afford isothiocyanate and harmless urea [63][64][65], but one should note that the instability of the nitrile oxides leads to many byproducts, turning this approach less attractive. The synthesis of isothiocyanates starting from isonitriles involves sulfur-containing reagents such as thallium

Novel solid-phase strategy for the synthesis of ligand-targeted fluorescent-labelled chelating peptide conjugates as a theranostic tool for cancer

• Sagnik Sengupta,
• Mena Asha Krishnan,
• Premansh Dudhe,
• Ramesh B. Reddy,
• Bishnubasu Giri,
• Sudeshna Chattopadhyay and
• Venkatesh Chelvam

Beilstein J. Org. Chem. 2018, 14, 2665–2679, doi:10.3762/bjoc.14.244

• and Sjogren's disease are caused by activated macrophages [16]. Recently EC17, (λex = 465–490 nm and λem = 520–530 nm) a conjugate of folic acid and fluorescein isothiocyanate has been used for intraoperative surgery of ovarian cancer [17], lung adenocarcinoma [18][19][20], and breast cancer [21

Non-native autoinducer analogs capable of modulating the SdiA quorum sensing receptor in Salmonella enterica serovar Typhimurium

• Matthew J. Styles and
• Helen E. Blackwell

Beilstein J. Org. Chem. 2018, 14, 2651–2664, doi:10.3762/bjoc.14.243

• ], which has an isothiocyanate (itc) at its acyl tail terminus installed for potential covalent capture in the AHL-binding site (vide infra). These 23 compounds were selected for further characterization to determine their relative inhibitory potencies in SdiA. Characterization of the efficacies and

Impact of Pseudomonas aeruginosa quorum sensing signaling molecules on adhesion and inflammatory markers in endothelial cells

• Carmen Curutiu,
• Florin Iordache,
• Veronica Lazar,
• Aurelia Magdalena Pisoschi,
• Aneta Pop,
• Mariana Carmen Chifiriuc and
• Alina Maria Hoban

Beilstein J. Org. Chem. 2018, 14, 2580–2588, doi:10.3762/bjoc.14.235

• -conjugated (FITC - fluorescein-isothiocyanate and PE - phycoerythrin) primary antibodies against IL-1β, IL-6, ICAM-1 PECAM-1, P-selectin, VE-cadherin (Beckman-Coulter). Endothelial cells were detached using trypsin (Sigma-Aldrich, USA) and washed in PBS. Cells were then incubated with the primary antibodies

β-Hydroxy sulfides and their syntheses

• Mokgethwa B. Marakalala,
• Edwin M. Mmutlane and
• Henok H. Kinfe

Beilstein J. Org. Chem. 2018, 14, 1668–1692, doi:10.3762/bjoc.14.143

• , hemithioacetal, various thioesters, thiocarbamate and isothiocyanate. This review article focuses on β-hydroxy sulfides and analogs; their presence in natural products, general protocols for their synthesis, and examples of their application in target oriented synthesis. Keywords: alkene thiofunctionalization

• , sulfide (acyclic or heterocyclic), disulfide, sulfoxide, sulfonate, thioaminal, hemithioacetal, various thioesters, thiocarbamate and isothiocyanate [3]. The three simplest sulfur-containing natural products are perhaps, (E)-2-butene-1-thiol (1), the principal ingredient of the repulsively malodorous

Oligonucleotide analogues with cationic backbone linkages

• Melissa Meng and
• Christian Ducho

Beilstein J. Org. Chem. 2018, 14, 1293–1308, doi:10.3762/bjoc.14.111

• '-amino-5'-deoxythymidine attached to CPG (37) served as the solid phase. The construction of the oligomer, achieved in 3'→5' direction, was based on the coupling of 3'-isothiocyanate 38 with the 5'-amino group of 37 to give 39 and, after acidic MMTr cleavage, 40. Iterative repetition of this coupling

Continuous-flow retro-Diels–Alder reaction: an efficient method for the preparation of pyrimidinone derivatives

• Imane Nekkaa,
• Márta Palkó,
• István M. Mándity and
• Ferenc Fülöp

Beilstein J. Org. Chem. 2018, 14, 318–324, doi:10.3762/bjoc.14.20

• lactim ethers [50]. For the preparation of 2-thioxopyrimidinones 7, 8a and 8b, the most common method is the reaction of the appropriate amino esters with phenyl isothiocyanate, followed by cyclization of the resulting thiourea with hydrogen chloride under reflux [45][49]. The starting materials were

5-Aminopyrazole as precursor in design and synthesis of fused pyrazoloazines

• Ranjana Aggarwal and
• Suresh Kumar

Beilstein J. Org. Chem. 2018, 14, 203–242, doi:10.3762/bjoc.14.15

• -Moghazy et al. [129] described the synthesis of pyrazolo[3,4-d]pyrimidine derivatives 187 using a similar approach by the reaction of ethyl 5-amino-1-phenyl-1H-pyrazolo-4-carboxylate (186) and phenyl isothiocyanate in pyridine. The pyrazolo[3,4-d]pyrimidine derivative 187 thus obtained was methylated with

• chlorides, chloroacetyl chloride, isothiocyanate and carbon disulfide under appropriate reaction conditions (Scheme 52). Hassan et al. [130] reported the synthesis of various pyrazolo[3,4-d]pyrimidine derivatives 193 (Scheme 53). 5-Aminopyrazole-4-carboxylic acid 190 on refluxing in acetic anhydride

• -carboxamide-5-aminopyrazole 199 for the synthesis of pyrazolo[3,4-d]pyrimidines 207 (Scheme 56). The condensation of 199 with benzoyl isothiocyanate under reflux conditions in dry acetone provided benzoylthioureido derivatives 201 which were converted to methylthio derivative 202 with iodomethane in aqueous