Copper-catalyzed monoselective C–H amination of ferrocenes with alkylamines

• Zhen-Sheng Jia,
• Qiang Yue,
• Ya Li,
• Xue-Tao Xu,
• Kun Zhang and
• Bing-Feng Shi

Beilstein J. Org. Chem. 2021, 17, 2488–2495, doi:10.3762/bjoc.17.165

• groups. Kumar and co-workers developed a Cu-mediated C–H chalcogenation and sulfonation of ferrocenes [27][28][29]. The use of a bidentate 1,10-phenathroline ligand was critical to achieve mono-selectivity in the chacogenation reactions [28]. Meanwhile, Co(III)-catalyzed ortho-C–H amidation of ferrocene

Progress and challenges in the synthesis of sequence controlled polysaccharides

• Giulio Fittolani,
• Theodore Tyrikos-Ergas,
• Denisa Vargová,
• Manishkumar A. Chaube and
• Martina Delbianco

Beilstein J. Org. Chem. 2021, 17, 1981–2025, doi:10.3762/bjoc.17.129

Synthetic reactions driven by electron-donor–acceptor (EDA) complexes

• Zhonglie Yang,
• Yutong Liu,
• Kun Cao,
• Xiaobin Zhang,
• Hezhong Jiang and
• Jiahong Li

Beilstein J. Org. Chem. 2021, 17, 771–799, doi:10.3762/bjoc.17.67

• aminosulfonylation, employing blue light as irradiation source (Scheme 5). It has to be said that nitrogen radicals played a coordinating role in the sulfonation step. Additionally, to verify the applicability of this approach, 1H-benzo[d][1,2]thiazine 2,2-dioxides have been prepared successfully. A possible

One-pot synthesis of isosorbide from cellulose or lignocellulosic biomass: a challenge?

• Isaline Bonnin,
• Raphaël Mereau,
• Thierry Tassaing and
• Karine De Oliveira Vigier

Beilstein J. Org. Chem. 2020, 16, 1713–1721, doi:10.3762/bjoc.16.143

• activity and recyclability of the catalyst was improved. A modification of the Ru/C hydrogenation catalyst’s surface by sulfonation and oxidative treatment was performed and had a significant effect on the catalyst properties in the isosorbide synthesis. Hence, strong acid sites are generated on the

Recent applications of porphyrins as photocatalysts in organic synthesis: batch and continuous flow approaches

• Rodrigo Costa e Silva,
• Luely Oliveira da Silva,
• Aloisio de Andrade Bartolomeu,
• Timothy John Brocksom and
• Kleber Thiago de Oliveira

Beilstein J. Org. Chem. 2020, 16, 917–955, doi:10.3762/bjoc.16.83

• , but accompanied by long reaction times (Scheme 16). In 2014, Yang, Huang, Wang and co-workers reported a photocatalytic sulfonation of alkenes to β-ketosulfones (widely used in the synthesis of compounds with biological activities [44]), using porphyrins supported in CN materials (Scheme 17) [45]. The

• mediated by 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS). The CNH was then applied as photocatalyst in the photoinduced sulfonation of styrene with p-methylbenzenesulfinic acid. The corresponding β-ketosulfone was obtained in 94% yield. However, the yield

• -rich and electron-deficient groups in the arylsulfinic acid and alkyl sulfinates, such as sodium ethylsulfinate and sodium methylsulfinate (Scheme 19). The authors also showed that the methodology can be applied to the sulfonation of steroid drug arimistane in 45% yield (Scheme 20). The mechanistic

An overview on recent advances in the synthesis of sulfonated organic materials, sulfonated silica materials, and sulfonated carbon materials and their catalytic applications in chemical processes

• Hashem Sharghi,
• Pezhman Shiri and
• Mahdi Aberi

Beilstein J. Org. Chem. 2018, 14, 2745–2770, doi:10.3762/bjoc.14.253

• 2900 cm−1 and 3400 cm−1 were the evidence of phenylic C–H bond and N–H stretching of carbazole, respectively. Peaks at 1022 cm−1 and 1039 cm−1 corresponded to additional crosslinking during the sulfonation process. The catalyst was investigated by BET, SEM, TEM, and TGA-DTA, as well. The BET surface

• area decreased from 913 m2 g−1 to 346 m2g−1 during the sulfonation process. The SEM images of HMP-1 (113) and HMP-1-SO3H (114) showed spherical particles. According to the TGA-DTA plot, HMP-1-SO3H (114) is less stable than HMP-1 (113). The resulted catalyst was tested in biodiesel synthesis at room

• copolymer synthesized by Friedel–Crafts alkylation of triphenylamine (115) with dibromo-p-xylene 112 was prepared (Scheme 21). After the sulfonation process, the resulted material has been employed as a heterogeneous, reusable, and environmentally benign catalyst in the multicomponent synthesis of

Rapid transformation of sulfinate salts into sulfonates promoted by a hypervalent iodine(III) reagent

• Elsa Deruer,
• Vincent Hamel,
• Samuel Blais and
• Sylvain Canesi

Beilstein J. Org. Chem. 2018, 14, 1203–1207, doi:10.3762/bjoc.14.101

• aromatic systems or cyclic ethers through a ring opening pathway. Keywords: hypervalent iodine; oxidation; sulfinates; sulfonation; sulfonium; Introduction Over the past few decades, hypervalent iodine reagents [1][2][3][4] have emerged as versatile and environmentally benign substitutes for heavy metal

Sulfation and amidinohydrolysis in the biosynthesis of giant linear polyenes

• Hui Hong,
• Markiyan Samborskyy,
• Katsiaryna Usachova,
• Katharina Schnatz and
• Peter F. Leadlay

Beilstein J. Org. Chem. 2017, 13, 2408–2415, doi:10.3762/bjoc.13.238

• mediomycin A formation involves quite distinctive late-stage processing: both an O-sulfonation step and a deamidination step. O-Sulfonation in particular is a rare and interesting modification seen in diverse microbial natural products (Scheme S1, Supporting Information File 1) including the non-glycosylated

• before or after the specific sulfonation step. The sequence of the sulfotransferase is a useful probe to uncover related gene clusters in public sequence databases. Sulfonation remains a rare and relatively poorly understood modification in natural product biosynthesis [27][28][29][30]. As our

• . Sulfonation has been suggested as a novel approach to block the development of antibiotic resistance [33][34] while the discovery of the sulfated metabolite FR901379 was a critical breakthrough in the successful clinical development of micafungin to combat systemic fungal infections [12]. HPLC–UV–MS analysis

Transition-metal-catalyzed synthesis of phenols and aryl thiols

• Yajun Liu,
• Shasha Liu and
• Yan Xiao

Beilstein J. Org. Chem. 2017, 13, 589–611, doi:10.3762/bjoc.13.58

• , classic methods for the synthesis of phenols included the sulfonation of benzene [11], the Dakin reaction [12][13] and the Sandmeyer-type reaction [14]. These methods are useful for the preparation of various phenols, however, they suffer from several drawbacks such as multistep syntheses, toxic solvents

Syntheses of 2-substituted 1-amino-4-bromoanthraquinones (bromaminic acid analogues) – precursors for dyes and drugs

• Enas M. Malik,
• Younis Baqi and
• Christa E. Müller

Beilstein J. Org. Chem. 2015, 11, 2326–2333, doi:10.3762/bjoc.11.253

• inert solvent (e.g., nitrobenzene) to form 1-aminoanthraquinone-2-sulfonic acid (4), the salt of which is then brominated to give bromaminic acid sodium salt (2). Sulfonation of 3 (oleum method) is achieved by the use of oleum followed by bromination in a one-pot reaction. Therefore, the oleum method is

Cyclodextrin-grafted polymers functionalized with phosphanes: a new tool for aqueous organometallic catalysis

• Jonathan Potier,
• Stéphane Menuel,
• David Mathiron,
• Véronique Bonnet,
• Frédéric Hapiot and
• Eric Monflier

Beilstein J. Org. Chem. 2014, 10, 2642–2648, doi:10.3762/bjoc.10.276

• ][15][16][17][18]. To access the expected CD-substituted polymer functionalized with water-soluble phosphanes, a sulfonation step of a commercially available phosphane was first required. 2-(Diphenylphosphino)ethanamine was sulfonated in an oleum/H2SO4 mixture at room temperature over a period of 15

• isolated in 55% yield as white crystals. The meta-sulfonation on the aromatic rings was confirmed by NMR. The COSY spectrum (Supporting Information File 1) was especially indicative of the meta-substitution. Indeed, H4 (Scheme 1) did not correlate with any other proton and appeared as an upfield shifted

Concise, stereodivergent and highly stereoselective synthesis of cis- and trans-2-substituted 3-hydroxypiperidines – development of a phosphite-driven cyclodehydration

• Peter H. Huy,
• Julia C. Westphal and
• Ari M. P. Koskinen

Beilstein J. Org. Chem. 2014, 10, 369–383, doi:10.3762/bjoc.10.35

• conditions (I2, PPh3) [81][82] surpassed by far Mitsunobu conditions and sulfonation (with MsCl, TsCl) induced cyclisations (see Supporting Information File 1 for more details): Under optimized conditions (1.1 equiv I2, Et3N in MeCN at −40 °C) the cyclic products 11a–c were isolated in 68–77% yield and 90–99

Shelf-stable electrophilic trifluoromethylating reagents: A brief historical perspective

• Norio Shibata,
• Andrej Matsnev and
• Dominique Cahard

Beilstein J. Org. Chem. 2010, 6, No. 65, doi:10.3762/bjoc.6.65

• synthesized sulfonated analogs of (trifluoromethyl)dibenzochalcogenium salts by sulfonation with fuming sulfuric acid. Further nitration of sulfonate 14 led to a more reactive nitro-substituted derivative 15 (Scheme 10). These reagents allow easy separation of by-products from the desired trifluoromethylated

Fused bicyclic piperidines and dihydropyridines by dearomatising cyclisation of the enolates of nicotinyl-substituted esters and ketones

• Heloise Brice,
• Jonathan Clayden and
• Stuart D. Hamilton

Beilstein J. Org. Chem. 2010, 6, No. 22, doi:10.3762/bjoc.6.22

• example) [39]. Even greater reactivity towards intramolecular nucleophilic attack is exhibited by isonicotinamides when activated by N-sulfonation [40][41]. For example, the N-furylmethyl isonicotinamide 3 cyclises to the doubly dearomatised bis-spirocycle 4 on treatment with triflic anhydride in the

Trifluoromethyl ethers – synthesis and properties of an unusual substituent

• Frédéric R. Leroux,
• Baptiste Manteau,
• Jean-Pierre Vors and
• Sergiy Pazenok

Beilstein J. Org. Chem. 2008, 4, No. 13, doi:10.3762/bjoc.4.13

• meta with respect to the nitrogen function and ortho to the trifluoromethoxy group!). The pronounced preference for para substitution of (trifluoromethoxy)benzene [52][63][64] holds for most electrophilic aromatic substitutions, in particular sulfonation [64], bromination [52], chloromethylation [68