Glycosylation reactions mediated by hypervalent iodine: application to the synthesis of nucleosides and carbohydrates

• Yuichi Yoshimura,
• Hideaki Wakamatsu,
• Yoshihiro Natori,
• Yukako Saito and
• Noriaki Minakawa

Beilstein J. Org. Chem. 2018, 14, 1595–1618, doi:10.3762/bjoc.14.137

• glycols, epoxides, and olefins takes place by the action of hypervalent iodine [38][71][72]. For example, Havare and Plattner reported the oxidative cleavage of α-aryl aldehydes using iodosylbenzene to give chain-shortened carbonyl compounds and formaldehyde [71]. In the field of carbohydrate chemistry

Synthesis and in vitro biochemical evaluation of oxime bond-linked daunorubicin–GnRH-III conjugates developed for targeted drug delivery

• Sabine Schuster,
• Beáta Biri-Kovács,
• Bálint Szeder,
• Viktor Farkas,
• László Buday,
• Zsuzsanna Szabó,
• Gábor Halmos and
• Gábor Mező

Beilstein J. Org. Chem. 2018, 14, 756–771, doi:10.3762/bjoc.14.64

• formaldehyde (e.g., from the softeners of the plastic tubes) not only during the reaction steps (cleavage, ligation) but also under the HPLC purification conditions which has a high impact on the yield [35]. Secondary structure determination by electronic circular dichroism spectroscopy ECD spectra of GnRH-III

Mannich base-connected syntheses mediated by ortho-quinone methides

• Petra Barta,
• Ferenc Fülöp and
• István Szatmári

Beilstein J. Org. Chem. 2018, 14, 560–575, doi:10.3762/bjoc.14.43

• reaction is an important, one-pot, multicomponent, C–C bond forming reaction that is widely used in the syntheses of many biologically active and natural compounds [1][2][3][4][5]. Originally, the Mannich product is formed through a three-component reaction containing a C–H acid, formaldehyde and a

• formaldehyde and 2,2-disubstituted acetaldehydes 28. Formaldehyde, as a non-enolizable compound is more likely to give Mannich base product 30. In contrast, enolizable 2,2-disubstituted aldehydes easily form enamines 31 that undergo cycloaddition with electron-deficient o-QMs giving 2,2-dialkyl-3-dialkylamino

Stimuli-responsive oligonucleotides in prodrug-based approaches for gene silencing

• Françoise Debart,
• Christelle Dupouy and
• Jean-Jacques Vasseur

Beilstein J. Org. Chem. 2018, 14, 436–469, doi:10.3762/bjoc.14.32

• formaldehyde to produce the phosphorothioate ON. Despite these promising results, further studies on the use of these prodrugs to control genetic expression have not been carried out. Thus far, most of these results were obtained for thymidine homopolymers [32]. The reason is that the synthesis of ON prodrugs

• shown to improve RNA nuclease resistance and not to hamper duplex dsRNA formation, and they are removed by cellular esterases. Indeed, 2’-O-acyloxymethyl ONs are converted to unmodified RNAs by carboxyesterase-mediated deacylation with the release of formaldehyde to produce the parent RNA (Scheme 10

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

• 58 and formaldehyde (R’= H, 47) were performed under microwave and conventional heating conditions by Quiroga et al. [65] (Scheme 18). Both the reaction conditions resulted in the formation of pyrazolo[3,4-b]pyridine-5-spirocycloalkanediones 76 but an additional compound 3-tert-butyl-1-phenylindeno

Binding abilities of a chiral calix[4]resorcinarene: a polarimetric investigation on a complex case of study

• Marco Russo and
• Paolo Lo Meo

Beilstein J. Org. Chem. 2017, 13, 2698–2709, doi:10.3762/bjoc.13.268

• ) [54] to a Mannich-type reaction with L-proline and formaldehyde (Figure 3). The precursor preCA, in turn, was obtained by an acid-catalysed condensation between resorcinol and butyraldehyde. Of course, the main difference between the syntheses of CAP and CAPS is constituted by the choice of the

Phosphonic acid: preparation and applications

• Charlotte M. Sevrain,
• Mathieu Berchel,
• Hélène Couthon and
• Paul-Alain Jaffrès

Beilstein J. Org. Chem. 2017, 13, 2186–2213, doi:10.3762/bjoc.13.219

• difficulties, some reactions are very efficient as reported below. 6.1. Moedritzer–Irani reaction The reaction of an amine (primary or secondary amine), formaldehyde (aqueous or solid paraformaldehyde) and phosphorous acid in acidic media produces amino-bis(methylenephosphonic acid, Figure 30A,B). This

• consequence, the stoichiometry must be adapted and 2 equivalents of both formaldehyde and phosphorous acid must be used. The reaction is also applicable to secondary amine and produce mono-aminomethylene phosphonic acid (Figure 30B). The yield of this reaction is variable as illustrated in Figure 30C. The

Novel approach to hydroxy-group-containing porous organic polymers from bisphenol A

• Tao Wang,
• Yan-Chao Zhao,
• Li-Min Zhang,
• Yi Cui,
• Chang-Shan Zhang and
• Bao-Hang Han

Beilstein J. Org. Chem. 2017, 13, 2131–2137, doi:10.3762/bjoc.13.211

• connecting phenolic molecules with formaldehyde or other aromatic aldehydes to form cross-linking structures through the simple Bakelite-type chemistry to obtain great number of polymers with different functionalities. Phloroglucinol has been utilized as a monomer by Kanatzidis and Katsoulidis [23][24] to

Pd(OAc)₂/Ph₃P-catalyzed dimerization of isoprene and synthesis of monoterpenic heterocycles

• Dominik Kellner,
• Maximilian Weger,
• Andrea Gini and
• Olga García Mancheño

Beilstein J. Org. Chem. 2017, 13, 1807–1815, doi:10.3762/bjoc.13.175

• of pyranes by a hetero-Diels–Alder reaction was realized. Thus, the reaction of 2-TT with formaldehyde in acetic acid at reflux led after 6 h exclusively to one regioisomer dihydropyrane 5 in 64% (Scheme 3, left) [42]. Next, the thermal Diels–Alder reaction with maleic anhydride and N-substituted

Oxidative dehydrogenation of C–C and C–N bonds: A convenient approach to access diverse (dihydro)heteroaromatic compounds

• Santanu Hati,
• Ulrike Holzgrabe and
• Subhabrata Sen

Beilstein J. Org. Chem. 2017, 13, 1670–1692, doi:10.3762/bjoc.13.162

• benzothiazolines 64 to substituted pyridines 65 and benzothiazoles 66, respectively, in moderate to excellent yields (Scheme 18) [82]. The reaction was performed in methanol at ambient temperature. The optimized procedure also generated 65 and 66 from a one-pot reaction of various dicarbonyls, formaldehyde

1-Imidoalkylphosphonium salts with modulated C_α–P⁺ bond strength: synthesis and application as new active α-imidoalkylating agents

• Jakub Adamek,
• Roman Mazurkiewicz,
• Anna Węgrzyk and
• Karol Erfurt

Beilstein J. Org. Chem. 2017, 13, 1446–1455, doi:10.3762/bjoc.13.142

• aldehydes or ketones (mainly formaldehyde) with ammonia or aliphatic amines and CH-acidic carbonyl compounds, known as the Mannich reaction, plays an important role in organic synthesis, despite some limitations of this reaction. α-Amidoalkylation reactions are considered an important extension of the

Aqueous semisynthesis of C-glycoside glycamines from agarose

• Juliana C. Cunico Dallagnol,
• Alexandre Orsato,
• Diogo R. B. Ducatti,
• Miguel D. Noseda,
• Maria Eugênia R. Duarte and
• Alan G. Gonçalves

Beilstein J. Org. Chem. 2017, 13, 1222–1229, doi:10.3762/bjoc.13.121

• see Supporting Information File 1. We could access pure 8 by reacting 7 and formaldehyde under reductive conditions. The reaction product 8 kept the original configuration of its parenting analogue, amine 7, because the reaction between such primary amine 7 and formaldehyde occurs via an imine

Sugar-based micro/mesoporous hypercross-linked polymers with in situ embedded silver nanoparticles for catalytic reduction

• Qing Yin,
• Qi Chen,
• Li-Can Lu and
• Bao-Hang Han

Beilstein J. Org. Chem. 2017, 13, 1212–1221, doi:10.3762/bjoc.13.120

• .13.120 Abstract Porous hypercross-linked polymers based on perbenzylated monosugars (SugPOP-1–3) have been synthesized by Friedel–Crafts reaction using formaldehyde dimethyl acetal as an external cross-linker. Three perbenzylated monosugars with similar chemical structure were used as monomers in order

• -linkers [4], and self-polycondensation of small molecular monomers [5]. Since the Tan group proposed the new synthetic strategy that "knits" low functionality rigid aromatic compounds with formaldehyde dimethyl acetal (FDA) as an external cross-linking agent through a Friedel–Crafts reaction to synthesize

• AgNPs/SugPOP-1 composite. Time-dependent UV–vis spectral changes (a) and the kinetic curve (b) for the catalytic reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) at room temperature. Preparation of polymers SugPOP-1–3 (FDA: formaldehyde dimethyl acetal). The preparation of AgNPs/SugPOP-1

NMR reaction monitoring in flow synthesis

• M. Victoria Gomez and
• Antonio de la Hoz

Beilstein J. Org. Chem. 2017, 13, 285–300, doi:10.3762/bjoc.13.31

• , Steinhof et al. [47] studied the equilibria and kinetics of the reaction of 1,3-dimethylurea with formaldehyde, which is a model for the industrially relevant urea–formaldehyde system. The reaction was performed in a batch reactor and the analysis was carried out using a commercial NMR flow probe (Figure

•  10). The design represented in Figure 10 allows the regulation of the molar ratio of reagents for the kinetic experiments (urea/formaldehyde from 1:1 to 4:1) as well as the temperature and pH, which were constantly measured. The reaction mixture flowed to the NMR instrument (400 MHz) by way of a pump

• . Design of the experimental setup used to combine on-line NMR spectroscopy and a batch reactor. Reproduced with permission from reference [47]. Copyright 2015 John Wiley and Sons. Reaction system 1,3-dimethylurea/formaldehyde. Main reaction pathway and side reactions [47]. (a) Experimental setup for the

Formose reaction controlled by boronic acid compounds

• Toru Imai,
• Tomohiro Michitaka and
• Akihito Hashidzume

Beilstein J. Org. Chem. 2016, 12, 2668–2672, doi:10.3762/bjoc.12.263

• solution of formaldehyde is warmed in the presence of a basic catalyst, a mixture of sugars and sugar alcohols, i.e., ‘formose’, is obtained. This reaction is called ‘formose reaction’ and was first reported by Butlerow, a Russian chemist, in 1861 [1]. Studies on formose reactions have revealed that the

• polymer, respectively (Scheme 1). The copolymer was prepared by radical copolymerization at a molar ratio of 1:10 in monomer feed. The formose reaction was carried out using a solution containing 200 mM formaldehyde and 20 mM calcium hydroxide at 60 °C. Fructose or glyceraldehyde was employed as a

• (ESIMS) data for the products of the formose reaction in the presence of SPB and pVPB/NaSS. The spectrum for SPB shows a series of signals at m/z = 215, 245, and 275, indicating an interval of 30 mass units, which corresponds to the formaldehyde unit. These signals are ascribable to potassium adducts of

Formose reaction accelerated in aerosol-OT reverse micelles

• Makoto Masaoka,
• Tomohiro Michitaka and
• Akihito Hashidzume

Beilstein J. Org. Chem. 2016, 12, 2663–2667, doi:10.3762/bjoc.12.262

• reaction using formaldehyde-13C as starting material are indicative of the formation of ethylene glycol as a major product. Keywords: aerosol-OT; formose reaction; hexadecyltrimethylammonium bromide; interfacial layer; reverse micelles; triton X-100; water pool; Findings The ‘formose reaction’ yields a

• mixture of sugars and sugar alcohols, called ‘formose’, from formaldehyde by heating under basic conditions. It has been considered that the formose reaction is a possible pathway for sugar formation under prebiotic conditions [1][2][3][4]. The formose reaction was first reported by Butlerow in 1861 [5

• ]. Studies on the formose reaction by a number of researchers have revealed that the formose reaction consists of three periods, i.e., the induction period, the sugar formation period, and the sugar degradation period [6]. In the induction period two formaldehyde molecules form glycolaldehyde, which is the

A direct method for the N-tetraalkylation of azamacrocycles

• Andrew J. Counsell,
• Angus T. Jones,
• Matthew H. Todd and
• Peter J. Rutledge

Beilstein J. Org. Chem. 2016, 12, 2457–2461, doi:10.3762/bjoc.12.239

• ][30], the simplest N-tetraalkyl cyclam derivative, this class of compounds has been extensively investigated [2]. While the N-tetramethyl derivative is readily accessed by treating cyclam with formaldehyde and formic acid [29], this transformation (the Eschweiler–Clarke methylation) [31] is not

Stereoselective synthesis of fused tetrahydroquinazolines through one-pot double [3 + 2] dipolar cycloadditions followed by [5 + 1] annulation

• Xiaofeng Zhang,
• Kenny Pham,
• Shuai Liu,
• Marc Legris,
• Alex Muthengi,
• Jerry P. Jasinski and
• Wei Zhang

Beilstein J. Org. Chem. 2016, 12, 2204–2210, doi:10.3762/bjoc.12.211

• formaldehyde through [5 + 1] annulation to afford a novel polycyclic scaffold bearing tetrahydroquinazoline, pyrrolidine, pyrrolidinedione, and N-substituted maleimide in stereoselective fashion. Keywords: [5 + 1] annulation; [3 + 2] cycloaddition; one-pot reactions; stereoselective synthesis

• exploring the reaction conditions, it was found that the reaction of 7a with formaldehyde in 1,4-dioxane at 110 °C afforded product 1a in 93% isolated yield (Table 2, entry 3). Other reactants such as HC(OEt)3, HCO2H, and paraformaldehyde (PFA) were also employed for the [5 + 1] annulation reactions. But

• only formaldehyde afforded tetrahydroquinazoline 1a in good yield under catalyst-free conditions. A number of [5 + 1] annulation reactions using selected compounds 7 were carried out to afford 10 analogs of tetrahydroquinazolines 1 in 88–95% isolated yields as single diastereomers (Figure 4). In

Hydroxy-functionalized hyper-cross-linked ultra-microporous organic polymers for selective CO₂ capture at room temperature

• Partha Samanta,
• Priyanshu Chandra and
• Sujit K. Ghosh

Beilstein J. Org. Chem. 2016, 12, 1981–1986, doi:10.3762/bjoc.12.185

• polymers (HCPs) are a subclass of this type of porous materials. Recently, hyper-cross-linked MOPs are emerged as a new subclass, synthesized by hyper-cross linking of basic small organic building blocks by Friedel–Crafts reaction in the presence of the Lewis acid FeCl3 (as catalyst) and formaldehyde

• synthesis, the cost-effective formaldehyde dimethyl acetal (FDA), FeCl3 and that organic small molecules can produce very low cost materials with high yield [28]. Hyper-cross-linking prevents the close packing of polymeric chains in this type of material to impart the intrinsic porosity. Hyper-cross-linked

Rearrangements of organic peroxides and related processes

• Ivan A. Yaremenko,
• Vera A. Vil’,
• Dmitry V. Demchuk and
• Alexander O. Terent’ev

Beilstein J. Org. Chem. 2016, 12, 1647–1748, doi:10.3762/bjoc.12.162

• ]. Carbonyl oxides (Criegee intermediates) are one of the most important compounds in tropospheric chemistry [309]. Direct investigations of formaldehyde oxide (CH2OO) or acetaldehyde oxide (CH3CHOO) reactions with water vapor, SO2, NO2 were carried out [310][311][312]. 1.3 Hock rearrangement The Hock

Towards the total synthesis of keramaphidin B

• Pavol Jakubec,
• Alistair J. M. Farley and
• Darren J. Dixon

Beilstein J. Org. Chem. 2016, 12, 1096–1100, doi:10.3762/bjoc.12.104

• turn be synthesised by an aminolysis/oxidation/olefination sequence of the terminal alcohol 6, following traceless nitro group removal. 5-Nitropiperidin-2-one 6 in turn could be accessed by a nitro-Mannich lactamisation cascade reaction between Michael adduct 7, formaldehyde and a suitable primary

• favoured attack at the more reactive δ-lactone carbonyl instead of that of the methyl ester. Pleasingly, this was indeed realised at the next stage; performing a nitro-Mannich lactamisation cascade on 13 with formaldehyde and butylamine in methanol afforded lactam 15 in 63% yield, possessing the

• the model system, identical levels of diastereo- and enantiocontrol were observed in the formation of 7 (92% yield). Treatment of the major diastereomeric product 7 with hept-5-yn-1-amine (16) and formaldehyde in boiling methanol afforded the lactam 6 in 56% yield as a single diastereomer in 91:9 er

Recent advances in N-heterocyclic carbene (NHC)-catalysed benzoin reactions

• Rajeev S. Menon,
• Akkattu T. Biju and
• Vijay Nair

Beilstein J. Org. Chem. 2016, 12, 444–461, doi:10.3762/bjoc.12.47

• , Inoue and co-workers reported the NHC-catalysed selective cross-benzoin reactions of aromatic and aliphatic aldehydes with formaldehyde leading to the formation of α-hydroxy ketones. Although an excellent selectivity was observed for the cross-benzoin product, the yields were low (Scheme 7) [20]. Later

A novel and practical asymmetric synthesis of dapoxetine hydrochloride

• Yijun Zhu,
• Zhenren Liu,
• Hongyan Li,
• Deyong Ye and
• Weicheng Zhou

Beilstein J. Org. Chem. 2015, 11, 2641–2645, doi:10.3762/bjoc.11.283

• -phenylpropan-1-amine, 7): To a 50 mL round-bottomed flask, 6 (6 g, 21.6 mmol), 98% HCOOH (3.9 mL, 54.1 mmol) and an aqueous solution of 30% formaldehyde (9.7 mL, 108 mmol) were added at room temperature. The reaction mixture was heated to 85 °C for 8 h and quenched with saturated aqueous NaHCO3 solution (pH ≈8

Synthesis of Xenia diterpenoids and related metabolites isolated from marine organisms

• Tatjana Huber,
• Lara Weisheit and
• Thomas Magauer

Beilstein J. Org. Chem. 2015, 11, 2521–2539, doi:10.3762/bjoc.11.273

• -catalyzed conjugate addition of silyl ketene acetal 81a to enone ent-80. Deprotonation and trapping of the resulting enolate with formaldehyde furnished lactone 82 in a regio- and stereoselective fashion. Introduction of the exocyclic double bond proved to be challenging and therefore salt-free, highly

Comparison of the catalytic activity for the Suzuki–Miyaura reaction of (η⁵-Cp)Pd(IPr)Cl with (η³-cinnamyl)Pd(IPr)(Cl) and (η³-1-t-Bu-indenyl)Pd(IPr)(Cl)

• Patrick R. Melvin,
• Nilay Hazari,
• Hannah M. C. Lant,
• Ian L. Peczak and
• Hemali P. Shah

Beilstein J. Org. Chem. 2015, 11, 2476–2486, doi:10.3762/bjoc.11.269

• formaldehyde (in the case of reaction performed in MeOH), are consistent with the previously reported pathway (Scheme 2) [16]. In this mechanism initial substitution of a Cl− ligand in Cp by the solvent gives rise to the alkoxide complex A. Subsequently, the η5-Cp ring can undergo slippage to form complex B

• , with an η1-Cp ligand. The η1-Cp ligand is nucleophilic and can abstract a β-hydrogen from the alkoxide ligand to generate a Pd(0) species with a coordinated cyclopentadiene ligand (C). In this step the formaldehyde or acetone byproduct originating from the solvent is released. Finally, dissociation of