Synthesis of monophosphorylated lipid A precursors using 2-naphthylmethyl ether as a protecting group

• Jundi Xue,
• Ziyi Han,
• Gen Li,
• Khalisha A. Emmanuel,
• Cynthia L. McManus,
• Qiang Sui,
• Dongmian Ge,
• Qi Gao and
• Li Cai

Beilstein J. Org. Chem. 2020, 16, 1955–1962, doi:10.3762/bjoc.16.162

• (3) was treated with Meldrum’s acid (2,2-dimethyl-1,3-dioxane-4,6-dione) followed by decarboxylation in methanol to give methyl 3-oxotetradecanoate (4) in 77% yield. The enantioselective hydrogenation of the β-carbonyl group using (R)-Ru(OAc)2(BINAP) at 65 °C and under 1.5 MPa H2 afforded methyl (R

• )-3-hydroxytetradecanoate (5) in 98% yield. The same hydrogenation reaction was carried out using the (S)-Ru(OAc)2(BINAP) catalyst. Then both the R and S products were compared using chiral HPLC to confirm the absolute configuration and enantiomeric purity (Figure S1, Supporting Information File 1

• of 29 was phosphorylated using tetrabenzyl diphosphate in the presence of LHMDS in THF at −78 °C. Then finally global deprotection (hydrogenation over Pd-black) was carried out to remove the naphthylidene acetal, Nap ethers, and the benzyl phosphate groups in compound 30. By this route the target

Synthesis, docking study and biological evaluation of ᴅ-fructofuranosyl and ᴅ-tagatofuranosyl sulfones as potential inhibitors of the mycobacterial galactan synthesis targeting the galactofuranosyltransferase GlfT2

• Marek Baráth,
• Jana Jakubčinová,
• Zuzana Konyariková,
• Stanislav Kozmon,
• Katarína Mikušová and
• Maroš Bella

Beilstein J. Org. Chem. 2020, 16, 1853–1862, doi:10.3762/bjoc.16.152

• hydrogenation provided target 1-O-phosphono-ᴅ-fructofuranosyl sulfones 1aα, 1bα, 1bβ and 1cα as white powders after freeze drying. Based on the molecular docking results, the series of ᴅ-tagatofuranose compounds can be divided into two groups. The first group represented the more flexible structures 2 with free

• gave 11 in good yield. Likewise, 6-O-benzyl derivative 12 was prepared to reduce reaction steps and to ensure a clean progress of the benzyl protecting group removal by catalytic hydrogenation (Scheme 2). The direct thioglycosylation of 11 with ethanethiol in the presence of BF3∙OEt2 afforded 2-thio-ᴅ

• protecting group in derivative 14 led to alcohol 15 as the common intermediate for the synthesis of target structures 2a and 3a. The fully deprotected target compound 2a was obtained in good yield by acidic hydrolysis of the acetonide protecting group with 3 M HCl in THF followed by catalytic hydrogenation

When metal-catalyzed C–H functionalization meets visible-light photocatalysis

• Lucas Guillemard and
• Joanna Wencel-Delord

Beilstein J. Org. Chem. 2020, 16, 1754–1804, doi:10.3762/bjoc.16.147

• towards various functional groups such as aldehydes, ketones, and esters. Of note is that in some cases, partial hydrogenation of the double bond was observed, resulting probably from the generation of a ruthenium–hydride complex. However, this consecutive reactivity and the ratio between the olefin and

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

• . Isosorbide is obtained after the hydrolysis of cellulose to glucose, followed by the hydrogenation of glucose to sorbitol that is then dehydrated to isosorbide. The one-pot process requires an acid and a hydrogenation catalyst. Several parameters are of importance during the direct conversion of (ligno

• a lot of interest due to the rarefaction of fossil oil and environmental concerns. One of the interesting reactions is the conversion of cellulose to isosorbide, a 1,4:3,6-dianhydrohexitol [1]. This reaction occurs in several steps: 1) hydrolysis of cellulose to glucose 2) hydrogenation of glucose

• dehydration of ᴅ-sorbitol using a strong acid catalyst [10][11]. ᴅ-Sorbitol is produced from the hydrogenation of glucose obtained mostly from the hydrolysis of starch, but also from sucrose or cellulose. Consequently, the cellulose valorization can be realized from the one-pot conversion of cellulose to

Synthesis of the tetrasaccharide repeating unit of the O-specific polysaccharide of Azospirillum doebereinerae type strain GSF71^T using linear and one-pot iterative glycosylations

• Arin Gucchait,
• Pradip Shit and
• Anup Kumar Misra

Beilstein J. Org. Chem. 2020, 16, 1700–1705, doi:10.3762/bjoc.16.141

• treatment with HClO4-SiO2 [34]; (c) selective acetylation of the primary hydroxy group, and (d) removal of the benzyl groups by catalytic transfer hydrogenation [35] using triethylsilane in the presence of Pearlman’s catalyst [36] to furnish the desired tetrasaccharide 1 in 50% overall yield with the two O

Synthesis of Streptococcus pneumoniae serotype 9V oligosaccharide antigens

• Sharavathi G. Parameswarappa,
• Claney L. Pereira and
• Peter H. Seeberger

Beilstein J. Org. Chem. 2020, 16, 1693–1699, doi:10.3762/bjoc.16.140

• mannosamine was obtained from 33, that in turn was a product of the benzylation of 32. Cleavage of the benzylidene group in 33 yielded 34 that was selectively acetylated at the primary alcohol at low temperature to obtain 35 [30]. The subsequent removal of the benzyl groups using hydrogenation with Pd/C in an

Pauson–Khand reaction of fluorinated compounds

• Jorge Escorihuela,
• Daniel M. Sedgwick,
• Alberto Llobat,
• Mercedes Medio-Simón,
• Pablo Barrio and
• Santos Fustero

Beilstein J. Org. Chem. 2020, 16, 1662–1682, doi:10.3762/bjoc.16.138

• corresponding aldehyde in a 41% global yield. Bicyclic product 49a underwent diastereoselective (dr > 20:1) hydrogenation using palladium over activated charcoal under an atmosphere of hydrogen to afford saturated derivative 50 (Scheme 26). On the other hand, the tert-butanesulfonyl group could be removed

Rearrangement of o-(pivaloylaminomethyl)benzaldehydes: an experimental and computational study

• Csilla Hargitai,
• Györgyi Koványi-Lax,
• Tamás Nagy,
• Péter Ábrányi-Balogh,
• András Dancsó,
• Gábor Tóth,
• Judit Halász,
• Angéla Pandur,
• Gyula Simig and
• Balázs Volk

Beilstein J. Org. Chem. 2020, 16, 1636–1648, doi:10.3762/bjoc.16.136

• [8], and isoindole [3][9][10] to dimerize and polymerize was observed long ago. A repeatedly mentioned example was the formation of type 5 dimers under various conditions. They were first isolated during the synthesis of 1-arylisoindoles 6 by hydrogenation of o-cyanobenzophenones 7 in the presence of

Facile synthesis of 7-alkyl-1,2,3,4-tetrahydro-1,8-naphthyridines as arginine mimetics using a Horner–Wadsworth–Emmons-based approach

• Rhys A. Lippa,
• John A. Murphy and
• Tim N. Barrett

Beilstein J. Org. Chem. 2020, 16, 1617–1626, doi:10.3762/bjoc.16.134

• tetrahydronaphthyridines predominantly revolve around late-stage hydrogenation of fully aromatic 1,8-naphthyridine derivatives 3, usually prepared via an acid or base-catalysed Friedländer reaction between 2-aminonicotinaldehyde (1) and the corresponding ketone 2 (Scheme 1). Both reactions employ harsh conditions with

• limited functional group tolerance and limited regiochemical control, which presents considerable purification issues during large-scale synthesis [8][9][10]. More recently, catalytic methodologies for the asymmetric hydrogenation of 1,8-naphythyridines have been reported [11][12]. Recently

• . This represents a 64% overall yield which was increased to 68% when no column chromatography was undertaken between transformations, with no loss of purity (Scheme 5). Olefin reduction and Cbz deprotection could not be performed simultaneously by palladium-catalysed hydrogenation as this resulted in

An overview on disulfide-catalyzed and -cocatalyzed photoreactions

• Yeersen Patehebieke

Beilstein J. Org. Chem. 2020, 16, 1418–1435, doi:10.3762/bjoc.16.118

• subsequent SET from the radical 60 to the thiyl radical yields the allylic cation 61 and a thiolate anion. The following proton abstraction by this thiolate anion from the intermediate 62 gives the enone 63 and thiophenol to complete the oxidation. In the hydrogenation step, the addition of a thiyl radical

Recent synthesis of thietanes

• Jiaxi Xu

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

Synthesis of esters of diaminotruxillic bis-amino acids by Pd-mediated photocycloaddition of analogs of the Kaede protein chromophore

• Esteban P. Urriolabeitia,
• Pablo Sánchez,
• Alexandra Pop,
• Cristian Silvestru,
• Eduardo Laga,
• Ana I. Jiménez and
• Carlos Cativiela

Beilstein J. Org. Chem. 2020, 16, 1111–1123, doi:10.3762/bjoc.16.98

• this lack of reactivity. Release of the 1,3-truxillic derivative by methoxycarbonylation The last step to achieve the synthesis of the 1,3-diaminotruxillic targets was the release of the cyclobutane from the Pd2(O2CCF3)2 template. We previously reported that hydrogenation and halogenation were adequate

• necessary in order to obtain a clean release of the truxillic esters. In addition to the methoxycarbonylation of the Pd–C, the reaction also involves ring opening of the oxazolone moiety to afford the corresponding ester and amido groups. This ring opening was also observed in the case of the hydrogenation

Fluorinated phenylalanines: synthesis and pharmaceutical applications

• Laila F. Awad and
• Mohammed Salah Ayoup

Beilstein J. Org. Chem. 2020, 16, 1022–1050, doi:10.3762/bjoc.16.91

• acetic anhydride to give the azalactone 56. The subsequent basic hydrolysis of 56 gave 57 that, on catalytic hydrogenation, afforded racemic difluorinated Phe 58. The isomers were separated by selective hydrolysis using a protease from Bacillius sp to generate the (S)-N-acetyl acid 59 with >99.5% ee and

• -catalyzed asymmetric hydrogenation of the α-amidocinnamic acid 63 using the less frequently used ferrocene-based ligand Me-BoPhoz led to the N-acetyl-ʟ-phenylalanine derivative 64 with complete conversion and with 94% ee. The desired enantiomer (S)-65 was obtained as a single isomer (>99% ee) after

• )-2,5-difluorophenylalanine derivative 115 was carried out by coupling the commercially available aldehyde 55 and N-Boc phosphonate glycinate 112 to generate the enamino ester intermediate 113. The asymmetric hydrogenation of this enamine afforded the N-Boc-protected (R)-2,5-difluorophenylalanine ester

Synthesis of new asparagine-based glycopeptides for future scanning tunneling microscopy investigations

• Laura Sršan and
• Thomas Ziegler

Beilstein J. Org. Chem. 2020, 16, 888–894, doi:10.3762/bjoc.16.80

• glycosylamines 2a–f by hydrogenation with Pd on charcoal in ethyl acetate. Since an anomeric mixture of glycosylamines was obtained in most cases, with a strong predominance of the corresponding β-anomers, and TLC analysis showed no formation of other unwanted side products during hydrogenation, the latter

Combining enyne metathesis with long-established organic transformations: a powerful strategy for the sustainable synthesis of bioactive molecules

• Valerian Dragutan,
• Ileana Dragutan,
• Albert Demonceau and
• Lionel Delaude

Beilstein J. Org. Chem. 2020, 16, 738–755, doi:10.3762/bjoc.16.68

• the total synthesis of the alkaloid (+)-lycoflexine (15). In this strategy, first a protected dienyne precursor was prepared that, by an enyne tandem ring-closing metathesis induced by the Grubbs second-generation Ru catalyst, produced a tricyclic diene in 52% yield. Next, a selective hydrogenation of

Synthesis of disparlure and monachalure enantiomers from 2,3-butanediacetals

• Adam Drop,
• Hubert Wojtasek and
• Bożena Frąckowiak-Wojtasek

Beilstein J. Org. Chem. 2020, 16, 616–620, doi:10.3762/bjoc.16.57

• the pheromone structures was attached giving compound 20 in 74% yield. Next, removal of the protecting group from the secondary alcohol followed by a Swern oxidation gave aldehyde 21 which was subjected to Wittig reactions with either of the two different alkyl derivatives and catalytic hydrogenation

• 25, followed by Swern oxidation. The second Wittig reactions with the longer alkyl derivative and hydrogenation gave compounds 28 and 29. The diols 7 and 8 were then obtained by cleavage of the butanediacetals and were used for the synthesis of pheromones 3 and 4 using the procedure described

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

• employed in diverse organic reactions, including Suzuki reactions [64], Sonogashira reactions [65], transesterifications of triglycerides [66], hydrogenation reactions [67], N-heterocycle syntheses [68], cleavage of propargyl phenol ethers [69], etc. [70][71][72][73][74][75]. In this review article, we

• delivery [93], and cancer detection [94]. In this regard, various functionalized MNPs were employed in diverse organic reactions, including Suzuki–Miyaura reactions, Sonogashira reactions, Ullmann coupling, hydrogenation reactions, oxidation reactions, hydroformylation reactions, and “click” reactions [89

KOt-Bu-promoted selective ring-opening N-alkylation of 2-oxazolines to access 2-aminoethyl acetates and N-substituted thiazolidinones

• Qiao Lin,
• Shiling Zhang and
• Bin Li

Beilstein J. Org. Chem. 2020, 16, 492–501, doi:10.3762/bjoc.16.44

• synthesis of β-nitrate ester carboxamides using tert-butyl nitrite as the nitro source and oxygen as the oxidant through the ring opening of 2-oxazolines [9] (Scheme 1a). Kappe reported a two-step continuous-flow synthesis of N-(2-aminoethyl)acylamides through ring opening/hydrogenation of oxazolines with

Synthesis of C-glycosyl phosphonate derivatives of 4-amino-4-deoxy-α-ʟ-arabinose

• Lukáš Kerner and
• Paul Kosma

Beilstein J. Org. Chem. 2020, 16, 9–14, doi:10.3762/bjoc.16.2

• α-ʟ-anomeric arabino- and ribo-configured methyl phosphonate esters. In addition, the monomethyl phosphonate glycal intermediates were converted into n-octyl derivatives followed by subsequent selective removal of the methyl phosphonate ester group and hydrogenation to give the octylphosphono

• ppm in compound 9). Full deprotection, including the conversion of the 4-azido group into an amino function, was accomplished by hydrogenation of 9 in the presence of palladium hydroxide in a 1:1 mixture of methanol/acetic acid to deliver the target derivative 11 in 30% yield after final HILIC

• envisaged to be prone to the facile formation of tautomers, which would then lead to different reduction products. Notably, however, the reduction proved to be highly selective, and hence might have involved a fast hydrogen addition from the bottom face of the pyranose ring [37]. After full hydrogenation

Automated glycan assembly of arabinomannan oligosaccharides from Mycobacterium tuberculosis

• Alonso Pardo-Vargas,
• Priya Bharate,
• Martina Delbianco and
• Peter H. Seeberger

Beilstein J. Org. Chem. 2019, 15, 2936–2940, doi:10.3762/bjoc.15.288

• during hydrogenation, giving a complex mixture of deletion sequences lacking one to six arabinose moieties. To overcome this challenge, hydrogenolysis with Pd(OH)2 was performed to access the fully deprotected arabinomannosides 13–15 (Figure 2). Conclusion A collection of AM oligosaccharides containing α

Chemical tuning of photoswitchable azobenzenes: a photopharmacological case study using nicotinic transmission

• Lorenzo Sansalone,
• Jun Zhao,
• Matthew T. Richers and
• Graham C. R. Ellis-Davies

Beilstein J. Org. Chem. 2019, 15, 2812–2821, doi:10.3762/bjoc.15.274

• catalytic hydrogenation to 4 followed by protection with TBDMS to give 5 in 63% yield for three steps. The synthesis of the other half of the photochrome started with bromination of difluorinated aniline to give 6 followed by copper-catalyzed cyanation to 7 in 62% overall yield. Diazonization of 7 with

A review of asymmetric synthetic organic electrochemistry and electrocatalysis: concepts, applications, recent developments and future directions

• Munmun Ghosh,
• Valmik S. Shinde and
• Magnus Rueping

Beilstein J. Org. Chem. 2019, 15, 2710–2746, doi:10.3762/bjoc.15.264

• asymmetric hydrogenation of ketones [22]. They showed that upon reduction with Raney nickel powder electrodes modified with (R,R)-(+)-tartaric acid, 2-hexanone 3 was converted to (S)-(+)-2-hexanol 4 with an average optical purity of 4%, whereas Raney nickel powder electrodes modified with (S,S)-(−)-tartaric

• catalyze the enantioselective hydrogenation of prochiral ketones 18. The prochiral ketones such as acetophenone, 1-tetralone and 1-indanone were reduced to their corresponding alcohols 20a, 20b and 20c, respectively, with moderate optical yields, with formation of (S) as major enantiomer (Scheme 5). After

• electrocatalytic hydrogenation of α-keto esters 12 to afford corresponding hydroxy esters 13b and 13c with appreciable enantioselectivities (Scheme 6). Following the pioneering works by Grimshaw et al. [28] in 1973, Gileadi and co-workers showed that the addition of quinidine or related alkaloids to the reaction

Chemical synthesis of the pentasaccharide repeating unit of the O-specific polysaccharide from Escherichia coli O132 in the form of its 2-aminoethyl glycoside

• Debasish Pal and
• Balaram Mukhopadhyay

Beilstein J. Org. Chem. 2019, 15, 2563–2568, doi:10.3762/bjoc.15.249

• -acetylation using NaOMe in MeOH followed by hydrogenolysis in a ThalesNano continuous flow hydrogenation assembly using a 10% Pd-C cartridge [29]. After three cycles of hydrogenation, formation of the target pentasaccharide 1 was evident from the mass spectrum (Scheme 4). Conclusion In conclusion, the

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

• has occasionally led to a mixture of isomers or even the Z-isomer as the predominant one [22]. Hydrogenation of 10a led to saturation of the double bond as well as concomitant removal of the O-benzyl group leading to SAHA (1) in an acceptable overall yield of 61% over three steps. On the other hand

Chiral terpene auxiliaries V: Synthesis of new chiral γ-hydroxyphosphine oxides derived from α-pinene

• Anna Kmieciak and
• Marek P. Krzemiński

Beilstein J. Org. Chem. 2019, 15, 2493–2499, doi:10.3762/bjoc.15.242

• ligands that were obtained from readily available natural (1S)-β-pinene and (1S)-α-pinene [18]. We applied these ligands for the formation of the ruthenium complexes, which were successfully used as catalysts in asymmetric transfer hydrogenation of prochiral ketones. In continuation of our studies on the

• -workers synthesized diphosphines with a pinane framework [19]. Results and Discussion Synthesis of allylic alcohols In the first step, commercially available natural (1R)-α-pinene (1) was oxidized with lead(IV) acetate to produce (+)-verbenone (2) in 58% yield (Scheme 1) [20]. Hydrogenation of 2 with