Recent developments in the asymmetric Reformatsky-type reaction

• Hélène Pellissier

Beilstein J. Org. Chem. 2018, 14, 325–344, doi:10.3762/bjoc.14.21

• to prepare these products. For example, this methodology was employed in 2014 by Kawanishi and Yamakoshi to develop the first total synthesis of naturally occurring prunustatin A, a novel inhibitor of glucose-regulated protein 78 expression [17]. As shown in Scheme 2, the key step of the synthesis

• under mild and neutral conditions. Among them, many syntheses of naturally occurring products have been described for the first time, such as those of the glucose-regulated protein 78 expression inhibitor agent prunustatin A, the antiproliferative agent apratoxin E and its C30 epimer, prebiscibactin

Aminosugar-based immunomodulator lipid A: synthetic approaches

• Alla Zamyatina

Beilstein J. Org. Chem. 2018, 14, 25–53, doi:10.3762/bjoc.14.3

• elegant solution consisted in the application of glucose attached at position 6’ via a glutaryl group as a long-chain hydrophilic linker in combination with biotin or the hydrophilic fluorescent label AlexaFluor. The appropriately protected tetraacylated disaccharide 19 was subjected to treatment with Zn

• -catalysed phosphitylation of the 4’-OH group with N,N-diethylaminophosphepane followed by oxidation of the intermediate phosphite with m-CPBA to furnish the corresponding phosphate, and subsequent deprotection of the 6’-O-TBDMS ether gave the hexaacylated phosphotriester 21. The glutaryl-glucose linker

• (prepared from O-benzyl-protected glucose and glutaric anhydride) was introduced at the free 6’-OH group using DCC and DMAP to give 22. The anomeric allyl group was cleaved by standard procedure, the phosphorylation of the 1-OH group was performed by 1-O-lithiation and subsequent treatment with tetrabenzyl

Synthesis and supramolecular properties of regioisomers of mononaphthylallyl derivatives of γ-cyclodextrin

• Markéta Bláhová,
• Sergey K. Filippov,
• Lubomír Kováčik,
• Jiří Horský,
• Simona Hybelbauerová,
• Zdenka Syrová,
• Tomáš Křížek and
• Jindřich Jindřich

Beilstein J. Org. Chem. 2017, 13, 2509–2520, doi:10.3762/bjoc.13.248

• 6, 7 or 8 glucose units, respectively. Both chemically modified and native CDs are used in numerous applications, e.g., in separation methods [2][3] or in the pharmaceutical industry [4][5]. CDs are well-known as host molecules for various guest substances in aqueous solutions [4]. Derivatives of

• of 6-O-isomers, (ii) the spacer of the 6-O-isomer is elongated by a CH2 group of glucose unit. The details of differences in behavior in water could not be fully assessed due to the low solubility of the 6-O-regioisomer. In fact, the low solubility of the 6-O-regioisomer is the most striking

Herpetopanone, a diterpene from Herpetosiphon aurantiacus discovered by isotope labeling

• Xinli Pan,
• Nicole Domin,
• Sebastian Schieferdecker,
• Hirokazu Kage,
• Martin Roth and
• Markus Nett

Beilstein J. Org. Chem. 2017, 13, 2458–2465, doi:10.3762/bjoc.13.242

• . aurantiacus 114-95T, we fed the strain with 13C-labeled glucose and, subsequently, searched for characteristic mass shifts in its metabolome. This approach led to the discovery of a new natural product, of which the isotope pattern is indicative for a diterpene originating from the methylerythritol phosphate

• terpenoids in their natural bacterial hosts, which is based on the feeding of isotopically labeled glucose. The linear oligoprenyl units, which constitute the carbon backbones of terpenoids, arise from the condensation of activated isoprene units, namely isopentenyl diphosphate (IPP) and dimethylallyl

• diphosphate (DMAPP). The latter two precursors are synthesized by either the mevalonate (MEV) or methylerythritol phosphate (MEP) pathway [7]. Both the MEV and MEP pathway branch from glycolysis. Depending on the respective route, the metabolism of singly labeled glucose gives rise to a characteristic carbon

Diosgenyl 2-amino-2-deoxy-β-D-galactopyranoside: synthesis, derivatives and antimicrobial activity

• Henryk Myszka,
• Patrycja Sokołowska,
• Agnieszka Cieślińska,
• Andrzej Nowacki,
• Maciej Jaśkiewicz,
• Wojciech Kamysz and
• Beata Liberek

Beilstein J. Org. Chem. 2017, 13, 2310–2315, doi:10.3762/bjoc.13.227

• , particularly antifungal [3][4][5][6] and antitumor [7][8][9]. The aglycone part of a saponin is termed sapogenin. Diosgenin, yamogenin, tigogenin, smilagenin and sarsapogenin are the most abundant sapogenins in nature [10]. They are linked via a glycosidic bond to a sugar unit, mainly D-glucose. Diosgenyl

Curcuminoid–BF₂ complexes: Synthesis, fluorescence and optimization of BF₂ group cleavage

• Henning Weiss,
• Jeannine Reichel,
• Helmar Görls,
• Kilian Rolf Anton Schneider,
• Mathias Micheel,
• Michael Pröhl,
• Michael Gottschaldt,
• Benjamin Dietzek and
• Wolfgang Weigand

Beilstein J. Org. Chem. 2017, 13, 2264–2272, doi:10.3762/bjoc.13.223

• ongoing research to increase the selectivity of antitumor active metal complexes [17][18][19][20][21][22], our focus was on the synthesis of curcuminoids that could serve as building blocks to attach sugars like D-fructose or D-glucose [23]. Due to the easy accessibility to azido sugars [24][25] we

Superstructures with cyclodextrins: Chemistry and applications IV

• Gerhard Wenz

Beilstein J. Org. Chem. 2017, 13, 2157–2159, doi:10.3762/bjoc.13.215

• repulsive. The first examples of superstructures formed by attractive intermolecular forces were complexes of crown ethers [1], cryptands [2] and spherands [3], which were recognized by the 1987 Nobel Prize in Chemistry. In addition, inclusion compounds of cyclodextrins (CDs), cyclic oligomers of glucose

Solid-state studies and antioxidant properties of the γ-cyclodextrin·fisetin inclusion compound

• Joana M. Pais,
• Maria João Barroca,
• Maria Paula M. Marques,
• Filipe A. Almeida Paz and
• Susana S. Braga

Beilstein J. Org. Chem. 2017, 13, 2138–2145, doi:10.3762/bjoc.13.212

• are liposome derivatives) [20], and cyclodextrin inclusion complexes [21][22][23]. Cyclodextrins (CDs) are naturally occurring cyclic oligosaccharides produced by bacterial degradation of starch. Native CDs have six to eight α-D-glucose units linked by α-1,4 bonds, being called α-, β- and γ-CDs

• include them. Having one glucose unit less, the cavity of β-CD is narrower and therefore the tilted structure of a flavonoid does not fit and one of the rings of the guest is positioned outside the cavity. This geometry was recently demonstrated for epigallocatechin, which has the same molecular backbone

Enzymatic separation of epimeric 4-C-hydroxymethylated furanosugars: Synthesis of bicyclic nucleosides

• Neha Rana,
• Manish Kumar,
• Vinod Khatri,
• Jyotirmoy Maity and
• Ashok K. Prasad

Beilstein J. Org. Chem. 2017, 13, 2078–2086, doi:10.3762/bjoc.13.205

• Neha Rana Manish Kumar Vinod Khatri Jyotirmoy Maity Ashok K. Prasad Bioorganic Laboratory, Department of Chemistry, University of Delhi, Delhi-110 007, India; Phone: 00-91-11-27662486 10.3762/bjoc.13.205 Abstract Conversion of D-glucose to 4-C-hydroxymethyl-1,2-O-isopropylidene-α-D-ribofuranose

• ribo-trihydroxy sugar derivative starting from diacetone-D-glucose led to the formation of an inseparable 1:1 mixture of the required compound and its C-3 epimer, i.e., 4-C-hydroxymethyl-1,2-O-isopropylidene-α-D-xylofuranose [10]. Lipases have been used extensively for the selective manipulation of

• -isopropylidene-α-D-ribofuranose (3a) can be obtained from D-glucose via diacetonylation followed by selective deprotection of 5,6-isopropylidene protection, sodium periodate oxidation of the vicinal diol and mixed aldol–Cannizaro reaction on the resulted aldehyde 2. However, this methodology always leads to the

Intramolecular glycosylation

• Xiao G. Jia and
• Alexei V. Demchenko

Beilstein J. Org. Chem. 2017, 13, 2028–2048, doi:10.3762/bjoc.13.201

• was glycosylated in the presence of NIS/TfOH to afford tetrasaccharide 32 in 78% as a pure β-diastereomer [70]. Schmidt demonstrated the usefulness of xylylene tethers in application to the iterative synthesis of maltotriose [70]. In this application, the xylylene tether was used to link two glucose

1,3-Dibromo-5,5-dimethylhydantoin as promoter for glycosylations using thioglycosides

• Fei-Fei Xu,
• Claney L. Pereira and
• Peter H. Seeberger

Beilstein J. Org. Chem. 2017, 13, 1994–1998, doi:10.3762/bjoc.13.195

• thioglycosides. Results and Discussion Initially, the capability of DBDMH to activate thioglycoside 1 [32] in order to glycosylate the primary hydroxy group present in D-glucose acceptor 2 [33] was explored without any additives (Table 1, entry 1). This initial experiment furnished disaccharide 3, albeit in

• investigated by using a variety of glycosyl donors 4–10 [34][35][36][37][38] containing C-2 participating groups to ensure 1,2-trans-glycoside formation (Table 2). Each glycosylating agent was reacted with D-glucose acceptors 2 (Table 2, entries 1–8) and 11 [39] (Table 2, entries 9–16) with a free hydroxy

Enzymatic synthesis of glycosides: from natural O- and N-glycosides to rare C- and S-glycosides

• Jihen Ati,
• Pierre Lafite and
• Richard Daniellou

Beilstein J. Org. Chem. 2017, 13, 1857–1865, doi:10.3762/bjoc.13.180

• aggression. Their biosynthetic pathway requires the action of a S-GT (UGT74B1) that catalyses the reaction between a thiohydroximate acceptor and UDP-α-D-glucose as sugar donor to yield the corresponding desulfoglucosinolate (Figure 2) [20][21]. UGT74B1 from A. thaliana is a versatile enzyme in terms of

• ][25], and thurandacin [26] revealed S-glycosylation of cysteines. Carbohydrates bound to these bacteriocins are glucose or N-acetylglucosamine. For two of these glycopeptides, the corresponding S-GTs have been characterized and their versatility for a wide range of sugar donors has been tested [26][27

• reported O-GT to catalyse S-glycosylation on thiol acceptors [30]. Genetic engineering of this enzyme has also led to S-GT activities on several thiols. UGT73AE1 from Carthamus tinctorius was able to transfer glucose on a wide range of acceptors, including a S-containing compound, dichlorothiophenol [31

The chemistry and biology of mycolactones

• Matthias Gehringer and
• Karl-Heinz Altmann

Beilstein J. Org. Chem. 2017, 13, 1596–1660, doi:10.3762/bjoc.13.159

A new member of the fusaricidin family – structure elucidation and synthesis of fusaricidin E

• Marcel Reimann,
• Louis P. Sandjo,
• Luis Antelo,
• Eckhard Thines,
• Isabella Siepe and
• Till Opatz

Beilstein J. Org. Chem. 2017, 13, 1430–1438, doi:10.3762/bjoc.13.140

• agar plates containing GYM medium (10 g/L glucose, 4 g/L yeast extract, 10 g/L malt extract; pH 5.5, adjusted before autoclaving) and 20 g/L agar. The submerged cultivation was carried out for 10 to 20 days at room temperature. For maintenance, agar slants containing the same medium were used and

Strategies toward protecting group-free glycosylation through selective activation of the anomeric center

• A. Michael Downey and
• Michal Hocek

Beilstein J. Org. Chem. 2017, 13, 1239–1279, doi:10.3762/bjoc.13.123

• aldehyde or ketone) making this center more electrophilic (Scheme 1) [3]. Secondly, the pKa value of the anomeric OH group (glucose pKa ≈ 12.5 [9] or 14 [10]) is several orders of magnitude lower than for the other hydroxy groups (pKa ≈ 16–18) [9][10] so a careful selection of the base should allow for the

• -glucose in the presence of HCl to provide the methyl glycoside (pathway a, Scheme 6). The reaction proceeds chemoselective at the anomeric position. More recent examples typically use Lewis acids [29][30][31][32][33][34] or microwave irradiation [35][36] to accelerate the reaction. However, shortcomings

• from β-D-glucose pentaacetate, α-fluoro-D-glucose can be obtained with the key fluorination effected by using Olah’s reagent. The appeal of this procedure is obvious. It is an operationally simple and stereo- and regioselective method to obtain tri- and oligosaccharides containing a sucrose moiety

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

• . As the prepared porous polymer SugPOP-1 is based on hemiacetal glucose, Ag nanoparticles (AgNPs) can be successfully incorporated into the polymer by an in situ chemical reduction of freshly prepared Tollens’ reagent. The obtained AgNPs/SugPOP-1 composite demonstrates good catalytic activity in the

• porous polymer SugPOP-1 is based on hemiacetal glucose, it was further postfunctionalized to embed the AgNPs into the material using an in situ chemical reduction of the freshly prepared Tollens’ reagent. The related catalytic reduction by the AgNPs/SugPOP-1 composite was also explored at room

• porous polymers containing a hemiacetal glucose motif (SugPOP-1), AgNPs were smoothly embedded into the material by chemical reduction of freshly prepared Tollens’ reagent, allowing in situ formation of AgNPs in the polymer matrix. With a high porosity and micro-/mesoporous features, the AgNP-loaded

Kinetic analysis of mechanoradical formation during the mechanolysis of dextran and glycogen

• Naoki Doi,
• Yasushi Sasai,
• Yukinori Yamauchi,
• Tetsuo Adachi,
• Masayuki Kuzuya and
• Shin-ichi Kondo

Beilstein J. Org. Chem. 2017, 13, 1174–1183, doi:10.3762/bjoc.13.116

• , Japan 10.3762/bjoc.13.116 Abstract A detailed electron spin resonance (ESR) analysis of mechanically induced free radicals (mechanoradicals) formation of glucose-based polysaccharides, dextran (Dx) and glycogen (Gly) was performed in comparison with amylose mechanoradicals. The ESR spectra of the

• initiate the polymerization is frequently used to synthesize such a graft polymer [7]. Dextran (Dx), a biodegradable polysaccharide, has been utilized as a graft copolymer backbone. The glycosidic linkages between the α-glucose units of Dx synthesized from Leuconostoc mesenteroides are composed of

• mechanoradical formation from Dx and Gly at room temperature in detail. To obtain fundamental insights into the mechanolysis of Dx and Gly, we conducted detailed ESR spectra analyses of the Dx and Gly mechanoradicals in comparison with those of amylose. Because amylose is an α-glucose-based polysaccharide and

Glycoscience@Synchrotron: Synchrotron radiation applied to structural glycoscience

• Serge Pérez and
• Daniele de Sanctis

Beilstein J. Org. Chem. 2017, 13, 1145–1167, doi:10.3762/bjoc.13.114

• considered a significant contribution to the field. A major breakthrough occurred in 1951, when Bijvoet confirmed, without ambiguity, the D-configuration of glucose, which had been assigned from indirect reasoning by Emil Fischer in 1891 [10]. At the present time, the Cambridge Structural Database contains a

• transport proteins GLUTs are responsible for the diffusion of glucose, galactose, fructose, urate, myoinositol, and dehydroascorbic acid. SGLTs are sodium-glucose symporters that couple the transport of glucose to sodium ions. SWEETs have been characterized the most recently. Major carbohydrate transporters

An eco-compatible strategy for the diversity-oriented synthesis of macrocycles exploiting carbohydrate-derived building blocks

• Sushil K. Maurya and
• Rohit Rana

Beilstein J. Org. Chem. 2017, 13, 1106–1118, doi:10.3762/bjoc.13.110

• sequence of protection-deprotection-functionalization reactions at appropriate position (Figure 1). D-glucose, D-xylose and L-arabinose were used as the key starting materials for the DOS protocol. It was expected that each given sugar building block (generated in the building phase of the DOS) could be

• propargyl ether on the secondary OH group (1c). We have observed relatively low yields (3e and 3f) when we used a combination of glucose (1e and 2c) and xylose (1b and 2a) derived building block whereas an excellent yield was obtained (3g and 3h) when both coupling partners were derived from glucose (1e, 1d

• ), except when both building blocks contain a secondary azide and a secondary propargyl ether group (3c). Cycloaddition of building blocks derived from glucose and xylose worked better with non-protected OH groups (3i, 3j and 3k) than with protected (3e and 3f). Whereas glucose–glucose did work better with

A concise and practical stereoselective synthesis of ipragliflozin L-proline

• Shuai Ma,
• Zhenren Liu,
• Jing Pan,
• Shunli Zhang and
• Weicheng Zhou

Beilstein J. Org. Chem. 2017, 13, 1064–1070, doi:10.3762/bjoc.13.105

• Sodium-glucose co-transporter 2 (SGLT2) inhibitors are a new class of antidiabetes drugs, and dapagliflozin [1], canagliflozin [2], empagliflozin [3], ipragliflozin [4], tofogliflozin [5], luseogliflozin [6] have been approved for the treatment of Type 2 diabetes mellitus (T2DM). One of them

Cycloheximide congeners produced by Streptomyces sp. SC0581 and photoinduced interconversion between (E)- and (Z)-2,3-dehydroanhydrocycloheximides

• Li Yang,
• Ping Wu,
• Jinghua Xue,
• Huitong Tan,
• Zheng Zhang and
• Xiaoyi Wei

Beilstein J. Org. Chem. 2017, 13, 1039–1049, doi:10.3762/bjoc.13.103

• grown on the PDA medium at 28 °C for 10 days and 6 pieces of PDA culture plugs of the strain were inoculated into each of two 500 mL Erlenmeyer flasks containing 150 mL of seed medium (glucose 0.4%, malt extract 1.0%, yeast extract 0.4%, pH 5.5) and shaken on a rotatory (150 rpm) at 28 °C for 2 days

Glyco-gold nanoparticles: synthesis and applications

• Federica Compostella,
• Olimpia Pitirollo,
• Alessandro Silvestri and
• Laura Polito

Beilstein J. Org. Chem. 2017, 13, 1008–1021, doi:10.3762/bjoc.13.100

• the “thiol for thiol” ligand exchange method, which allows the superficial diversification by introducing small amounts of different ligands after the AuNP synthesis [11][12][18]. Recently, the Seeberger group reported a straightforward one-pot method to prepare glucose-stabilized ultrasmall AuNPs, by

• [69][70][71]. Moya and co-workers deeply studied the intracellular dynamics and aggregation of glucose-AuNPs by employing fluorescence correlation spectroscopy (FCS) [12]. They demonstrated that GAuNPs were ubiquitous distributed inside the cell as single NP or small aggregates, suggesting a strong

• binding properties of the glucose moiety displayed on a metal surface with insulin, a peptide hormone [86]. By means of a UV–vis spectroscopy assay, the authors confirmed the successful use of dextran-coated AuNPs to selectively bind low concentrations of insulin (at 1 pM), even in serum samples, and

Synthesis of D-manno-heptulose via a cascade aldol/hemiketalization reaction

• Yan Chen,
• Xiaoman Wang,
• Junchang Wang and
• You Yang

Beilstein J. Org. Chem. 2017, 13, 795–799, doi:10.3762/bjoc.13.79

• ; Introduction D-manno-Heptulose is a rare naturally occurring seven-carbon sugar first isolated from avocado [1], which exhibited promising diabetogenic effects through suppression of the glucose metabolism and insulin secretion via competitive inhibition of the glucokinase pathway [2][3][4][5][6]. Accordingly

Cyclodextrins tethered with oligolactides – green synthesis and structural assessment

• Cristian Peptu,
• Mihaela Balan-Porcarasu,
• Alena Šišková,
• Ľudovít Škultéty and
• Jaroslav Mosnáček

Beilstein J. Org. Chem. 2017, 13, 779–792, doi:10.3762/bjoc.13.77

• of the esterified CDs was supported in Harada’s work [17] by comparing the NMR spectra with those obtained for a monoesterified β-cyclodextrin at C2 position (mono-2-O-(6-benzyloxypentanoyl)-β-cyclodextrin). The peak at 63.4 ppm was assigned as C2’ of the monosubstituted glucose ring belonging to

Membrane properties of hydroxycholesterols related to the brain cholesterol metabolism

• Malte Hilsch,
• Ivan Haralampiev,
• Peter Müller,
• Daniel Huster and
• Holger A. Scheidt

Beilstein J. Org. Chem. 2017, 13, 720–727, doi:10.3762/bjoc.13.71

• iXon 888 EMCCD camera (1024 × 1024 pixels, Andor, Belfast, Northern Ireland) were used. N-Rh-DOPE was excited by a 561 nm diode laser. Fife µL GUVs were mixed with 15 µL 250 mM glucose buffer (5.8 mM NaH2PO4, 5.8 mM Na2HPO4, osmolarity of 300 mOsm/kg, pH 7.2) in tissue culture treated microscopy