bluuebunny/crossref_metadata_2025_split huggingface dataset:
Sulfonation of 1, 2‐(methylenedioxy)benzene, 1, 2‐(ethylenedioxy)benzene, 2‐methylanisole, 2, 3‐dihydrobenzofuran, chromane, benzo‐15‐crown‐5 and dibenzo‐30‐crown‐10 in concentrated sulfuric acid and with sulfur trioxide
Authors: Ansink Harold R. W. , Cerfontain Hans 
Published: September 2010

AbstractThe sulfonation of 1, 2‐(methylenedioxy)benzene (2), 1,2‐(ethylenedioxy)benzene (3), benzo‐15‐crown‐5 (4), 2‐methylanisole (5), 2,3‐dihydrobenzofuran (7), 2, 3‐dihydrobenzopyran (chromane, 8) and dibenzo‐30‐crown‐10 (9) in concentrated sulfuric acid and with sulfur trioxide mainly in nitromethane has been studied. Upon dissolution in sulfuric acid, 3 yields a mixture of 3‐3‐sulfonic acid (3‐3‐S) and 3–4‐S in a ratio of 0.8, independent of the H2SO4 concentration. In sulfuric acid with a concentration greater than 83% H2SO4, the two monosulfonic acids both eventually yield 3‐3,5‐S2. The ratio of rate coefficients of sulfonation of 3‐3‐S and 3‐4‐S is approximately 70. The reaction of the crown ethers 4 and 9 in sulfuric acid leads to formation of 4‐4‐S and to an equimolar mixture of 9‐4,4′‐S2 and 9‐4,5′‐S2, respectively.Sulfonation of 5 in 85 and 98% H2SO4 yields a mixture of 5–4‐S and 5‐5‐S in a ratio of approximately 7:1 and 11:1, respectively; in 98% H2SO4, these products are converted into 5‐4,6‐S2 and 5‐3,5‐S2, respectively. On dissolving 5 in 105% H2SO4, the initially observed product is 5–4,6‐S2, which exhibits O demethylation.Sulfonation of both 7 and 8 in 85% H2SO4 yields a mixture of 4‐S and 6‐S in an initial ratio of 1.4. These acids eventually yield 7‐4,6‐S2 and 8‐4,6‐S2. The rate coefficients of sulfonation of 7‐6‐S and 8‐6‐S are both approximately 50 times those of the corresponding 4‐sulfonic acid isomers. Upon sulfonation with 1.0 equiv of SO3 in nitromethane, all the substrates studied yield the corresponding 4‐sulfonic acid. Upon reaction with 2.0‐4.0 equiv of SO3, 2, 3, 7 and 8 all yield the 4,6‐S2 almost quantitatively; 4 does not yield any disulfonic acid. Reaction of 9 with ≥2.0 equiv of SO3 yields a 1:1 mixture of 4,4′‐S2 and 4,5′‐S2.The routes of the sulfonation of 1,2‐(methylenedioxy)‐ (2) and 1, 2‐(ethylenedioxy)benzene (3) and their monosulfonic acids have been compared with those of 1,2‐dimethoxybenzene (1) and its 4‐sulfonic acid and the differences are discussed in terms of the Curtin‐Hammett principle. The differences observed between the mono‐ and disulfonation of 2,3‐dihydroxybenzofuran (7) and 2,3‐dihydrobenzopyran (8) on the one hand and those of 2‐methylanisole (5) on the other are discussed along similar lines.
Glucose 1‐phosphate oxidation on platinum‐on‐carbon catalysts: Side‐reactions and effects of catalyst structure on selectivity (Pt/C oxidation catalysts, part 7)
Authors: van Dam H. E. , Kieboom A. P. G. , van Bekkum H. 
Published: September 2010

AbstractThe selectivity aspects of the platinum‐catalyzed oxidation of glucose 1‐phosphate into glucuronic acid 1‐phosphate have been studied. A partial loss of starting material occurs through side‐reactions starting with oxidation of secondary hydroxyl groups, followed by CC bond cleavage. The ring‐CHOH oxidation is retarded by the substituent at C(5); its protecting ability follows the order COO− > CH2OH > H. The maximum selectivity (∼ 70%) is independent of the usual reaction variables (e.g. pH, metal dispersion), but can be increased upto 85% by an oxidative pretreatment of the activated carbon used as catalyst carrier.
A structural study of phosphate‐methylated d(CpG)n and d(GpC)n DNA oligomers. Implications of phosphate shielding for the isomerisation of B‐DNA into Z‐DNA
Authors: Quaedflieg Peter J. L. M. , Koole Leo H. , van Genderen Marcel H. P. , Buck Henk M. 
Published: September 2010

AbstractIt is shown that the phosphate‐methylated DNA miniduplex d(CpG)2 adopts a left‐handed Z‐type structure, whereas the phosphate‐methylated miniduplex d(GpC)2 is right‐handed. Furthermore, it is shown that elongation of the systems to the tetramer level results in right‐handed duplexes with rather low stability. The phosphate‐methylated hexamer d(CpGpCpGpCpG) is present in the single‐strand form. It is suggested that these results are of interest in the understanding of the exact role of salt cations in stabilizing the Z‐DNA structure of natural duplexes d(CpG…CpG)2 in high salt solution, since the methylated phosphate groups in fact mimic the situation of complete phosphate‐charge shielding. Therefore, it is concluded that exclusive cation‐phosphate complexation in the d(CpG)2 segments stabilizes the Z structure. 31P‐NMR experiments on the natural duplex d(CpGpCpGpCpG)2 at different concentrations of Mg2+ provided independent proof for the proposed model.
Synthesis of 3‐methyl‐, 4‐methyl‐ and 3,4‐dimethylcyclopenta[cd]pyrenes
Authors: Kellenbach E. R. , Lugtenburg J. , Cornelisse J. 
Published: September 2010

AbstractA convenient synthesis of three cyclopenta[ad]pyrene derivatives methylated on the five‐membered ring is described. The starting materials were easily available ketones which were either Wolff‐Kishner‐reduced or treated with methyllithium followed by dehydration with p‐toluene‐sulfonic acid to give the partially saturated derivatives. Careful aromatization with DDQ gave the novel methylated compounds in reasonable yields.
Substituent effects on the photocycloaddition reactions of anisoles to acrylonitriles
Authors: Al‐Jalal Nader , Gilbert Andrew 
Published: September 2010

AbstractMethyl‐, ethoxy‐, and phenyl‐substituted acrylonitriles undergo efficient 1,2‐photocyclo‐addition to 4‐cyanoanisole, but the azocine formation of the parent addend is inhibited by these groups. The regiochemistry, selectivity and efficiency of the cycloaddition of acrylonitrile to cyanomethoxyanisoles vary markedly with the position of the arene substituents and reflect competition between the influences of the cyanoanisole and dimethoxybenzene moieties.
Models for the adsorption of dioxygen on metal chelates
Authors: Elzing A. , van der Putten A. , Visscher W. , Barendrecht E. 
Published: September 2010

AbstractMetal chelates are suitable electrocatalysts for the reduction of dioxygen. The selectivity of the reduction process (H2O2 or H2O as end product) depends on which catalyst is used. Comparable compounds, such as cobalt and iron phthalocyanine (CoPc and FePc), show different selectivities. CoPc catalyzes the dioxygen reduction pathway with H2O2 as the end product, whereas FePc gives H2O. The interaction between the catalyst and dioxygen is crucial for the selectivity of the reduction process. In this review, the most important models for the adsorption of dioxygen on metal chelates are discussed.Most of these models predict that dioxygen is adsorbed in a so‐called “end‐on (bent)” configuration on to the metal phthalocyanines. The models also predict that, for the dioxygen adduct of CoPc, the oxygen fragment is more negatively charged than for the adduct of FePc, and that this may be the reason for the observed difference in selectivity. Alternatively, dioxygen can bind in between two metal phthalocyanine molecules. For these dioxygen‐bridged dimers, as can be derived from adsorption (bonding) models, the cleavage of the oxygen‐oxygen bond occurs more easily in the case of the FePc dioxygen dimer than in the corresponding Co complex.
Acid‐catalyzed transfer sulfonation of anisole using overcrowded polymethylbenzenesulfonic acids
Authors: Koeberg‐Telder Ankie , Cerfontain Hans 
Published: September 2010

AbstractTransfer sulfonations of anisole using various polymethylbenzenesulfonic acids (PoMBR's) catalyzed by trifluoromethanesulfonic acid at 25 °C are described. The observed reactivity order for transfer sulfonation increases in the order 2,4‐DiMBS, 2,6‐DiMBS, 2,3,4,5‐TeMBS (all non‐reactive) < 2,3,5,6‐TeMBS ≈︁ 2,4,6‐TrMBS < 2,3,4,6‐TeMBS < PeMBS. This order illustrates that the main factor in determining the transfer sulfonation reactivity is ‐ in addition to the electronic activation by the 4‐methyl ‐ the degree of overcrowding around the sulfonic acid group of the PoMBS. A mechanism is suggested in which the essential step involves the transfer of SO3H+ from the 1‐arenonium‐1‐sulfonic acid ion to the anisole.
On Shustorovich's Bond‐Order conservation method as applied to chemisorption
Authors: van Santen R. A. 
Published: September 2010

AbstractThe Bond‐Order Conservation principle is shown to be rigorously true within the Valence‐Bond approximation excluding ionogenic terms. After a short discussion of Shustorovich's adaptation of this method to chemisorption on metals, a new improved expression for the activation energy of dissociation is derived, based on a transition‐state model derived from Extended Hückel calculations.It appears to be essential to account for the weakening of the surface‐surface metal bonds.New expressions for atomic and molecular adsorption energies are derived.A major result of this work is a significant reduction in the activation energy for dissociation due to loss of surface metal‐metal atom bonding upon chemisorption.
Kinetics and mechanism of the gas‐phase oxidation of styrene to benzaldehyde, acetophenone and trans‐cinnamaldehyde over a heterogeneous surface‐vanadate Wacker catalyst
Authors: van der Heide Evert , Schenk John , Gerritsen Albert W. , Scholten Joseph J. F. 
Published: September 2010

AbstractA study has been made of the kinetics and mechanism of the oxidation of styrene over a heterogeneous vanadate‐monolayer Li2PdCl4 Wacker catalyst in the temperature range 348 K to 453 K at 0.11 MPa total pressure. The kinetics of the reaction, with respect to the dependence of the reaction rate on the partial pressures of styrene and water, as well as on the surface LiCl concentration, appear to be logically related to the kinetics of the homogeneous Wacker process.In addition to acetophenone (initial selectivity 45 mol %), benzaldehyde, probably originating from phenylacetaldehyde, is formed with gradually increasing selectivity (initial selectivity 55 mol %). Formation of benzoic acid can sometimes be detected but in all cases with a selectivity lower than 5 mol %. Initially no other products are detected but, after a short period, trans‐cinnamaldehyde is formed with increasing selectivity (15 mol % after three days).Deactivation of the catalyst is due to carbonaceous deposits and removal of these deposits by oxidation with air at 473 K leads to partial regeneration.
Basket‐shaped hosts with semi‐flexible handles
Authors: Smeets J. W. H. , Visser H. C. , Kaats‐Richters V. E. M. , Nolte R. J. M. 
Published: September 2010

AbstractBasket‐shaped hosts were synthesized starting from the concave building block 4magnified image To this end, oligo(oxyethylene) bridges, containing different aromatic rings, were attached to the 3,6‐ and 3′,6′‐positions of the xylylene rings of 4. These bridges include 5,6‐benzo‐1,4,7,10‐tetraoxadec‐5‐ene, 5,6,7‐benzo‐1,4,8,11‐tetraoxaundeca‐5,6‐diene, 5,6‐(2,3‐naphtho)‐1,4,7,10‐tetraoxa‐dec‐5‐ene, 8,9‐benzo‐1,4,7,10,13,16‐hexaoxahexadec‐8‐ene and 8,9‐(2,3‐naph‐tho)‐1,4,7,10,13,16‐hexaoxahexadec‐8‐ene chains. Alkali‐metal ions and protonated aliphatic or aromatic diamines are bound in these baskets in a 1:1 host/guest ratio. For the metal ions, a clamshel‐llike or a sandwich‐like complex is proposed. Aliphatic diammonium guests are bound in such a way that the methylene chains are wedged in between the o‐xylylene units of the host, as concluded from the upheld shifts observed in the 1H NMR spectra of the guest CH2 protons. Free energies of binding of the new hosts with nineteen guests were measured using the picrate extraction technique. The highest ‐ ΔG° values were obtained for the complexes with the diammonium salts (‐ ΔG° values up to 13.4 kcal/mol).
Cation complexation with functionalized 9‐arylacridinium ions. Part II: Conformational and spectral response upon metal‐ion complexation
Authors: Jonker S. A. , Verhoeven J. W. , Reiss C. A. , Goubitz K. , Heijdenrijk D. 
Published: September 2010

AbstractThe chromoionophoric behaviour of compound 1 in solution was studied in relation to the X‐ray structure of its complexes with Na+, Ba2+ and Ag+. Interaction between the metal ion and the “soft” nitrogen atom, which forms part of the aza crown ether of 1, is concluded to be of crucial importance. It is shown that in solution a soft cation such as Ag+ induces a greater special spectral shift than do hard cations of equal charge and almost the same size, such as Na+ and K+. Solid‐state structures of the Ag+ and Na+ complexes of 1 show a relatively short Ag+ ‐N distance and a relatively long Na+ ‐ N distance.Netherlands Organization for Chemical Research (SON) with financial aid from the Netherlands Organization for Scientific Research (NWO).
Synthesis of specifically deuteriated 9‐ and 13‐demethylretinals
Authors: van den Berg Ellen M. M. , van der Bent Arie , Lugtenburg Johan 
Published: September 2010

Abstract(13–2H) 13‐Demethylretinal, (11,12,13‐2H,) 13‐demethylretinal, (9‐2H)9‐demethylretinal and (9,10‐2H2)9‐demethylretinal were prepared in all‐E, 9Z, 11Z and 13Z isomeric form with high deuterium incorporation. In the synthesis of (9,10‐2H2)9‐demethylretinal, a Horner‐Emmons reaction with deuteriated diethyl (cyanomethyl)phosphonate was used. This synthon was subsequently used for the synthesis of (10‐2H)‐ and (14‐2H)retinal in high yield and with high deuterium incorporation. From the 13C NMR spectra of the demethylretinals (all‐E, 9Z and 13Z), he effect of a methyl group on the 13CNMR parameters of polyene‐chain carbons was determined.
X‐Ray‐excited luminescence of organic gadolinium compounds
Authors: Blasse G. , Brixner L. H. 
Published: September 2010

AbstractThe X‐ray excited emission spectra of gadolinium acetate tetrahydrate, [Gd ⊂ 2.2.1]Cl3·2H2O and Gd[C3F7COCHCOC(CH3)3]3 (or Gd[FOD3), are reported. The first two compounds show strong Gd3+ emission (6P←8S) at room temperature, while the third compound gives rise to strong ligand emission, but only at very low temperature. Eu(FOD)3, however, shows intense Eu3+ emission upon X‐ray excitation. The Gd3+ emission spectra show many vibronic lines and, although their intensity is weak, it is much higher than generally accepted. These vibronic lines indicate which groups coordinate the Gd3+ ion and it is shown that their intensity increase as the ligand polarizability increases.
Rate‐limiting deprotonation of (arylsulfonyl)methyl perchlorates in dichloromethane. Evidence for proton tunneling and the high dynamic basicity of HMPA in a nonaqueous solvent
Authors: van Andel Maarten A. , Engberts Jan B. F. N. 
Published: September 2010

AbstractKinetic data are reported for the water‐catalyzed hydrolysis of several (arylsulfonyl)‐methyl perchlorates in water and for the HMPA‐catalyzed decomposition of the same substrates in dichloromethane. Under both conditions, the reaction exhibits general base catalysis and the covalent perchlorates react via rate‐limiting deprotonation at the α‐sulfonyl methylene moiety. Primary kinetic deuterium isotope effects (KDIE's) in water are indicative for a complete loss of zero‐point energy in the transition state. The high symmetry of the transition state is supported by the Brönsted β value of ca. 0.5.HMPA was found to be an effective general base catalyst in dichloromethane as the solvent. This reaction shows primary KDIE's (kH/kD = 9.3 at 25°C) which are about 1.5 times higher than the (semi)classical limit. In addition, the ratio of the pre‐exponential Arrhenius factors is abnormally small (AH/AD = 0.14). These classically anomalous results are interpreted in terms of a contribution of quantum‐mechanical tunneling to the transition state for HMPA‐induced deprotonation. Possible reasons for the different kinetic characteristics of the deprotonation reaction in the aqueous and nonaqueous medium are given.
Transduction of host‐guest complexation into electronic signals: Favoured complexation of potassium ions by synthetic macrocyclic polyethers using membrane‐modified, ion‐sensitive field‐effect transistors (ISFETs)
Authors: Sudhölter Ernst J. R. , van der Wal Peter D. , Skowronska‐Ptasinska Maria , van den Berg Albert , Reinhoudt David N. , Bergveld Piet 
Published: September 2010

AbstractThe selective complexation of K+ and Na+ salts with a series of synthetic macrocyclic polyethers has been studied on the SiO2 gate surface of an Ion‐Sensitive Field‐Effect Transistor (ISFET). The synthetic macrocycles were incorporated in a PVC membrane directly attached to the SiO2 gate surface. The selectivities were measured either with tetraethylammonium chloride or lithium chloride as background electrolyte or by direct comparison. The slope of the response curves generally shows near‐Nernstian behaviour (53‐56 mV/pK+). Hemispherands 2 and 3, which have molecular cavities composed of 21 ring atoms and 1,3‐dimethyl‐p‐(tert‐butyl)calix[4]arene crown‐5 (11), show high selectivities of K+ over Na+ (log K(K+/Na+)= −2.9 to 3.2). The (substituted) benzo‐27‐crown‐9 derivatives (5‐7) show moderate selectivities (log K(K+/Na+) ≃ −2). The 18‐membered pyrido hemispherand hardly discriminates. Our results correlate well with reported data of picrate extraction experiments and with the relative‐association constants in methanol.
Iodine‐doped “crowned” phthalocyanines
Authors: Sielcken O. E. , Nolte R. J. M. , Schoonman J. 
Published: September 2010

AbstractIn this paper, we describe the effect of iodine doping on the structure and electrical properties of crown‐ether‐substituted phthalocyanines. For the doped phthalocyanines, a layered two‐dimensional structure was found. A.c. impedance spectroscopy revealed that doping strongly increases the bulk electronic conductivity of the “crowned” phthalocyanines and their alkali‐metal picrate complexes. The intermolecular barriers for conductivity were not affected by the iodine dopant.
Orbital control in the reductive cleavage of tris(methoxyphenyl)phosphines
Authors: Budzelaar Peter H. M. , van Doom Johannes A. , Meijboom Nico 
Published: September 2010

AbstractThe character of the LUMO of (methoxyphenyl)phosphines determines the reductive cleavage of the C‐P bond; a high LUMO energy prevents reduction whereas a small coefficient at the C‐P carbon atom leads to a poor cleavage.
Rigid etheno‐bridged metopon analogues from Diels‐Alder reaction of 5‐methylthebaine. (Chemistry of opium alkaloids, Part XXXII)
Authors: Woudenberg R. H. , Lie T. S. , Maat L. 
Published: September 2010

AbstractDiels‐Alder reaction of 5‐methylthebaine (2) with ethyl acrylate, methyl vinyl ketone or p‐benzoquinone yielded ethyl 4,5α‐epoxy‐3,6‐dimethoxy‐5,N‐dimethyl‐6α,14α‐ethenoisomorphinan‐7α‐carboxylate (3), 7α‐acetyl‐4,5α‐epoxy‐3,6‐dimethoxy‐5,N‐dimethyl‐6α,14α‐ethenoisornorphinan (4), and 4,5α‐epoxy‐3,6‐dimethoxy‐5,N‐dimethyl‐6α,14α‐ethenobenzo[7,8]isomorphinan‐3′,6′‐diol (5b), respectively.Both ester 3 and ketone 4 were converted into 4,5α‐epoxy‐3,6‐dimethoxy‐α,α,5,N‐tetramethyl‐6α,14α‐ethenoisomorphinan‐7α‐methanol (7) with methylmagnesium iodide. The 3‐methoxy group was hydrolysed to give 4,5α‐epoxy‐3‐hydroxy‐6‐methoxy‐α,α,5,N‐tetramethyl‐6α,14α‐etheno‐isomorphinan‐7α‐methanol (8). Demethylation of 3 with boron tribromide afforded ethyl 4,5α‐epoxy‐3,6‐dihydroxy‐5,N‐dimethyl‐6α,14α‐ethenoisomorphinan‐7α‐carboxylate (6). Structure elucidation was mainly based on1H and13CNMR spectroscopy. It is remarkable that, in all cases, β‐face approach of the diene system of 2 has taken place. The new rigid metopon analogues 6, 7, and 8, will be tested for biological activity**.magnified image
An overlooked short entry to 2‐ alkyliden‐1,3‐dioxolanes. Highly reactive ketene acetals
Authors: Aben R. W. M. , Scheeren J. W. 
Published: September 2010

Abstract2‐Alkyliden‐1,3‐dioxolanes can be prepared surprisingly easily from the corresponding 2‐bromoacetals by dehydrobromination with potassium tert. butoxide. The method has a wide scope and gives access to ketene acetals which cannot be prepared by other methods. The application of mono substituted cyclic ketone acetals in the lewis acid catalyzed stereoselective formation of cis oxetanes from aldehydes is illustrated.
Sulfonation of norbornene with sulfur trioxide
Authors: Bakker B. H. , Schonk R. M. , Cerfontain H. 
Published: September 2010

AbstractSulfonation of norbornene 1 with the SO3‐dioxane complex affords the β‐sultone 2, which rearranges at room temperature to the γ‐sultone 3. Reaction of 1 with 2 equiv of SO3‐nitromethane yields the carbyl sulfate 4. Carbocations are not involved in the formation of either the β‐sultone or the carbyl sulfate.
The oxygenation of cyclopalladated N,N‐dimethylbenzylamine derivatives with tert‐butyl hydroperoxide
Authors: Alsters Paul L. , Teunissen Herman T. , Boersma Jaap , van Koten Gerard 
Published: September 2010

AbstractCyclopalladated N,N‐dimethylbenzylamine complexes can be oxygenated with tert‐butyl hydroperoxide to the corresponding phenolates in good yield (> 80%); the rate of oxygenation is highly enhanced by increasing the nucleophilicity of the metal center or by addition of a vanadium catalyst.
The effect of pH and temperature on the periodate oxidation of sucrose
Authors: de Wit D. , van Rantwijk F. , Maat L. , Kieboom A. P. G. 
Published: September 2010

AbstractThe oxidation of sucrose with periodate was studied at different pH and temperature. Open‐chain di‐ and tetraaldehydes thus obtained were analyzed using HPLC. The ratio of singly oxidized glucose rings to doubly oxidized glucose rings proved to be dependent on the pH. This behaviour of the glucose ring in sucrose was compared with that of methyl α‐D‐glucopyranoside. At higher temperatures, the direction of the oxidation shifted to the glucose part of sucrose. At 95°C and pH 7, sucrose appeared to be oxidized selectively to the dialdehyde GOO‐F.
Towards a rational design of resolving agents. Part II: Correlation between resolution results and physical properties of diastereomeric salts
Authors: van der Haest A. D. , Wynberg H. , Leusen F. J. J. , Bruggink A. 
Published: September 2010

AbstractSix closely related cyclic phosphoric acids (1a‐f) were compared with respect to their resolving ability towards ephedrine. Variation of the aromatic substituent in the phosphoric acids significantly influences this ability. Studying the results of the resolution experiments as a function of some physico‐chemical properties of the diastereomeric salts reveals a relationship between the resolving ability of a particular phosphoric acid and the difference in heat of fusion of its diastereomeric salts.
Reactions of cyclopalladated compounds and alkynes: New pathways for organic synthesis?
Authors: Pfeffer Michel 
Published: September 2010

AbstractCyclometallated compounds, obtained by direct intramolecular C–H activation of a ligand by transition metals, are fairly reactive [especially those derived from palladium(II)] towards insertion of internal alkynes into their metal‐carbon bond. This reaction leads to either new organometallic compounds by inclusion of one to three alkynes into the M‐C bond, or organic compounds which are either carbocyclic or heterocyclic, their nature depending upon the alkyne substituents as well as upon the cyclometallated ligand.
Analogues of uridine 5′‐diphosphate glucose and guanosine 5′‐diphosphate mannose
Authors: Broxterman H. J. G. , Kooreman P. A. , van den Elst H. , Roelen H. C. P. F. , van der Marel G. A. , van Boom J. H. 
Published: September 2010

AbstractOne‐pot coupling of 2′,3′‐di‐O‐benzoyl‐uridine and 4,5,6,8‐tetra‐O‐acetyl‐3,7‐anhydro‐2‐deoxy‐D‐glycero‐D‐ido‐octitol with appropriate bifunctional phosphoro‐, phosphono‐ and thiophosphonylation reagents gave, after removal of the base‐labile protecting groups, analogues of UDP‐Glc containing charged phosphate, neutral alkyl‐ and arylphosphonate and phosphonothioate linkages. In an analogous manner, GDP‐Man analogues, in which guanosine and octitol units are similarly linked via phosphate, alkyl phosphate or phosphotriester bonds, were prepared.