Synthesis of α,β- and β-Unsaturated Acids and Hydroxy Acids by Tandem Oxidation,Epoxidation, and Hydrolysis/Hydrogenation of Bioethanol Derivatives

We report a reaction platform for the synthesis of three different high-value specialty chemical building blocks starting from bio-ethanol, which might have an important impact in the implementation of biorefineries. First, oxidative dehydrogenation of ethanol to acetaldehyde generates an aldehyde-containing stream active for the production of C₄ aldehydes via base-catalyzed aldol-condensation. Then, the resulting C₄ adduct is selectively converted into crotonic acid via catalytic aerobic oxidation (62 % yield). Using a sequential epoxidation and hydrogenation of crotonic acid leads to 29 % yield of β-hydroxy acid (3-hydroxybutanoic acid). By controlling the pH of the reaction media, it is possible to hydrolyze the oxirane moiety leading to 21 % yield of α,β-dihydroxy acid (2,3-dihydroxybutanoic acid). Crotonic acid, 3-hydroxybutanoic acid, and 2,3-dihydroxybutanoic acid are archetypal specialty chemicals used in the synthesis of polyvinyl-co-unsaturated acids resins, pharmaceutics, and bio-degradable/ -compatible polymers, respectively.     

Novel and Stereospecific Synthesis of (2S)‐3‐(2,4,5‐Trifluorophenyl)propane‐1,2‐diol from D‐Mannitol

A stereospecific synthesis of (2S)‐3‐(2,4,5‐trifluorophenyl)propane‐1,2‐diol from D ‐mannitol has been developed. The reaction of 2,3‐O‐isopropylidene‐D ‐glyceraldehyde with 2,4,5‐trifluorophenylmagnesium bromide gave [(4R)‐2,2‐dimethyl‐1,3‐dioxolan‐4‐yl](2,4,5‐trifluorophenyl)methanol in 65% yield as a mixture of diastereoisomers (1 : 1). The Ph₃P catalyzed reaction of the latter with C₂Cl₆ followed by reduction with Pd/C‐catalyzed hydrogenation gave (2S)‐3‐(2,4,5‐trifluorophenyl)propane‐1,2‐diol with >99% ee and 65% yield.     

Synthesis of ϵ‐Caprolactam from Cyclohexanone Oxime Using Zeolites Hβ, HZSM‐5, and Alumina Pillared Montmorillonite

The Beckmann rearrangement of cyclohexanone oxime (CHO) to ?‐caprolactam (?‐C) was studied in a plug flow reactor at 300–400°C under atmospheric pressure by using Hβ, ZSM‐5, and alumina pillared montmorillonite. With Hβ(X) Y zeolites, raising the SiO₂/Al₂O₃ molar ratio (X) results in the enhancement of catalyst acid strength with concomitant decrease of the total acid amount. In creasing the calcination temperature (Y) causes remarkable diminution of catalyst surface area, acid strength, and acid amount. A similar trend was found for AlPMY catalysts. In there action of CHO, the initial catalytic activity correlates well with the total acid amount of various catalysts except for Hβ(10) Y (Y > 600°C). The reaction proceeds on both Brönsted and Lewis acid sites and the catalyst deactivation most likely occurs at the strong Brönsted acid sites. The effect of solvents in the feed on the catalytic results was also investigated; it was found that polar solvents such as ethanol or n‐butanol give high ?‐C yield and longer catalyst life time. In the reaction of CHO/C₂H₅OH over Hβ(10)800 at 400°C and W/F 74.6 gh/mol, the CHO conversion and ?‐C yield remain 100% and 92%, respectively, for at least 20 h time‐on‐stream. The reaction paths and the mechanism for ?‐C formation are proposed.     

Triterpenoide. XIX. 3β‐Hydroxy‐11‐oxo‐18α‐olean‐12‐en‐28‐säure‐methyl­ester und 3,11‐Dioxo‐18α‐olean‐12‐en‐28‐säure‐methyl­ester

The X‐ray crystal structure analyses of 3β‐hydroxy‐11‐oxo‐18α‐olean‐12‐en‐28‐oic acid methyl ester ethanol solvate, C₃₁H₄₈O₄·C₂H₆O, (I), and 3,11‐dioxo‐18α‐olean‐12‐en‐28‐oic acid methyl ester, C₃₁H₄₆O₄, (II), are described. These two compounds differ only in the structure of ring A. In (I), ring A has a chair conformation, while in (II), it has a twisted boat conformation. In both compounds, ring C has a slightly distorted sofa conformation, rings B, D and E are in chair conformations, and rings D and E are trans‐fused. The asymmetric unit of (I) contains one mol­ecule of ethanol linked by hydrogen bonds with two different mol­ecules of (I).     

Tandem β‐Boration/Arylation of α,β‐Unsaturated Carbonyl Compounds by Using a Single Palladium Complex To Catalyse Both Steps

Diphenyl(3‐methyl‐2‐indolyl)phosphine (C₉H₈NPPh₂, 1 ) gives stable dimeric palladium(II) complexes that contain the phosphine in P,N‐bridging coordination mode. On treating 1 with [Pd(O₂CCH₃)₂], the new complexes [Pd(μ‐C₉H₇NPPh₂)(NCCH₃)]₂ ( 2 ) or [Pd(μ‐C₉H₇NPPh₂)(μ‐O₂CCH₃)]₂ ( 3 ) were isolated, depending on the solvent used, acetonitrile or toluene, respectively. Further reaction of 3 with the ammonium salt of 1 led to the substitution of one carboxylate ligand to afford [Pd(μ‐C₉H₇NPPh₂)₃(μ‐O₂CCH₃)] ( 4 ), in which the bimetallic unit is bonded by three C₉H₇NPPh₂^? moieties and one carboxylate group. Using this methodology, [Pd₂(μ‐C₆H₄PPh₂)₂(μ‐C₉H₇NPPh₂)(μ‐O₂CCX₃)] (X=H ( 7 ); X=F ( 8 )) were synthesised from the ortho‐metalated compounds [Pd(C₆H₄PPh₂)(μ‐O₂CCX₃)]₂ (X=H ( 5 ); X=F ( 6 )). Complexes 3 , 4 , 7 , and 8 have been found to be active in the catalytic β‐boration of α,β‐unsaturated esters and ketones under mild reaction conditions. Hindrance of the carbonyl moiety has an influence on the reaction rate, but quantitative conversion was achieved in many cases. More remarkably, when aryl bromides were added to the reaction media, complex 7 induced a highly successful consecutive β‐boration/cross‐coupling reaction with dimethyl acrylamide as the substrate (99 % conversion, 89 % isolated yield).     

Efficient conversion of fructose to 5‐hydroxymethylfurfural by functionalized γ‐Al2O3 beads

Millimeter size γ‐Al₂O₃ beads were prepared by alginate assisted sol–gel method and grafting organic groups with propyl sulfonic acid and alkyl groups as functionalized γ‐Al₂O₃ bead catalysts for fructose dehydration to 5‐hydroxymethylfurfural (5‐HMF). Experiment results showed that the porous structure of γ‐Al₂O₃ beads was favorable to the loading and dispersion of active components, and had an obvious effect on the properties of the catalyst. The lower calcination temperature of γ‐Al₂O₃ beads increased the specific surface area, the hydrophobicity and the activity of catalysts. Competition between the reaction of alkyl groups and ‐SH groups with surface hydroxyl during the preparation process of the catalyst influenced greatly the acid site densities, hydrophobic properties and activity of the catalyst. With an increase in the alkyl group chain, the hydrophobicity of catalysts increased obviously and the activity of the catalyst was enhanced. The most hydrophobic catalyst C₁₆‐SO₃H‐γ‐Al₂O₃–650°C exhibited the highest yield of 5‐HMF (84%) under the following reaction conditions: reaction medium of dimethylsulfoxide/H₂O (V/V, 4:1), catalyst amount of 30 mg, temperature of 110°C and reaction time of 4 hr.     

Efficient and Expeditious Synthesis of Pyrano‐pyrimidines,Multi‐substituted γ‐Pyrans,and Their Antioxidant Activity

An efficient, expeditious catalytic route for the synthesis of ethyl 6‐amino‐5‐cyano‐2‐methyl‐4‐aryl‐4H‐pyran‐3‐carboxylates 2 was achieved via a three‐component, one‐pot reaction of malononitrile, ethyl acetoacetate, and various aromatic aldehydes in water as a solvent at room temperature. The key advantages are excellent yield, reaction time, and inexpensive catalyst. Also, cyclization of 4H‐pyrans 2 to the corresponding 4H‐pyrano[2,3‐d]pyrimidines 3 using silica sulfuric acid in the presence of acetic anhydride was described. Some synthesized compounds exhibited promising antioxidant activities.     

Stereoselective Synthesis and Retentive Trapping of α‐Chiral Secondary Alkyllithiums Leading to Stereodefined α,β‐Dimethyl Carboxylic Esters

The treatment of α‐chiral secondary alkyl iodides with tBuLi at ?100 °C leads to the corresponding secondary alkyllithiums with high retention of configuration. Subsequent quenching with various electrophiles such as Bu₂S₂, DMF, MeOB(OR)₂, or Et₂CO provides the desired products with retention of configuration. Furthermore, a transmetalation with CuBr?P(OEt)₃ also allows retentive trapping with acid chlorides and ethylene oxide. The quenching of the resulting alkyllithiums with ClCO₂Et furnishes stereoselectively syn‐ and anti‐ethyl‐2,3‐dimethyl ester carboxylates (d.r.>94 %). Related esters bearing three adjacent stereo‐controlled centers (stereotriads) have also been prepared. This method has been applied to the synthesis of the ant pheromone (±)‐lasiol in 26 % overall yield (four steps) with d.r.=97:3 starting from commercially available cis‐2,3‐epoxybutane.     

Facile Chemoselective synthesis of 2‐(2‐(Methoxycarbonyl)‐3‐oxo‐2,3‐dihydrobenzofuran‐2‐yl)benzoic acids and 3H,3’H‐Spiro[benzofuran‐2,1′‐isobenzofuran]‐3,3′‐dione derivatives

Oxidation of some derivatives of 4b,9b–dihydroxyindeno[1,2‐b]benzofuran‐10‐one have been investigated in detail using lead(IV) acetate in acetic acid under reflux conditions and periodic acid in aqueous ethanol at room temperature. We realized that during the first 5–15 minutes of the oxidation reactions in lead(IV) acetate/acetic acid system, 3H,3’H‐spiro[benzofuran‐2,1′‐isobenzofuran]‐3,3′‐dione derivatives have been synthesized chemo selectively, while, if the reaction mixtures stirred for additional 3 hours, the main products would be 2‐(2‐(Methoxycarbonyl)‐3‐oxo‐2,3‐dihydrobenzofuran‐2‐yl)benzoic acids. Moreover, room temperature oxidation of 4b,9b–dihydroxyindeno[1,2‐b]benzofuran‐10‐ones by periodic acid (H₅IO₆), leads to the formation of 3H,3’H‐spiro[benzofuran‐2,1′‐isobenzofuran]‐3,3′‐dione derivatives in good to excellent yields.     

Interconversion of Metallabenzenes and Cyclic η2‐Allene‐Coordinated Complexes

Treatment of the osmabenzene [Os{CHC(PPh₃)CHC(PPh₃)CH} Cl₂(PPh₃)₂]Cl ( 1 ) with excess 8‐hydroxyquinoline produces monosubstituted osmabenzene [Os{CH C(PPh₃) CHC(PPh₃)CH}(C₉H₆NO)Cl(PPh₃)]Cl ( 2 ) or disubstituted osmabenzene [Os{CHC(PPh₃)CHC(PPh₃)CH} (C₉H₆NO)₂]Cl ( 3 ) under different reaction conditions. Osmabenzene 2 evolves into cyclic η²‐allene‐coordinated complex [Os{CH?C(PPh₃)CH=(η²‐C?CH₂)}(C₉H₆NO)(PPh₃)₂]Cl ( 4 ) in the presence of excess PPh₃ and NaOH, presumably involving a P? C bond cleavage of the metallacycle. Reaction of 4 with excess 8‐hydroxyquinoline under air affords the S_NAr product [(C₉H₆NO)Os{CHC(PPh₃)CHCHC} (C₉H₆NO)(PPh₃)]Cl ( 5 ). Complex 4 is fairly reactive to a nucleophile in the presence of acid, which could react with water to give carbonyl complex [Os{CH?C(PPh₃)CH?CH₂}(C₉H₆NO) (CO)(PPh₃)₂]Cl ( 6 ). Complex 4 also reacts with PPh₃ in the presence of acid and results in a transformation to [Os {CHC(PPh₃)CHCHC}(C₉H₆NO)Cl (PPh₃)₂]Cl ( 7 ) and [Os{CH?C(PPh₃) CH=(η²‐C?CH(PPh₃))}(C₉H₆NO) Cl(PPh₃)]Cl ( 8 ). Further investigation shows that the ratio of 7 and 8 is highly dependent on the amount of the acid in the reaction.     

Synthesis and characterization of new α,β‐unsaturated γ‐lactones: Alkyl 3‐acetyl‐4‐hydroxy‐2‐methyl‐5‐oxo‐2,5‐dihydrofuran‐2‐ylcarbamates

A convenient procedure for the preparation of carbamate derivatives of 5‐oxo‐2,5‐dihydrofuran ( 3 ) was described. The method is based on the Michael type addition of three alkyl carbamates ( 2 ) with 4‐acetyl‐5‐methyl‐2,3‐dihydro‐2,3‐furandione ( 1 ). According to ¹H nmr spectra of compounds show tautomeric forms ( 3,4,5 ) in CDC1₃. In the solid state the synthesized compounds are enol forms ( 3 ). The products were characterized with molecular spectroscopic methods.     

Synthesis and NMR Analysis in Solution of Oligo(3‐hydroxyalkanoic acid) Derivatives with the Side Chains of Alanine,Valine, and Leucine (β‐Depsides): Coming Full Circle from PHB to β‐Peptides to PHB

Oligomers of 3‐hydroxyalkanoic acids that contain two, three, and six residues with and without O‐terminal (tBu)Ph₂Si and C‐terminal PhCH₂ protection have been synthesized in such a way that the side chains on the oligoester backbone were those of the proteinogenic amino acids Ala (Me), Val (CHMe₂), and Leu (CH₂CHMe₂). The enantiomerically pure 3‐hydroxyalkanoates were obtained by Noyori hydrogenation of the corresponding 3‐oxo‐alkanoates with [Ru((R)‐binap)Cl₂](binap=2,2′bis(diphenylphosphanyl)‐1,1′‐binaphthalene)/H₂ (Scheme 1), and the coupling was achieved under the conditions (pyridine/(COCl)₂, CH₂Cl₂, −78°) previously employed for the synthesis of various oligo(3‐hydroxybutanoic acids) (Schemes 2 and 3). The Cotton effects in the CD spectra of the new oligoesters provided no hints about chiral conformation (cf. a helix) in MeOH, MeCN, octan‐1‐ol, or CF₃CH₂OH solutions (Figs. 1 and 2). Detailed NMR investigations in CDCl₃ solution (Figs. 3–6, and Tables 1–5) of the hexa(3‐hydroxyalkanoic acid) with the side chains of Val (HC), Ala (HB), Leu (HH), Val, Ala, Leu (from O‐ to C‐terminus; 3 ) gave, on the NMR time‐scale, no evidence for the presence of any significant amount of a 2₁‐ or a 3₁‐helical conformation, comparable to those identified in stretched fibers of poly[(R)‐3‐hydroxybutanoic acid], or in lamellar crystallites and in single crystals of linear and cyclic oligo[(R)‐3‐hydroxybutanoic acids], or in the corresponding β‐peptide(s) (the oligo(3‐aminoalkanoic acid) analogs; 1 – 3 ). Thus, the extremely high flexibility (averaged or ‘random‐coil' conformation) of the polyester chain (CO−O rotational barrier ca. 13 kcal/mol; no hydrogen bonding), as compared to polyamide chains (CO−NH barrier ca. 18 kcal/mol; hydrogen bonding) has been demonstrated once again. The possible importance of this structural flexibility, which goes along with amphiphilic properties, for the role of PHB in biology, in evolution, and in prebiotic chemistry is discussed. Structural similarities of natural potassium‐channeling proteins and complexes of oligo(3‐hydroxybutanoates) with Na⁺, K⁺, or Ba²⁺ are alluded to (Figs. 7–9).     

Two succinic acid derivatives of 2‐ethyl‐6‐methylpyridin‐3‐ol

Crystals of bis(2‐ethyl‐3‐hydroxy‐6‐methylpyridinium) succinate–succinic acid (1/1), C₈H₁₂NO⁺·0.5C₄H₄O₄²⁻·0.5C₄H₆O₄, (I), and 2‐ethyl‐3‐hydroxy‐6‐methylpyridinium hydrogen succinate, C₈H₁₂NO⁺·C₄H₅O₄⁻, (II), were obtained by reaction of 2‐ethyl‐6‐methylpyridin‐3‐ol with succinic acid. The succinate anion and succinic acid molecule in (I) are located about centres of inversion. Intermolecular O—H...O, N—H...O and C—H...O hydrogen bonds are responsible for the formation of a three‐dimensional network in the crystal structure of (I) and a two‐dimensional network in the crystal structure of (II). Both structures are additionally stabilized by π–π interactions between symmetry‐related pyridine rings, forming a rod‐like cationic arrangement for (I) and cationic dimers for (II).     

Preparation of new 2‐amino‐ and 2,3‐diamino‐pyridine trifluoroacetyl enamine derivatives and their application to the synthesis of trifluoromethyl‐containing 3H‐pyrido[2,3‐b][1,4] diazepinols

The synthesis of a novel series of the intermediates N²(N³)‐[1‐alkyl(aryl/heteroaryl)‐3‐oxo‐4,4,4‐trifluoroalk‐1‐en‐1‐yl]‐2‐aminopyridines [F₃CC(O)CH?CR¹(2? NH?C₅H₃N)] and 2,3‐diaminopyridines [F₃CC(O)CH?CR¹(2‐NH₂‐3‐NH? C₅H₃N)], where R¹ = H, Me, C₆H₅, 4‐FC₆H₄, 4‐CIC₆H₄, 4‐BrC₆H₄, 4‐CH₃C₆H₄, 4‐OCH₃C₆H₄, 4,4′‐biphenyl, 1‐naphthyl, 2‐thienyl, 2‐furyl, is reported. The corresponding series of 2‐aryl(heteroaryl)‐4‐trifluoromethyl‐3H‐pyrido[2,3‐b][1,4]diazepin‐4‐ols obtained from intramolecular cyclization reaction of the respective trifluoroacetyl enamines or from the direct cyclocondensation reaction of 4‐methoxy‐1,1,1‐trifluoroalk‐3‐en‐2‐ones with 2,3‐diaminopyridine, under mild conditions, is also reported.     

Transfer Hydrocyanation of α‐ and α,β‐Substituted Styrenes Catalyzed by Boron Lewis Acids

A straightforward gram‐scale preparation of cyclohexa‐1,4‐diene‐based hydrogen cyanide (HCN) surrogates is reported. These are bench‐stable but formally release HCN and rearomatize when treated with Lewis acids. For BCl₃, the formation of the isocyanide adduct [(CN)BCl₃]^? and the corresponding Wheland complex was verified by mass spectrometry. In the presence of 1,1‐di‐ and trisubstituted alkenes, transfer of HCN from the surrogate to the C?C double bond occurs, affording highly substituted nitriles with Markovnikov selectivity. The success of this transfer hydrocyanation depends on the Lewis acid employed; catalytic amounts of BCl₃ and (C₆F₅)₂BCl are shown to be effective while B(C₆F₅)₃ and BF₃?OEt₂ are not.     

From α‐carbamoyl‐α‐cyano­oxiranes to 3‐halogenopyruv­amides

The crystal structures of the first stable α‐diol from the α‐halogenopyruv­amide series, 3‐chloro‐2,2‐di­hydroxy‐3‐phenyl­propan­amide, C₉H₁₀­ClNO₃, and three products [3‐(4‐chloro­phenyl)‐2‐cyano‐2,3‐epoxy­propan­amide, C₁₀H₇­ClN₂O₂, 3‐bromo‐2‐cyano‐2‐hydroxy‐3‐p‐tolyl­propan­amide, C₁₁H₁₁Br­N₂O₂, 3‐bromo‐2‐oxo‐3‐p‐tolyl­propan­amide, C₁₀H₁₀­BrNO₂] obtained during the systematic synthesis of α‐halogenopyruv­amides are reported. The crystal structures are dominated by hydrogen bonds involving an amide group. The stability of the geminal diol could be ascribed to hydrogen bonds which involve both hydroxyl groups.     

Four oxoindole‐linked α‐alkoxy‐β‐amino acid derivatives

Four structures of oxoindolyl α‐hydroxy‐β‐amino acid derivatives, namely, methyl 2‐{3‐[(tert‐butoxycarbonyl)amino]‐1‐methyl‐2‐oxoindolin‐3‐yl}‐2‐methoxy‐2‐phenylacetate, C₂₄H₂₈N₂O₆, (I), methyl 2‐{3‐[(tert‐butoxycarbonyl)amino]‐1‐methyl‐2‐oxoindolin‐3‐yl}‐2‐ethoxy‐2‐phenylacetate, C₂₅H₃₀N₂O₆, (II), methyl 2‐{3‐[(tert‐butoxycarbonyl)amino]‐1‐methyl‐2‐oxoindolin‐3‐yl}‐2‐[(4‐methoxybenzyl)oxy]‐2‐phenylacetate, C₃₁H₃₄N₂O₇, (III), and methyl 2‐[(anthracen‐9‐yl)methoxy]‐2‐{3‐[(tert‐butoxycarbonyl)amino]‐1‐methyl‐2‐oxoindolin‐3‐yl}‐2‐phenylacetate, C₃₈H₃₆N₂O₆, (IV), have been determined. The diastereoselectivity of the chemical reaction involving α‐diazoesters and isatin imines in the presence of benzyl alcohol is confirmed through the relative configuration of the two stereogenic centres. In esters (I) and (III), the amide group adopts an anti conformation, whereas the conformation is syn in esters (II) and (IV). Nevertheless, the amide group forms intramolecular N—H...O hydrogen bonds with the ester and ether O atoms in all four structures. The ether‐linked substituents are in the extended conformation in all four structures. Ester (II) is dominated by intermolecular N—H...O hydrogen‐bond interactions. In contrast, the remaining three structures are sustained by C—H...O hydrogen‐bond interactions.     

4‐(2‐Hydroxyphenyl)‐2‐phenyl‐2,3‐dihydro‐1H‐1,5‐benzodiazepine and the 2‐(2,3‐dimethoxyphenyl)‐, 2‐(3,4‐dimethoxyphenyl)‐ and 2‐(2,5‐dimethoxyphenyl)‐substituted derivatives

The 1,5‐benzodiazepine ring system exhibits a puckered boat‐like conformation for all four title compounds [4‐(2‐hydroxyphenyl)‐2‐phenyl‐2,3‐dihydro‐1H‐1,5‐benzodiazepine, C₂₁H₁₈N₂O, (I), 2‐(2,3‐dimethoxyphenyl)‐4‐(2‐hydroxyphenyl)‐2,3‐dihydro‐1H‐1,5‐benzodiazepine, C₂₃H₂₂N₂O₃, (II), 2‐(3,4‐dimethoxyphenyl)‐4‐(2‐hydroxyphenyl)‐2,3‐dihydro‐1H‐1,5‐benzodiazepine, C₂₃H₂₂N₂O₃, (III), and 2‐(2,5‐dimethoxyphenyl)‐4‐(2‐hydroxyphenyl)‐2,3‐dihydro‐1H‐1,5‐benzodiazepine, C₂₃H₂₂N₂O₃, (IV)]. The stereochemical correlation of the two C₆ aromatic groups with respect to the benzodiazepine ring system is pseudo‐equatorial–equatorial for compounds (I) (the phenyl group), (II) (the 2,3‐dimethoxyphenyl group) and (III) (the 3,4‐dimethoxyphenyl group), while for (IV) (the 2,5‐dimethoxyphenyl group) the system is pseudo‐axial–equatorial. An intramolecular hydrogen bond between the hydroxyl OH group and a benzodiazepine N atom is present for all four compounds and defines a six‐membered ring, whose geometry is constant across the series. Although the molecular structures are similar, the supramolecular packing is different; compounds (I) and (IV) form chains, while (II) forms dimeric units and (III) displays a layered structure. The packing seems to depend on at least two factors: (i) the nature of the atoms defining the hydrogen bond and (ii) the number of intermolecular interactions of the types O—H...O, N—H...O, N—H...π(arene) or C—H...π(arene).     

Syntheses of β‐C(1→3)‐Glucopyranosides of 2‐ and 4‐Deoxy‐D‐hexoses

The Oshima? Nozaki (Et₂AlI) condensation of isolevoglucosenone ( 4 ) with 2,6‐anhydro‐3,4,5,7‐tetra‐O‐benzyl‐D ‐glycero‐D ‐gulo‐heptose ( 5 ) gave an enone 6 that was converted with high stereoselectivity to 3‐C‐[(1R)‐2,6‐anhydro‐D ‐glycero‐D ‐gulo‐heptitol‐1‐C‐yl]‐2,3‐dideoxy‐D ‐arabino‐hexose ( 1 ; 1 : 1 mixture of α‐ and β‐D ‐pyranose), and to 3‐C‐[(1R)‐2,6‐anhydro‐D ‐glycero‐D ‐gulo‐heptitol‐1‐C‐yl]‐2,3‐dideoxy‐D ‐lyxo‐hexose ( 2 ; 2.7 : 1.4 : 1.0 : 1.4 mixture of α‐D ‐furanose, β‐D ‐furanose, α‐D ‐pyranose, and β‐D ‐pyranose). The Oshima? Nozaki (Et₂AlI) condensation of levoglucosenone ( 17 ) with aldehyde 5 gave an enone 18 that was converted with high stereoselectivity to 3‐C‐[(1R)‐2,6‐anhydro‐D ‐glycero‐D ‐gulo‐heptitol‐1‐C‐yl]‐3,4‐dideoxy‐α‐D ‐arabino‐hexopyranose ( 3 ; single anomer).     

β,β‐(1,4‐Dithiino)subporphyrin Dimers Capturing Fullerenes with Large Association Constants

β,β‐(1,4‐Dithiino)subporphyrin dimers 7‐syn and 7‐anti were synthesized by the nucleophilic aromatic substitution reaction of 2‐bromo‐3‐(4‐methoxyphenylsulfonyl)subporphyrin 4 with 2,3‐dimercaptosubporphyrin 5 under basic conditions followed by axial arylation. Additions of C₆₀ or C₇₀ to a dilute solution of 7‐anti (ca. 10^?6 m ) in toluene did not cause appreciable UV/Vis spectral changes, while similar additions to a concentrated solution (ca. 10^?3 m ) resulted in precipitation of complexes. In contrast, dimer 7‐syn captured C₆₀ and C₇₀ in different complexation stoichiometries in toluene; a 1:1 manner and a 2:1 manner, respectively, with large association constants; K_a=(1.9±0.2)×10⁶ m ^?1 for C₆₀@ 7‐syn , and K₁=(1.6±0.5)×10⁶ and K₂=(1.8±0.9)×10⁵ m ^?1 for C₇₀@( 7‐syn )₂. These association constants are the largest for fullerenes‐capture by bowl‐shaped molecules reported so far. The structures of C₆₀@ 7‐anti , C₇₀@ 7‐anti , C₆₀@ 7‐syn , and C₇₀@ 7‐syn have been determined by single‐crystal X‐ray diffraction analysis.