Solid–liquid equilibria of acenaphthene with o-, m-, or p-dichlorobenzene

A differential scanning calorimetry (DSC) was used to determine binary solid–liquid equilibria (SLE) for acenaphthene  + o-dichlorobenzene, +m-dichlorobenzene, and +p-dichlorobenzene over the whole concentration range. It was found that all systems are simple eutectic systems. The eutectic point of the (acenaphthene + o-dichlorobenzene) system is at 254.95 K and 0.0334 mole fraction of acenaphthene, that of the (acenaphthene + m-dichlorobenzene) system at 246.15 K and 0.0460 mole fraction of acenaphthene and that of the (acenaphthene + p-dichlorobenzene) system at 307.75 K and 0.2940 mole fraction of acenaphthene. Furthermore, the activity coefficients of the components in the binary mixtures have been correlated by the Scatchard–Hildebrand expression with one adjustable parameter. This approach offers a useful procedure for estimating with good accuracy.     

p-tert-Butyl thiacalix[4]arenes functionalized at the lower rim by o-, m-, p-amido and o-, m-, p-(amidomethyl)pyridine fragments as receptors for α-hydroxy- and dicarboxylic acids

A series of new p-tert-butyl thiacalix[4]arenes with o-, m-, p-amido and o-, m-, p-(amidomethyl)pyridine substituents at the lower rim in cone, partial cone, and 1,3-alternate conformations were synthesized. The ability of the obtained compounds to recognize the α-hydroxy (glycolic, tartaric) and dicarboxylic (oxalic, malonic, succinic, fumaric, and maleic) acids was investigated by UV-vis spectroscopy. Also, the efficiency and selectivity of binding, the association constants log K_a (10² to 10⁷ M⁻¹) and the stoichiometry were determined for the complexes of p-tert-butyl thiacalix[4]arenes with the acids. The receptors based on p-tert-butyl thiacalix[4]arenes with (amidomethyl)pyridine substitutes are most efficient in complexation in many cases.     

Stereospecific interconversion of cis- and trans-γ,δ-epoxy α,β-unsaturated ester systems

The unprecedented, stereospecific interconversion of cis- and trans-γ,δ-epoxy α,β-unsaturated ester systems has been realized, which involves the palladium-catalyzed stereospecific alkoxy or hydroxy substitution reaction with double inversion of configuration at the γ-position as the key step. The new methodology is not only applicable to various disubstituted and trisubstituted epoxy unsaturated esters, but also these interconversions proceed with an extremely high degree of stereoselectivity and efficiency.     

Total synthesis of (6Z,9S)-3,4-trans-9-hydroxy-3-methyldodec-cis-6-en-4-olide and (6Z)-3,4-trans-9-oxo-3-methyldodec-cis-6-en-4-olide γ-butyrolactones

The first total synthesis of (6Z,9S)-3,4-trans-9-hydroxy-3-methyldodec-cis-6-en-4-olide and (6Z)-3,4-trans-9-oxo-3-methyldodec-cis-6-en-4-olide was achieved in a convergent pathway. The salient features of our synthesis include Ohira–Bestmann reaction, regioselective alkyne addition to terminal epoxide, TEMPO/BAIB mediated oxidative lactonization, and partial hydrogenation.     

Stereoselective synthesis of 1-O-β-feruloyl and 1-O-β-sinapoyl glucopyranoses

1-O-β-Feruloyl and 1-O-β-sinapoyl glucopyranoses are two common substrates for serine carboxypeptidase-like acyltransferases and serve as acyl donors in the biosynthesis of numerous secondary metabolites. In addition, they are involved in plant cell wall cross-linking and are also ideal substrates for studying the kinetics of lignification involving hydroxycinnamates. We report the first chemical (and multi-gram scale) synthesis of 1-O-β-feruloyl and 1-O-β-sinapoyl glucopyranoses.     

Total synthesis of two γ-butyrolactone containing compounds (Z,11S)-3,4-trans-11-hydroxy-3-methyldodec-cis-6-en-4-olide and (Z)-3,4-trans-11-oxo-3-methyldodec-cis-6-en-4-olide

The first total synthesis of (Z,11S)-3,4-trans-11-hydroxy-3-methyldodec-cis-6-en-4-olide and (Z)-3,4-trans-11-oxo-3-methyldodec-cis-6-en-4-olide was accomplished using Jacobsen hydrolytic kinetic resolution, Ohira–Bestmann reaction, regioselective alkyne addition to terminal carbon atom of epoxide, intramolecular TEMPO/BAIB mediated oxidative lactonization and partial hydrogenation as the key steps.     

Syntheses of β- and γ-fluorophenyl cis- and trans-α-methylene-γ-butyrolactones

Preparation of a series of cis-γ-fluorophenyl-β-phenyl-α-methylene-γ-butyrolactones is reported via ‘allylboration’ of fluorobenzaldehydes with (E)-methyl 3-phenyl-2-((4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)methyl)acrylate. The corresponding trans-γ-fluorophenyl lactones were prepared either (i) via ‘allylboration’ using the (Z)-reagents or (ii) via an indium triflate-mediated isomerization of the cis-products. The difficulty in isomerizing difluorinated cis-products confirms the probable intermediacy of carbocations. Finally, the synthesis of cis-β-fluorophenyl-γ-phenyl-α-methylene-γ-butyrolactones was achieved via an indium-catalyzed allylation–lactonization of aldehydes with (Z)-2-(bromomethyl)-3-(fluorophenyl)acrylates.     

Asymmetric synthesis of erythro-β-hydroxyasparagine

erythro-Hydroxyasparagine (eHyAsn, 1) occurs in a number of naturally occurring peptides and proteins. Previous syntheses have relied on enzyme-catalyzed reactions to produce relevant, optically active intermediates. We report herein a completely chemical synthesis that intercepts Boger’s synthesis of the diastereomer (tHyAsn, 4), utilizing a Sharpless asymmetric aminohydroxylation reaction to introduce the two stereocenters. Boc-HyAsn(OTBS)-OH (10) was coupled effectively with phenylalanine methyl ester using EDC/HOBt.     

Flavonol 3-O-robinobiosides and 3-O-(2″-O-α-rhamnopyranosyl)-robinobiosides from Sesuvium portulacastrum

Six new flavonol 3-O-robinobiosides and 3-O-(2″-O-α-l-rhamnopyranosyl)-robinobiosides, sesuviosides A-F, were isolated from the aerial portion of Sesuvium portulacastrum together with ecdysterone, adenosine, 2′-O-methyladenosine, and l-tryptophan. The structure elucidations were based on analyses of chemical and spectroscopic data including 1D and 2D-NMR. Sesuviosides A-F and their aglycones exhibited radical scavenging activity using DPPH and ORAC assays.     

Dy(OTf)3-mediated selective substitution of N-(α-benzotriazolyl-alkyl)amides with active methylene compounds for synthesis of benzotriazole derivatives

A Dy(OTf)₃-mediated selective substitution reaction of N-(α-benzotriazolyl-alkyl)amides with active methylene compounds is reported. The present procedure provides a facile method for the synthesis of benzotriazole derivatives.     

Synthesis of cis- and trans-(±)-3-mercaptoproline and pipecolic acid derivatives via thio-Michael addition

The reactivity of 2,3-dehydroproline and 2,3-dehydropipecolic acid methyl ester derivatives with S-nucleophiles in the thio-Michael addition reaction has been explored. The addition of triphenylmethanethiol and subsequent trityl cleavage led to the corresponding cis- and trans-(±)-3-mercaptoproline and pipecolic acid derivatives in good yields.     

Host compounds (+)-(2R,3R)-1,1,4,4-tetraphenylbutane-1,2,3,4-tetraol (TETROL) and (2R,3R)-(−)-2,3-dimethoxy-1,1,4,4-tetraphenylbutane-1,4-diol (DMT) with guests o-, m- and p- toluidine: A comparative investigation

In this work, we have compared the host abilities of closely related compounds (+)-(2R,3R)-1,1,4,4-tetraphenylbutane-1,2,3,4-tetraol (TETROL) and (2R,3R)-(?)-2,3-dimethoxy-1,1,4,4-tetraphenylbutane-1,4-diol (DMT) when these were recrystallized from single and mixed toluidine guests. Significant differences in host behaviour and selectivities were revealed and these were explained by means of single crystal diffraction experiments. Thermal analyses were used to determine the relative complex stabilities, and these data correlated exactly with the host selectivity orders for both TETROL and DMT.     

Facile rearrangement of N-(α-aminoacyl)cytidines to N-(4-cytidinyl)amino acid amides

Under near neutral and mildly basic conditions, primary N⁴-(α-aminoacyl)cytidines (4a-g) undergo a facile rearrangement to form N-(4-cytidinyl)amino acid amides (5a-g). Secondary aminoacyl derivatives rearrange with other competing pathways. Tertiary aminoacyl derivatives do not rearrange.     

New polymer-supported phosphonate reagents for the synthesis of Z-α,β-unsaturated esters

New polymer-supported phosphonate reagents have been prepared and evaluated for the synthesis of Z-α,β-unsaturated esters. High Z-selectivity was obtained using the reagent having two o-t-BuC₆H₄ groups.     

Synthesis and conformational studies of chiral meso-(α,β-unsaturated)-porphyrins

We describe a method to improve the yield and the kinetics of the difficult syntheses of α,β-unsaturated porphyrins, which enabled us to obtain a new chiral porphyrin derived from (S)-(−)-perillaldehyde in a 6% yield. Variable temperature NMR experiments on the free base, the zinc(II) and the nickel(II) complexes showed that two distinct and consecutive dynamic processes linked with the meso substituents rotation occurred. These processes can be analyzed as an evolution of the conformer composition upon temperature change. Higher values are found for the free energies of rotation of the substituent (measured by variable temperature ¹H NMR) compared to those of other equivalent porphyrins like meso-tetraphenyl porphyrin or meso-tetracyclohexyl porphyrin.     

Comprehensive study towards the desulfonylation/desulfinylation of cis-3-functionalized 3-phenylsulfonyl/sulfinyl-β-lactams to access novel cis-3-monosubstituted-β-lactams

An inclusive study towards the stereospecific synthesis of novel cis-3-monosubstituted-β-lactams from cis-3-functionalized 3-phenylsulfonyl/sulfinyl-β-lactams is described. 3-Sulfinyl-β-lactams 5/5? successfully furnished stereospecific cis-3-monosubstituted-β-lactams 6, however 3-sulfonyl-β-lactams 2 failed to give the desulfurized product 6?. The final stereochemical and structural conformations of novel β-lactams were established by single crystal X-ray crystallographic study (5c). The cis configuration of the β-lactams 5/5? and 6 was assigned in relevance to E and C4-H and C3-H and C4-H respectively.     

Regiospecific synthesis of quercetin O-β-d-glucosylated and O-β-d-glucuronidated isomers

Quercetin, the polyphenolic compound, which has the highest daily intake, is well known for its protective effects against aging diseases and has received a lot of attention for this reason. Both quercetin 3-O-β-d-glucuronide and quercetin 3′-O-β-d-glucuronide are human metabolites, which, together with their regioisomers, are required for biological as well as physical chemistry studies. We present here a novel synthetic route based on the sequential and selective protections of the hydroxyl functions of quercetin allowing selective glycosylation, followed by TEMPO-mediated oxidation to the glucuronide. This methodology enabled us to synthesize the five O-β-d-glucosides and four O-β-d-glucuronides of quercetin, including the major human metabolite, quercetin 3-O-β-d-glucuronide.     

A simple one-pot 2-step N-1-alkylation of indoles with α-iminoketones toward the expeditious 3-step synthesis of N-1-quinoxaline-indoles

A straightforward procedure for the preparation of N-quinoxaline-indoles is presented. A base-catalyzed one-pot addition of indoles to a preformed α-iminoketone proceeds on the N-1 indole and the subsequent adduct undergoes an acid-mediated deprotection of an internal amino nucleophile, intramolecular cyclization, and final oxidation generating N-1-quinoxaline-indoles in good yield.     

syn-π-Face- and endo-selective, inverse electron-demand Diels-Alder reactions of 3,4-di-tert-butylthiophene 1-oxide with electron-rich dienophiles

Diels-Alder reactions of 3,4-di-tert-butylthiophene 1-oxide with oxygen (or sulfur)-substituted dienophiles and with simple alkenic dienophiles, which are classified as an inverse electron-demand Diels-Alder reaction on the basis of DFT calculations, took place exclusively at the syn-π-face of the diene with respect to the SO bond to provide the corresponding adducts in high yields.     

Synthesis of 2,3-disubstituted benzofurans and indoles by π-Lewis acidic transition metal-catalyzed cyclization of ortho-alkynylphenyl O,O- and N,O-acetals

The PtCl₂-catalyzed cyclization reaction of ortho-alkynylphenyl acetals 1 in the presence of COD (1,5-cyclooctadiene) produces 3-(α-alkoxyalkyl)benzofurans 2 in good to high yields. For example, the reaction of acetaldehyde ethyl 2-(1-octynyl)phenyl acetal (1a), acetaldehyde ethyl 2-(cyclohexylethynyl)phenyl acetal (1c), and acetaldehyde ethyl 2-(phenylethynyl)phenyl acetal (1f) in the presence of 2 mol % of platinum(II) chloride and 8 mol % of 1,5-cycloocatadiene in toluene at 30 °C gave the corresponding 2,3-disubstituted benzofurans 2a, 2c, and 2f in 91, 94, and 88% yields, respectively. Moreover, the reaction of N-methoxymethyl-2-alkynylanilines 3 was catalyzed by PdBr₂, affording the corresponding 2,3-disubstituted indoles 4 in moderate yields. For example, the reaction of N-methoxymethyl-2-(1-pentynyl)-N-tosylaniline (3a) and N-methoxymethyl-2-(phenylethynyl)-N-tosylaniline (3b) in the presence of 10 mol % of PdBr₂ in toluene at 80 °C gave 3-methoxymethyl-2-propyl-1-tosylindole (4a) and 3-methoxymethyl-2-phenyl-1-tosylindole (4b) in 33 and 33% yields, respectively.