Supercritical CO2 as a superior solvent for the cyclization of diallylmalonate catalyzed by palladium-containing zeolites

Palladium-containing zeolites catalyze the cycloisomerization of diethyl diallylmalonate to dimethylcyclopentenes. When the reaction is carried out in toluene, the performance of the palladium catalyst depends on the pore size of the zeolites. At 60 °C, palladium adsorbed on large pore size Beta zeolite (pore size ∼7.4 Å) is more active than medium pore size ZSM-5 (pore size ∼5.4 Å). This lower activity of ZSM-5 compared to Beta is attributable to the restricted diffusion of reagent and products through the ZSM-5 channels as compared to Beta zeolite. However, due to the gas-like diffusion characteristic of the supercritical state, the activity of ZSM-5 increases and becomes identical to that of Beta zeolite using supercritical CO₂ as medium.     

Alkenylidenes in Organic Synthesis

Alkenylidenes R₂C?C: (= alkylidene carbenes) undergo regio- and stereoselective intramolecular C? H insertion reactions that are excellently suited for the synthesis of cyclopentenes. The 1, 2-shifts occurring with R?H and R?Ar are useful for the preparation of alkynes. Alkenylidenes are efficiently generated from carbonyl compounds by diazomethylation, from vinyl halides by α-elimination, from alkynyliodonium salts by addition of nucleophiles, and from alkynes by retro-1, 2-shifts. Specific applications of the various methods, particularly in the synthesis of natural products, are discussed.     

Mass Spectral Fragmentation of (S,S)-N,N′-Bis [1-(hydroxymethyl)alkyl]anthracene/Naphthalene-1,8-dicarboxamides under Electron Impact Ionization Conditions

IntroductionN,N′-Bis [1-( hydroxymethyl) alkyl] dicarboxa-mides are important intermediates for the syntheses ofbis-oxazolines, which are a class of the most importantand widely used ligands in catalytic asymmetric reac-tions[1,2]. On determining the str…     

Olefinic-ester cyclizations using Takai-Utimoto reduced titanium alkylidenes

The scope and limitations of the Takai-Utimoto reagent to induce the cyclization of olefinic-esters is described. Critical is the steric environment about both the ester and the olefin. Mechanistically, these results support the hypothesis that cyclized product comes from an olefin metathesis, carbonyl-olefination sequence.     

Intra- and intermolecular trapping of cyclopentapyrazine carbenes derived from 1,2-dialkynylimidazoles

The thermolysis of 1,2-dialkynylimidazoles in benzene solution affords high yields of 7-phenyl-5H-cyclopentapyrazines, which presumably form by solvent trapping of cyclopentapyrazine carbene intermediates. In cases where dialkynylimidazole contains side chains that can participate in intramolecular carbene C-H insertion or olefin addition, these processes compete with solvent addition to afford novel tri- and tetracyclic pyrazines, which can be obtained in good yield when the thermolysis is carried out in hexafluorobenzene.     

Synthesis of 2-methylidene-1-silacyclohexanes from 2,6-dibromohex-1-ene and polyhalosilanes

Various 2-methylidene-1-silacyclohexanes were prepared by straightforward syntheses from readily available polychloro- or polyfluorosilanes, magnesium and 2,6-dibromohex-1-ene using Barbier-type conditions or a previously synthesized Grignard reagent. Good yields were obtained considering the low stability of the products in the reaction conditions.     

An efficient synthesis of 5-aminoimidazol-2-ones via cyclization reactions of 2-aminoacetonitriles and isocyanates

The scope of a cyclization reaction between amino-acetonitriles and isocyanates was investigated. The study revealed that this reaction tolerates various functional groups leading to highly functionalized 5-amino-imidazole-2-ones, which are useful intermediates for purine synthesis.     

Homolytic Cyclizations of N-Chloroalkenylamines

Many N-chloroalkylamines with double bond(s) dissociate homolytically to give chlorine atoms and aminyl radicals which undergo intramolecular cyclization reactions. Here, the nature of the aminyl radicals (neutral, protonated, or complexed to metal salts) appears to be important. The reactivity varies strongly from one species to another, and their selectivities can be different towards addition, substitution, abstraction, or dimerization reactions. A good synthetic tool appears to be the “complexed radical”, which is generated under mild conditions. A variety of β-functionalized, substituted, fused, or bridged azaheterocycles with alkaloid part structures thus become easily accessible in high yields, in a regio- and, possibly, stereoselective manner. Many examples are discussed illustrating the synthetic possibilities, limitations, and mechanistic features of this cyclization process.     

Formation of azatitanacyclopentanes from ene-imines and a Ti(O-i-Pr)4/2i-PrMgX reagent and their synthetic reactions

ω-Vinylimines reacted with a Ti(O-i-Pr)₄/2i-PrMgX reagent to generate the corresponding azatitanacyclopentanes in quantitative yield, which in turn reacted with H₂O, I₂ and O₂ to give 2-methyl-, 2-iodomethyl-, 2-hydroxymethyl-1-aminocyclic compounds, respectively. The azatitanacyclopentanes thus generated reacted with formaldehyde to afford the corresponding 2,3-annulated pyrrolidines in good yield.     

The “Facilitated Transition” hypothesis as an explanation for the gemdialkyl effect

A new technique of searching the conformational space of transition states was used to explore the cause of the rate acceleration in the gem-dialkyl effect in intramolecular cyclization reactions. Several previous hypotheses were discarded and a new hypothesis was advanced based on this new data. This hypothesis, the “Facilitated Transition” hypothesis, states that increased steric hindrance reduces the overall activation energy by facilitating rotation through the transition state. The older “Reactive Rotamer” hypothesis was eliminated by generating all conformations of the starting materials using the and computer programs and demonstrating that no relationship is found between rate increase and a change in the concentration of “reactive rotamers”.