Synthesis of functionalized polyhedral oligomeric silsesquioxane (POSS) macromers by microwave assisted 1,3-dipolar cycloaddition

In this paper we report the first synthesis of isoxazolidine and isoxazoline-POSS macromers by 1,3-dipolar cycloaddition reactions of vinyl- and styryl-POSS with N-methyl-C-ethoxycarbonylnitrone and ethoxycarbonyl nitrile oxide, promoted by microwave irradiation. The nature of the resulting cycloadducts has been determined by NOE experiments and supported by computational studies at PM3 and DFT B3LYP/6-31G* levels.     

13C NMR examination of some N-thioaroylmorpholine–bromine adducts

The ¹³C NMR chemical shifts of three N-thioaroylmorpholine–bromine adducts, previously used as synthetic intermediates, are compared and discussed in the light of the corresponding shifts of the parent thioamides and suitable model compounds. Chemical shift changes are interpreted in terms of the electronic perturbation resulting from bromine coordination at sulphur.     

Stereodefined ring contraction-rearrangement of thiocoumarins to new fused benzo[b]thiophene derivatives

Mesoionic 1,3-oxazolium-5-olates (münchnones) react with thiocoumarins having an electron-withdrawing group at the 3-position to afford stereodefined fused polycyclic thienopyrroles. The reaction sequence seems to be triggered by a regiospecific dipolar cycloaddition followed by ring opening of the initial 1:1 cycloadduct and intramolecular rearrangement with an unusual ring contraction.     

The site-selectivity of cycloadditions of nitrile oxides to β-aminocinnamonitriles. A remarkable solvent dependence

Cycloadditions of nitrile oxides to N-mono and unsubstituted β-aminocinnamonitriles are remarkably affected by the hydrogen acceptor ability of the solvent. Addition to C ? N bond predominates in non and weak hydrogen bond acceptor solvents because of the assistance of favourable hydrogen bonding effects. In strong hydrogen bond acceptor solvents the assistance is fully relieved and the regular addition to C ? C bond becomes prevalent.     

An integral for the scalar propagator

Using a convenient contour in the complex plane, an integral representation is obtained for the hypergeometric function, in the case when this function does not reduce to the polynomial case. As an application, a contour integral associated with the massive scalar propagator used in Feynman diagrams is discussed.     

Local behaviour of singular solutions for nonlinear elliptic equations in divergence form

We consider the following class of nonlinear elliptic equations $$\begin{array}{ll}{-}{\rm div}(\mathcal{A}(|x|)\nabla u) +u^q=0\quad {\rm in}\; B_1(0)\setminus\{0\}, \end{array}$$ where q > 1 and ${\mathcal{A}}$ is a positive C ¹(0,1] function which is regularly varying at zero with index ${\vartheta}$ in (2?N,2). We prove that all isolated singularities at zero for the positive solutions are removable if and only if ${\Phi\not\in L^q(B_1(0))}$ , where ${\Phi}$ denotes the fundamental solution of ${-{\rm div}(\mathcal{A}(|x|)\nabla u)=\delta_0}$ in ${\mathcal D'(B_1(0))}$ and δ₀ is the Dirac mass at 0. Moreover, we give a complete classification of the behaviour near zero of all positive solutions in the more delicate case that ${\Phi\in L^q(B_1(0))}$ . We also establish the existence of positive solutions in all the categories of such a classification. Our results apply in particular to the model case ${\mathcal{A}(|x|)=|x|^\vartheta}$ with ${\vartheta\in (2-N,2)}$ .     

Diastereofacial selectivity in azomethine ylide cycloaddition reactions derived from chiral α-cyanoaminosilanes

A series of α-cyanoaminosilanes has been found to act as azomethine ylide equivalents. Treatment of these compounds with silver fluoride in the presence of electron deficient olefins gives substituted pyrrolidines in high yield. The extent ofdiastereoselectivity associated with the 1,3-dipolar cycloaddition of chiral azomethine ylides with several dipolarophiles has been studied. Reasonable levels of such diastereoselectivity have been found when optically active α-cyanoaminosilanes are employed as azomethine ylide equivalents. These compounds can be prepared in multigram quantities by treating the appropriate chiral amine with chlorotrimethylsilane followed by reaction of the resulting secondary amine with formaldehyde in the presence of potassium cyanide. It was found that N-benzyl-N-cyanomethyl-N-trimethylsilylmethylamine undergoes stereospecific cycloaddition with dimethyl fumarate and maleate. The stereospecificity of the reaction is consistent with a concerted cycloaddition reaction.     

Stereoselective synthesis of new bicyclic N,O-iso-homonucleoside analogues

The synthesis of two new bicyclic nucleoside analogues is reported. These compounds are iso-homonucleoside and are synthesised through a 1,3-dipolar cycloaddition of an enantiopure cyclic nitrone to protected allyl acohol and subsequent introduction of thymine by a Mitsunobu reaction.     

Steric course of some cyclopropanation reactions of L-threo-hex-4-enopyranosides

Completely protected 4-deoxy-α-L-threo-hex-4-enopyranosides 1c,d undergo the dichlorocarbene addition affording exclusively diastereomeric adducts 5c,d with the cyclopropane ring anti to the C-3 alkyloxy substituent, while the reaction with 3-unprotected derivatives 1a,b affords a mixture of syn and anti derivatives. Under the Simmons-Smith cyclopropanation adducts 2a-d with a syn stereochemistry are obtained. Starting from 5b, the cyclopropanated sugar 3b is obtained by reduction with LiAlH₄, thus the two diastereomers 2b and 3b can be stereoselectively obtained through the two different pathways. For a useful comparison, 4-deoxy-β-L-threo-hex-4-enopyranoside 1e was also subjected to the above two cyclopropanation methods affording the expected cycloadduct 2e and a diastereomeric mixture of dichlorocycloadducts 4e and 5e (4e/5e=2.8:1).