Synthesis of C2-symmetric trans-2,6-diarylpiperidinones via aryl cuprate addition: an unexpected stereochemical outcome

An efficient procedure for the preparation of trans-2,6-diaryl piperidinones has been developed. Addition of aryl Grignard reagents to 2-aryl dihydropyridones under catalytic copper promoted conditions generates the trans isomer exclusively, an unprecedented stereochemical event. The X-ray structures of both starting material and product have been solved and shed light on the steric constraints and substrate geometry leading to the observed product. The reaction conditions tolerate a variety of aromatic nucleophiles to generate C₂-symmetric products in good overall yields.     

Strong intramolecular secondary si.N bonds in trifluorosilylhydrazines

The simple silylhydrazines F(3)SiN(Me)NMe(2) (1), F(2)Si(N(Me)NMe(2))(2) (2), and F(3)SiN(SiMe(3))NMe(2) (3) have been prepared by reaction of SiF(4) with LiN(Me)NMe(2) and LiN(SiMe(3))NMe(2), while F(3)SiN(SnMe(3))NMe(2) (4) was prepared from SiF(4) and (Me(3)Sn)(2)NNMe(2) (5). The compounds were characterized by gas-phase IR and multinuclear NMR spectroscopy ((1)H, (13)C, (14/15)N, (19)F, (29)Si, (119)Sn), as well as by mass spectrometry. The crystal structures of compounds 1-5 were determined by X-ray crystallography. The structures of free molecules 1 and 3 were determined by gas-phase electron diffraction. The structures of 1, 2, and 4 were also determined by ab initio calculations at the MP2/6-311+G** level of theory. These structural studies constitute the first experimental proof for the presence of strong Si.N beta-donor-acceptor bonds between the SiF(3) and geminal NMe(2) groups in silylhydrazines. The strength of these non-classical Si.N interactions is strongly dependent on the nature of the substituent at the alpha-nitrogen atom of the SiNN unit, and has the order 3>4>1. The valence angles at these extremely deformed alpha-nitrogen atoms, and the Si.N distances are (crystal/gas): 1 104.2(1)/106.5(4) degrees, 2.438(1)/2.510(6) A; 3 83.6(1)/84.9(4) degrees, 2.102(1)/2.135(9) A; 4 89.6(1) degrees, 2.204(2) A.     

Collective and single-molecule interactions of alpha5beta1 integrins

A novel biomimetic system was used to study collective and single-molecule interactions of the alpha5beta1 receptor-GRGDSP ligand system with an atomic force microscope (AFM). Bioartificial membranes, which display peptides that mimic the cell adhesion domain of the extracellular matrix protein fibronectin, are constructed from peptide-amphiphiles. The interaction measured with the immobilized alpha5beta1 integrins and GRGDSP peptide-amphiphiles is specifically related to the integrin-peptide binding. It is affected by divalent cations in a way that accurately mimics the adhesion function of the alpha5beta1 receptor. The recognition of the immobilized receptor was significantly increased for a surface that presented both the primary recognition site (GRGDSP) and the synergy site (PHSRN) compared to the adhesion measured with surfaces that displayed only the GRGDSP peptide. At the collective level, the separation process of the receptor-ligand pairs is a combination of multiple unbinding and stretching events that can accurately be described by the wormlike chain (WLC) model of polymer elasticity. In contrast, stretching was not observed at the single-molecule level. The dissociation of single alpha5beta1-GRGDSP pairs under loading rates of 1-305 nN/s revealed the presence of two activation energy barriers in the unbinding process. The high-strength regime above 59 nN/s maps the inner barrier at a distance of 0.09 nm along the direction of the force. Below 59 nN/s a low-strength regime appears with an outer barrier at 2.77 nm and a much slower transition rate that defines the dissociation rate (off-rate) in the absence of force (k(off) degrees = 0.015 s(-1)).     

Cluster Chemsitry. 96. Penta- and hexa-nuclear ruthenium cluster complexes derived from reactions of cyclopentadienes with Ru5(μ5-C2PPh2)(μ-PPh2)(CO)13

The reactions between Ru₅( ₅-C₂PPh₂)(gm-PPh₂(CO)₁₃ (1) and cyclopentadienes afforded the hexanuclear clusters Ru₆( ₆-C)( ₃-PPh₂)₂(CO)₁₀(-C₅ R ₅) [R ₅ = H₅ (2), H₄Me (3), Me₅ (4)] which contain an encapsulated carbide and a face-capping ₃-CH group, formed by cleavage of CC and CP bonds of the C₂PPh₂ moiety in1. In the reaction with cyclopentadiene, the unusual ligand C₁₃H₁₂O, formed by combination of C₂, CO and two molecules of C₅H₆ (or one molecule of dicyclopentadien), was characterized in the complex Ru₅( ₄-PPh) ( ₄-C₁₃H₁₂O)(-PPh₂(CO)₁₁(-C₅H₅) (5). In the reaction with pentamethylcyclopentadiene, the vinylidene complex Ru₅( ₃-CCHPh)( ₄-PPh)( ₄-PPh) (-PPh₂)(CO)₉(-C₅Me₅) (6) was also formed.     

Efficient synthesis of cellulose furoates in 1-<Emphasis Type="Italic">N</Emphasis>-butyl-3-methylimidazolium chloride

The ionic liquid 1-N-butyl-3-methylimidazolium chloride ([C₄mim]⁺Cl⁻) was investigated as reaction media for the homogeneous acylation of cellulose with 2-furoyl chloride in the presence of pyridine. The preparation of cellulose furoate depending on the reaction conditions, the cellulose type and the pyridine content was studied. Cellulose furoates with a degree of substitution in the range from 0.46 to 3.0 were accessible, i.e., under mild conditions, with a low excess of reagent and in a short reaction time. The products were characterized by elemental analysis, perpropionylation, ¹H- and ¹³C NMR spectroscopy and FTIR spectroscopy. Thomas Heinze is the member of the European Polysaccharide Network of Excellence (EPNOE), www.epnoe.eu     

First organocatalyzed asymmetric Michael addition of aldehydes to vinyl sulfones

[reaction: see text] The first asymmetric direct Michael addition of aldehydes to vinyl sulfones catalyzed by N-iPr-2,2'-bipyrrolidine is described. 1,4-Adducts are obtained in good yields and enantioselectivities. The determination of absolute configuration allowed us to postulate a Si,Si transition state model, as shown previously for nitroolefins.     

Determination of trace impurities in tin by neutron activation analysis

A method was developed for the determination of 15 trace elements in tin. High-purity tin samples (99.9999% and 99.999%) as well as tin of technical quality were analysed. Reactor neutron activation of the tin samples was followed by distillation of the matrix activities from a HBr−H₂SO₄ medium and Ge(Li) gamma-ray spectrometry of the distillation residue. The sensitivity of the method is generally high. For the high-purity samples the detection limits vary from 0.02 ppb (scandium) to 200 ppb (iron) for irradiation of 1 g of tin for 1 week at a thermal flux of 5·10¹²n·cm⁻². ·sec⁻¹. To decontaminate the surface of the tin samples, pre- and post-irradiation etching procedures were applied. The efficiency of these etching techniques was studied.     

Automorphism groups of finite distributive lattices with a given sublattice of fixed points

For a latticeL, aL is a fixed point ofL if and only iff(a)=a for every automorphismf ofL. Let Aut (L) andS (L) denote the group of automorphisms ofL and the sublattice of fixed points ofL, respectively. It is shown that ifG is a finite group other thanZ ₂ ² ,Z ₂ ³ ,Z ₂ ⁴ ,Z ₃ ² or the quaternion group of order 8 andL is a finite automorphism free distributive lattice that is not near Boolean then there is a finite distributive latticeL such that Aut (L)G andS(L)L.The support of the National Research Council of Canada is gratefully acknowledged.     

On the representation of electrostatic fields around ab initio charge distributions

Summary We compare two methods (Mulliken charges and a distributed multipole analysis, DMA) of representing an ab initio charge distribution for calculating the electrostatic field and potential outside the molecule, using pyrimidine and the RNA base uracil as examples. This is done using a 3-D graphical display of the electrostatic fields, which, when used with real-time rotation, zooming and clipping, has many advantages for qualitatively assessing the electrostatic interactions of a molecule. The errors involved in using Mulliken point charges may be of similar magnitude to the total electrostatic field in regions which are important in recognition processes. The DMA representation automatically includes the anisotropic electrostatic effects of non-spherical features in the charge distribution of each atom, and yet the displayed electrostatic fields around the atoms which have lone-pair density do not show marked anisotropy.