Effect of ether versus ester tethering on Heck cyclizations

Ether tethers allow Heck cyclizations to proceed in high yields. Ester tethers lead to low yields. Styrene trapping experiments indicate that ester reactions form viable organopalladium intermediates that cannot cyclize efficiently.     

End-to-end correlation for a C-12 hydrocarbon chain

The 19F nuclear spin-lattice relaxation rate constants were measured as a function of magnetic field strength for 1,12-diaminododecane labeled at one end with a nitroxide radical and at the other with a trifluoromethyl group. The magnetic relaxation dispersion profile (MRD) reports the spectral density function appropriate to the end-to-end correlation function for the doubly labeled molecule. After extrapolation to zero concentration to eliminate the intermolecular relaxation contribution to relaxation, the resulting intramolecular MRD profile was compared with several model approaches. The rotational model for the spectral density functions as included in the Solomon-Bloembergen-Morgan equations does not describe the data well. The earlier model of Freed for nuclear spin relaxation induced by a freely diffusing paramagnetic co-solute is not rigorous for this case because the paramagnet is tethered to the observed nuclear spin and only a restricted space in the immediate vicinity of the nuclear spin is accessible for pseudo-translational diffusion of one end of the molecule with respect to the other. A generalization of the Torrey model for magnetic relaxation by translational diffusion developed by Nevzorov and Freed, which includes the effect of restrictions imposed by the finite length of the chain, describes the experiment within experimental errors. A simple modification of the Hwang-Freed model that does not specifically include the dynamical effects of the finite tether also provides a good approximation to the data when the tether chain is sufficiently long.     

An alternative route to tethered Ru(II) transfer hydrogenation catalysts

A new route towards a series of tethered η⁶-arene/Ru(II) catalysts for use in the transfer and pressure hydrogenation of ketones and aldehydes to alcohols is reported. The route proceeds through the formation of an amide from the diamine precursor, followed by reduction, rather than the direct alkylation of the diamine. This has the advantage that dialkylation of the amine is avoided during the synthesis. Through this new route, both racemic and enantiomerically-pure η⁶-arene/Ru(II) tethered catalysts can be prepared in high yield.     

Stereodivergent total asymmetric synthesis of polyhydroxylated pyrrolidines via tandem allylic epoxidation and intramolecular cyclization reactions

Epoxidation of the allylic alcohols 10 and 11 using the VO(acac)₂/t-BuOOH system followed by an intramolecular 5-exo cyclization of the resulting δ-epoxycarbamates 12, 13, 18, and 19 has been shown to provide a general and efficient solution for the asymmetric synthesis of polyhydroxy pyrrolidines. The requisite vicinal amino alcohol functionality was enantio-/regio-selectively installed by the Os-catalyzed asymmetric aminohydroxylation reaction of the designed achiral olefin 6.     

1,4-双(9-O-奎宁)-2,3-二氮杂萘-OsO4催化烯烃的不对称氨羟化反应

在氧化-供氮试剂N-氯代氨基甲酸苄酯存在下,1,4-双(9-O-奎宁)-2,3-二氮杂萘-OsO4催化剂在5种烯烃的不对称氨羟化反应中表现出极高的对映选择性(85%～99%e.e.)和区域选择性,产率48%～68%.     

Colloidal particle motion as a diagnostic of DNA conformational transitions

Tethered particle motion is an experimental technique to monitor conformational changes in single molecules of DNA in real time, by observing the position fluctuations of a micrometer-size particle attached to the DNA. This article reviews some recent work on theoretical problems inherent in the interpretation of TPM experiments, both in equilibrium and dynamical aspects.     

The Influence of Exocyclic Stereochemistry on the Tethered Aminohydroxylation Reaction

A new strategy that employs an exocyclic stereocenter to effect diastereocontrol in the tethered aminohydroxylation (TA) reaction is applied to the stereoselective synthesis of a range of amino alcohols in good to excellent yields, and with anti selectivities of up to 20:1. The influence of the reaction conditions and substrate parameters on the level of diastereocontrol is described. Furthermore, an “inside alkoxy” model is employed to rationalize the sense and degree of stereoselectivity observed in these systems.     

Model Biological Membranes and Possibilities of Application of Electrochemical Impedance Spectroscopy for their Characterization

Biological membranes are essential parts of living systems. They represent an interface between intracellular and extracellular space. Depending on their structure, they often perform very complex functions and play an important role in the transport of both charged and uncharged particles in any organism. Structure of the biological membranes, which play very important role in electrochemical processes inside living organisms, is very complicated and still not precisely defined and explained. Model lipid membranes are used to gain detail information about properties of real biological membranes and about associated electrochemical processes. Electrochemistry, especially electrochemical impedance spectroscopy (EIS), can play a useful role in the characterization of properties of model lipid membranes (planar and supported lipid bilayers, tethered lipid membranes, liposomes, etc.). This review is focused on model biological membranes and the possibilities and limitations of electrochemical methods and namely of EIS in this field.     

Inside back cover: highly stereoselective metal-free oxyaminations using chiral hypervalent iodine reagents (angew. Chem. Int. Ed. 14/2012)

About 30?% of the world's iodine production comes from the Chiba area in Japan, shown in the background of the picture (Map data (?) 2012 ZENRIN Imagery (?) 2012 TerraMetrics). Enantiomerically pure hypervalent iodine compounds are the key for metal-free, highly stereoselective oxyaminations of alkenes. In their Communication on page?3462?ff., T. Wirth and U. Farid report the use of the reaction for the facile synthesis of 2-arylprolinols.