A Samarium(II)-mediated, stereoselective cyclization for the synthesis of azaspirocycles

Unsaturated keto-lactams undergo sequential conjugate reduction-aldol cyclization on treatment with SmI 2 to give syn-spirocyclic pyrrolidinones and piperidinones containing vicinal, fully substituted stereocenters with complete diastereocontrol. The substituent on nitrogen and the lactam ring size have a marked impact on the efficiency of the spirocyclization.     

Multicomponent synthesis of 3-heteroarylpropionic acids

A four component one-pot procedure (4-MC) was developed to assemble 3-heteroarylpropionic acids from commercially available materials. This new methodology affords the title compounds in high yields and without the use of chromatography. [reaction: see text]     

Fragmentation of Neutral Amino Acids and Small Peptides by Intense, Femtosecond Laser Pulses

High power femtosecond laser pulses have unique properties that could lead to their application as ionization or activation sources in mass spectrometry. By concentrating many photons into pulse lengths approaching the timescales associated with atomic motion, very strong electric field strengths are generated, which can efficiently ionize and fragment molecules without the need for resonant absorption. However, the complex interaction between these pulses and biomolecular species is not well understood. To address this issue, we have studied the interaction of intense, femtosecond pulses with a number of amino acids and small peptides. Unlike previous studies, we have used neutral forms of these molecular targets, which allowed us to investigate dissociation of radical cations without the spectra being complicated by the action of mobile protons. We found fragmentation was dominated by fast, radical-initiated dissociation close to the charge site generated by the initial ionization or from subsequent ultrafast migration of this charge. Fragments with lower yields, which are useful for structural determinations, were also observed and attributed to radical migration caused by hydrogen atom transfer within the molecule.

Characterization of the Oxygen Binding Motif in a Ruthenium Water Oxidation Catalyst by Vibrational Spectroscopy

For homogeneous mononuclear ruthenium water oxidation catalysts, the Ru–O₂ complex plays a crucial role in the rate determining step of the catalytic cycle, but the exact nature of this complex is unclear. Herein, the infrared spectra of the [Ru(tpy)(bpy)(O₂)]²⁺ complex (tpy=2,2′:6′,2′′‐terpyridine; bpy=2,2′‐bipyridine) are presented. The complex [Ru(tpy)(bpy)(O₂)]²⁺, formed by gas‐phase reaction of [Ru(tpy)(bpy)]²⁺ with molecular O₂, was isolated by using mass spectrometry and was directly probed by cryogenic ion IR predissociation spectroscopy. Well‐resolved spectral features enable a clear identification of the O?O stretch using ¹⁸O₂ substitution. The band frequency and intensity indicate that the O₂ moiety binds to the Ru center in a side‐on, bidentate manner. Comparisons with DFT calculations highlight the shortcomings of the B3LYP functional in properly depicting the Ru–O₂ interaction.     

Estimating Loynes�� exponent

Loynes?? distribution, which characterizes the one dimensional marginal of the stationary solution to Lindley??s recursion, possesses an ultimately exponential tail for a large class of increment processes. If one can observe increments but does not know their probabilistic properties, what are the statistical limits of estimating the tail exponent of Loynes?? distribution? We conjecture that in broad generality a consistent sequence of non-parametric estimators can be constructed that satisfies a large deviation principle. We present rigorous support for this conjecture under restrictive assumptions and simulation evidence indicating why we believe it to be true in greater generality.     

New products

The Seventh International Workshop on Infrared Microscopy and Spectroscopy with Accelerator-Based Sources (WIRMS 2013) was hosted by the Australian Synchrotron at the Mantra Resort in the coastal town of Lorne on the Great Ocean Road west of Melbourne, Australia, from November 10 to 14, 2013. In common with previous WIRMS meetings, the conference saw a coming together of staff and users from the world's synchrotron and free electron laser facilities, several of which were represented at the meeting for the first time. Scientific highlights of WIRMS 2013 included reports on FTIR spectro-microtomography, near-field infrared imaging, and cultural heritage applications.