Molecular and crystal structure of ethylene acetal of <Emphasis Type="Italic">endo</Emphasis>-<Emphasis Type="Italic">endo</Emphasis>-3-trityloxymethylbicyclo[3.3.1]nonane-2-on-7-ol

Molecular structure of ethylene acetal of 3-trityloxymethylbicyclo[3.3.1]nonane-2-on-7-ol (3) was determined by X-ray investigation. It was revealed that 3 has endo-endo-configuration and adopt chair-boat-conformation. The distortion of rings was evaluated by calculation of the Zefirov–Palyulin and Cremer–Pople puckering parameters. Failure of esterification of 3 was rationalized in terms of steric hindrance and intramolecular hydrogen bonding.

Polarizing agents and mechanisms for high-field dynamic nuclear polarization of frozen dielectric solids

This article provides an overview of polarizing mechanisms involved in high-frequency dynamic nuclear polarization (DNP) of frozen biological samples at temperatures maintained using liquid nitrogen, compatible with contemporary magic-angle spinning (MAS) nuclear magnetic resonance (NMR). Typical DNP experiments require unpaired electrons that are usually exogenous in samples via paramagnetic doping with polarizing agents. Thus, the resulting nuclear polarization mechanism depends on the electron and nuclear spin interactions induced by the paramagnetic species. The Overhauser Effect (OE) DNP, which relies on time-dependent spin–spin interactions, is excluded from our discussion due the lack of conducting electrons in frozen aqueous solutions containing biological entities. DNP of particular interest to us relies primarily on time-independent, spin-spin interactions for significant electron–nucleus polarization transfer through mechanisms such as the Solid Effect (SE), the Cross Effect (CE) or Thermal Mixing (TM), involving one, two or multiple electron spins, respectively. Derived from monomeric radicals initially used in high-field DNP experiments, bi- or multiple-radical polarizing agents facilitate CE/TM to generate significant NMR signal enhancements in dielectric solids at low temperatures (<100 K). For example, large DNP enhancements (∼300 times at 5 T) from a biologically compatible biradical, 1-(TEMPO-4-oxy)-3-(TEMPO-4-amino)propan-2-ol (TOTAPOL), have enabled high-resolution MAS NMR in sample systems existing in submicron domains or embedded in larger biomolecular complexes. The scope of this review is focused on recently developed DNP polarizing agents for high-field applications and leads up to future developments per the CE DNP mechanism. Because DNP experiments are feasible with a solid-state microwave source when performed at <20 K, nuclear polarization using lower microwave power (<100 mW) is possible by forcing a high proportion of biradicals to fulfill the frequency matching condition of CE (two EPR frequencies separated by the NMR frequency) using the strategies involving hetero-radical moieties and/or molecular alignment. In addition, the combination of an excited triplet and a stable radical might provide alternative DNP mechanisms without the microwave requirement.     

Ceric ammonium nitrate-mediated detritylation of tritylated amines

Efficient deprotection of tritylated amines to the corresponding amines mediated by 20 mol % ceric ammonium nitrate [Ce(NH₄)₂(NO₃)₆, CAN], 10 equiv of acetic acid and 15 equiv of water in dichloromethane is presented. This method equally worked well in the case of morpholino nucleosides.     

Facile synthesis of N-(benzyl, methyl)-lysine as a building block for site-specifically lysine monomethylated peptides

Facile, mild and efficient one-pot preparation of N^α-Fmoc-N^ε-(benzyl, methyl)-lysine, a building block for monomethylated peptide synthesis, was described. This building block was proved to be efficient for the synthesis of site-specifically monomethylated peptide. Benzyl group, which was incorporated by reductive benzylation and removed via catalytic hydrogenolysis, served as an excellent protecting group.     

Zinc chloride homogeneous catalysis in the tritylation of hydroxyl- and amide-bearing molecules

A tritylation protocol based on the transfer of the triphenylmethylcarbenium ion from trityl acetate to substrates having hydroxyls, in the presence of catalytic amounts of ZnCl₂, is described. The advantages of this method are broad scope, mild conditions, and easy handling. The comparison with the procedure based on the use of equimolar mixture of TrCl and ZnCl₂ in the presence of TEA shows that comparable results are obtained. However, only this method allows reactions of secondary or benzylic alcohols such as oxidation or formation of symmetric ethers to be suppressed. Both procedures are successfully extended to simple and substituted amides. Irrespective of its low solubility in acetonitrile, even asparagine can be directly tritylated on its amide group.     

Fast EPR imaging at 300 MHz using spinning magnetic field gradients

Electron paramagnetic resonance imaging (EPRI) technology has rapidly progressed in the last decade enabling many important applications in the fields of biology and medicine. At frequencies of 300-1200 MHz a range of in vivo applications have been performed. However, the requisite imaging time duration to acquire a given number of projections, limits the use of this technique in many in vivo applications where relatively rapid kinetics occur. Therefore, there has been a great need to develop approaches to accelerate EPRI data acquisition. We report the development of a fast low-frequency EPRI technique using spinning magnetic field gradients (SMFG). Utilizing a 300 MHz CW (continuous wave) EPRI system, SMFG enabled over 10-fold accelerated acquisition of image projections. 2D images with over 200 projections could be acquired in less than 3s and with 20s acquisitions good image quality was obtained on large aqueous free radical samples. This technique should be particularly useful for in vivo studies of free radicals and their metabolism.     

Deconvolution of sinusoidal rapid EPR scans

In rapid scan EPR the magnetic field is scanned through the signal in a time that is short relative to electron spin relaxation times. Previously it was shown that the slow-scan lineshape could be recovered from triangular rapid scans by Fourier deconvolution. In this paper a general Fourier deconvolution method is described and demonstrated to recover the slow-scan lineshape from sinusoidal rapid scans. Since an analytical expression for the Fourier transform of the driving function for a sinusoidal scan was not readily apparent, a numerical method was developed to do the deconvolution. The slow scan EPR lineshapes recovered from rapid triangular and sinusoidal scans are in excellent agreement for lithium phthalocyanine, a trityl radical, and the nitroxyl radical, tempone. The availability of a method to deconvolute sinusoidal rapid scans makes it possible to scan faster than is feasible for triangular scans because of hardware limitations on triangular scans.     

An Efficient and Environmentally Friendly Method for Directly Converting Trityl and Benzyl Ethers to the Corresponding Acetates

Acid sensitive benzyl and trityl ethers are frequently used as protecting groups to mask alcohols. They are also needed to be transformed into more stable ester groups toward acids in multistep synthesis. A mild and efficient one‐pot protocol for the selective transformation of benzyl and trityl ethers into their corresponding acetates was successfully developed. Several distinct advantages to this procedure include direct transformation, minimal generation of waste, a non‐aqueous workup and the recovery and recycling of the benzyl acetate and trityl alcohol by‐products, which were readily recovered in greater than 90% yields.     

Friedel-Crafts catalysts as assistants in the tritylation of less reactive hydroxyls

Less reactive hydroxyls, such as those present in secondary alcohols and in some primary alcohols, phenols and carboxylic acids, were easily tritylated with the homogeneous assistance of equimolar quantities of chlorides of di- and trivalent metals in aprotic solvents. The metal ions allowed both high concentration of the effective reagent triphenylmethylcarbenium ion and mobilisation of the hydroxyl proton, thus giving rise to rapid, room temperature substitution reactions. The experimental conditions were so mild that other protected groups, such as alkyl- or trityl-protected carboxyls and (9-fluorenylmethoxycarbonyl)- or trityl-protected amino groups, remained unaffected.     

Molecular and supramolecular helicity induction in trityl group-containing compounds: The case of chiral 3,3,3-triphenylpropionic acid derivatives

The process of dynamic chirality transmission from permanent chirality element to stereodynamic triphenylmethyl group placed in the distance of 4 bonds, has been studied for series of optically active 3,3,3-triphenylpropionic acid derivatives. Structural analysis, carried out with the use of complementary methods and supported by theoretical calculations, enabled us to determine the mechanism of chirality transmission. The observed chirality transfer phenomenon, demonstrated unequivocally as raising of non-zero Cotton effects in the region of UV absorption of trityl group, is a cascade process driven by weak intramolecular interactions. Despite the much larger inductor-effector distance, the sensitivity in chirogenesis is comparable to other stereodynamic probes reported so far. In the crystalline phase, the combination of trityl group with amino acid moiety results in the formation of helical superstructures, where individual molecules are held together by hydrogen bonding cascades. The proper combination of functionalities in the molecule skeleton allows, to some extent, the control over the association process and authorizes determination of the trityl group as the supramolecular synthon.