Homoatomic polyanions of post-transition main-group metals, namely, Zintl anions, are precast in analogous Zintl phases and can react in solution to form new materials. Despite comprehensible reaction approaches, the formed products cannot be planned in advance, as hitherto undetected and therefore disregarded side reactions take place. The outcomes and interpretations of the reactions of Zintl anions are so far based mainly on crystal structures, which only allow characterization of the product that has the lowest solubility. Here we present the results of our investigation of the stability of highly charged tin Zintl anions in liquid ammonia, which is not exclusively based on solution effects but also on the oxidative influence of the solvent. This allows for a deeper understanding of the ongoing processes in solution and opens doors to the directed synthesis of transition metal complexes of Sn₄⁴⁻, here shown by its reactivity towards MesCu.

During the last decade, phosphoramidites have been established as a so-called privileged class of ligands in various transition metal catalyses. However, the interactions responsible for their favorable properties have hitherto remained elusive. To address this issue, the formation trends, structural features, and interligand interaction patterns of several trans- and cis-[PdLL′Cl₂] complexes have been investigated by NMR spectroscopy. The energetic contribution of their interligand interactions has been measured experimentally using the supramolecular balance for transition-metal complexes. The resulting energetics combined with an analysis of the electrostatic potential surfaces reveal that in phosphoramidites not only the aryl groups but the complete (CH)CH₃Ph moieties of the amine side chains form extended quasi-planar CH-π and π-π interaction surfaces. Application of the supramolecular balance has shown that modulations in these extended interaction surfaces cause energetic differences that are relevant to enantioselective catalysis. In addition, the energetics of these interligand interactions are quite independent of the actual structures of the complexes. This is shown by similar formation and aggregation trends of complexes with the same ligand but different structures. The extended quasi-planar electrostatic interaction surface of the (CH)CH₃Ph moiety explains the known pattern of successful ligand modulation and the substrate specificity of phosphoramidites. Thus, we propose modulations in these extended CH-π and π-π interaction areas as a refined stereoselection mode for these ligands. Based on the example of phosphoramidites, this study reveals three general features potentially applicable to various ligands in asymmetric catalysis. First, specific combinations of alkyl and aryl moieties can be used to create extended anisotropic interaction areas. Second, modulations in these interaction surfaces cause energetic differences that are relevant to catalytic applications. Third, bulky substituents with matching complementary interaction surfaces should not only be considered in terms of steric hindrance but also in terms of attractive and repulsive interactions, a feature that may often be underestimated in asymmetric catalysis.

As part of our ongoing studies to provide an experimental basis for the improved understanding of organocatalytic reaction mechanisms we present a study on the influence of amine bases on enamine intermediate stabilization in proline catalysis. The (partial) deprotonation of the proline acid function is displayed by characteristic shifts of certain proton resonances and is also manifested by an increase of the amount of enamine intermediate upon reaching a critical pK_aH. Strong bases, such as 1,8-diazabicyclo[5.4.0]-undec-7-ene (DBU), allow for outstanding enamine stabilization in various solvents and, hence, permit the detection of enamine species that have been inaccessible until now (illustrated by the observation of minor amounts of Z enamines). The in situ NMR detection of a prolinate–DBUH⁺ ion pair supports the well-documented reversal of enantioselectivity of proline-catalyzed aminations in the presence of amine bases by disabling the bifunctional activity and switching to a “simple” stereocontrol effect (as known from the Jørgensen/Hayashi-type diarylprolinol ethers). In addition, the possibility of attractive ionic interactions between both the iminium ion and prolinate enamines available in the presence of strong amine bases suggests promotion of the Mannich pathway in aldol reactions to mainly form condensation products.

Monoalkylated acylguanidines are important functional groups in many biologically active compounds and additionally applied in coordination chemistry. Yet a straightforward assignment of the individual NH chemical shifts and the acylguanidine conformations is still missing. Therefore, in this study, NMR spectroscopic approaches for the chemical and especially the conformational assignment of protonated monoalkylated acylguanidines are presented. While NOESY and ³J_{H, H} scalar couplings cannot be applied successfully for the assignment of acylguanidines, ⁴J_{H, H} scalar couplings in ¹H,¹H COSY spectra allow for an unambiguous chemical shift and conformational assignment. It is shown that these ⁴J_{H, H} long-range couplings between individual acylguanidinium NH resonances are observed solely across all-trans (w) pathways. Already one cis orientation in the magnetisation transfer pathway leads to signal intensities below the actual detection limit and significantly lower than cross-peaks from ²J_{NH, NH} couplings or chemical exchange. However, it should be noted that also in the case of conformational exchange being fast on the NMR time scale, averaged cross-peaks from all-trans⁴J_{H, H} scalar couplings are detected, which may lead at first glance to an incomplete or even wrong conformational analysis. Copyright © 2010 John Wiley & Sons, Ltd.

Short relaxation times and small diffusion coefficients often impede reliable diffusion experiments due to insufficient signal to noise ratios, especially in low temperature studies, where in the case of small diffusion coefficients in combination with very short T₂ times and substantial convection, double-stimulated-echo experiments are required as last resort of convection-compensating DOSY pulse sequences. Therefore, the combination of a strong gradient amplifier of a diffusion unit with Z-gradient high resolution probes is tested for low temperature applications to combine the advantages of high ¹H resolution, flexible temperature, and multinuclear applications with short gradient durations and diffusion delay. The experimental spectra on phosphoramidite ligands and phosphoramidite-copper complexes show that signal to noise improvements up to 176% were achieved despite longer eddy current delays and increased noise levels. Calculational estimations of the enhancement factors predict special benefits for systems with short transversal relaxation times and small diffusion coefficients and promise even higher enhancement factors for noise level optimized combinations. In addition, an easy way is presented to find fast and effectively relaxation optimized DOSY parameters for the convection-compensated double-stimulated-echo pulse sequence of Jerschow and Müller. Copyright © 2009 John Wiley & Sons, Ltd.

A straightforward convergent synthesis of [¹⁵N]-Bz-Arg(N^η-propionyl)-OEt^*TFA is presented. In this approach, the guanidinylation reagent [¹⁵N₂]-N(boc)-N′(propionyl)-S-methylisothiourea is reacted with the side chain amino group of the title compound's ornithine precursor. The guanidinylation step is promoted by stoichiometric addition of HgCl₂ to force completion. This method leads directly to the N^G-acylated product and the acyl residue is principally modifiable in the last synthetic step of the guanidinylation reagent. Copyright © 2008 John Wiley & Sons, Ltd.