Ambident Reactivity of Imidazolium Cations as Evidence of the Dynamic Nature of N-Heterocyclic Carbene-Mediated Organocatalysis

This work reveals ambident nucleophilic reactivity of imidazolium cations towards carbonyl compounds at the C2 or C4 carbene centers depending on the steric properties of the substrates and reaction conditions. Such an adaptive behavior indicates the dynamic nature of organocatalysis proceeding via a covalent interaction of imidazolium carbenes with carbonyl substrates and can be explained by generation of the H-bonded ditopic carbanionic carbenes.     

Highly Enantioselective,Organocatalytic, and Scalable Synthesis of a Rare cis,cis-Tricyclic Diterpenoid

A highly enantioselective, organocatalytic, and scalable synthesis of a very unusual cis-decalin-cis-hydrindane tricyclic diterpenoid system has been achieved. Despite the prevalent pharmacological space that the related trans,trans and trans,cis-systems occupy, there have been no reports of an asymmetric synthesis of the cis,cis systems in the literature until now. We demonstrate the flexibility of our approach not only through access to a diverse range of products, all of which are attained in exceptionally high selectivities, but also by showing their easy conversion to the corresponding trans,cis-system and other derivatives.     

One Way Traffic: Base-to-Backbone Hole Transfer in Nucleoside Phosphorodithioate

The directionality of the hole-transfer processes between DNA backbone and base was investigated by using phosphorodithioate [P(S⁻)=S] components. ESR spectroscopy in homogeneous frozen aqueous solutions and pulse radiolysis in aqueous solution at ambient temperature confirmed initial formation of G^.+-P(S⁻)=S. The ionization potential of G-P(S⁻)=S was calculated to be slightly lower than that of guanine in 5′-dGMP. Subsequent thermally activated hole transfer from G^.+ to P(S⁻)=S led to dithiyl radical (P-2S^.) formation on the μs timescale. In parallel, ESR spectroscopy, pulse radiolysis, and density functional theory (DFT) calculations confirmed P-2S^. formation in an abasic phosphorodithioate model compound. ESR investigations at low temperatures and higher G-P(S⁻)=S concentrations showed a bimolecular conversion of P-2S^. to the σ²-σ*¹-bonded dimer anion radical [-P-2S 2S-P-]⁻ [ΔG (150 K, DFT)=−7.2 kcal mol⁻¹]. However, [-P-2S 2S-P-]⁻ formation was not observed by pulse radiolysis [ΔG° (298 K, DFT)=−1.4 kcal mol⁻¹]. Neither P-2S^. nor [-P-2S 2S-P-]⁻ oxidized guanine base; only base-to-backbone hole transfer occurs in phosphorodithioate.     

Regioselective Hydroformylation of Internal and Terminal Alkenes via Remote Supramolecular Control

Regioselective catalytic transformations using supramolecular directing groups are increasingly popular as it allows for control over challenging reactions that may otherwise be impossible. In most examples the reactive group and the directing group are close to each other and/or the linker between the directing group is very rigid. Achieving control over the regioselectivity using a remote directing group with a flexible linker is significantly more challenging due to the large conformational freedom of such substrates. Herein, we report the redesign of a supramolecular Rh–bisphosphite hydroformylation catalyst containing a neutral carboxylate receptor (DIM pocket) with a larger distance between the phosphite metal binding moieties and the DIM pocket. For the first time regioselective conversion of internal and terminal alkenes containing a remote carboxylate directing group is demonstrated. For carboxylate substrates that possess an internal double bond at the Δ-9 position regioselectivity is observed. As such, the catalyst was used to hydroformylate natural monounsaturated fatty acids (MUFAs) in a regioselective fashion, forming of an excess of the 10-formyl product (10-formyl/9-formyl product ratio of 2.51), which is the first report of a regioselective hydroformylation reaction of such substrates.     

Organoboron Derivatives of Stereoregular Phenylcyclosilsesquioxanes

This study presents the synthesis of organoboron derivatives of stereoregular 4-, 6-, and 12-unit phenylcyclosilsesquioxanes. All compounds obtained were isolated in good yields (70–80 %) and were fully characterized by ¹H, ¹³C, ²⁹Si, ¹¹B NMR, IR spectroscopy, HRMS ESI, and elemental microanalysis. The structure of the key modifier, obtained for the first time, 4-(tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl) dimethylvinylsilane, was also confirmed by single-crystal XRD.     

Directed Gas Phase Formation of Silene (H2SiCH2)

The silene molecule (H₂SiCH₂; X¹A₁) has been synthesized under single collision conditions via the bimolecular gas phase reaction of ground state methylidyne radicals (CH) with silane (SiH₄). Exploiting crossed molecular beams experiments augmented by high-level electronic structure calculations, the elementary reaction commenced on the doublet surface through a barrierless insertion of the methylidyne radical into a silicon-hydrogen bond forming the silylmethyl (CH₂SiH₃; X²A′) complex followed by hydrogen migration to the methylsilyl radical (SiH₂CH₃; X²A′). Both silylmethyl and methylsilyl intermediates undergo unimolecular hydrogen loss to silene (H₂SiCH₂; X¹A₁). The exploration of the elementary reaction of methylidyne with silane delivers a unique view at the widely uncharted reaction dynamics and isomerization processes of the carbon–silicon system in the gas phase, which are noticeably different from those of the isovalent carbon system thus contributing to our knowledge on carbon silicon bond couplings at the molecular level.     

Melamine–Barbiturate Supramolecular Assembly as a pH-Dependent Organic Radical Trap Material

In the last two decades, a large number of self-assembled materials were synthesized and they have already found their way into large-scale industry and science. Hydrogen-bond-based supramolecular adducts are found to have unique properties and to be perfect host structures for trapping target molecules or ions. Such chemical systems are believed to resemble living matter and can substitute a living cell in a number of cases. Herein, a report on an organic material based on supramolecular assembly of barbituric acid and melamine is presented. Surprisingly, the structure is found to host and stabilize radicals under mild conditions allowing its use for biological applications. The number of free radicals is found to be easily tuned by changing the pH of the environment and it increases when exposed to light up to a saturation level. We describe a preparation method as well as stability properties of melamine–barbiturate self-assembly, potentiometric titration, and hydrogen ions adsorption data and EPR spectra concerning the composite.     

Structure and conductivity of AOT solutions in n-hexadecane-chloroform mixtures

The structure and conductivity of AOT (sodium bis(2-ethylhexyl) sulfosuccinate) solutions (2.5 × 10⁻⁴–2.5 × 10⁻¹ M) in n-hexadecane-chloroform mixture at the chloroform concentration from 50 to 100 vol% were studied. The diffusion ordered spectroscopy NMR study revealed that in the indicated range, the observed hydrodynamic diameter of micelles depends only on the AOT concentration and does not depend on the chloroform content. Molar fractions of free AOT molecules and those aggregated into micelles were calculated using the Lindman's law: at concentrations above 2.5 × 10⁻¹ М, the solutions contain mostly the micelles, whereas at concentrations below 2.5 × 10⁻⁴ M, the solutions contain AOT molecules. The transition region contains both the AOT molecules and the micelles. Conductivity measurements were used to determine free charge carriers in the bulk of solutions and their contributions to conductivity.