Halide Anion Triggered Reactions of Michael Acceptors with Tropylium Ion

Tropylium bromide undergoes noncatalyzed, regioselective additions to a large variety of Michael acceptors. In this way, acrylic esters are converted into β‐bromo‐α‐cycloheptatrienylpropionic esters. The reactions are interpreted as nucleophilic attack of bromide ions at the electron‐deficient olefins and the approach of the tropylium ion to the incipient carbanion. Quantum chemical calculations were performed to elucidate the analogy to the amine‐ or phosphine‐catalyzed Rauhut–Currier reactions. Subsequent synthetic transformations of the bromo‐cycloheptatrienylated adducts are reported.     

Cycloaddition reactions of 2H-benzo[b]thiete and conjugated cyclic dienes

2H-Benzo[b]thiete 1 reacts with cyclopentadiene 3 in consecutive [8π + 2π]cycloadditions yielding the condensed heterocycles 6–8 . Tetracyclone 9 on the other hand gives only the monoadduct 10 . An [8π + 8π]cycloaddition can be observed for 1 and diphenylisobenzofuran 11 . The related π system 13 shows again consecutive [477π + 27π]processes ( 1 + 13 ← 14, 15 ).     

Polymer membranes in medicine

Mass transfer within the human body primarily occurs across biological membranes. Medicine mimics nature and uses synthetic membranes for therapeutic purposes. The state of the art of polymer membrane applications in medicine is reviewed. The target for membrane material developments is mainly the improvement of the patients' safety and convenience. To provide optimal blood compatibility a new biocompatible polymer for hemodialysis membranes has been developed in our group: a polycarbonate with polyether blocks. The copolymer is suitable for production of membranes with excellent performance. In addition to therapeutic purposes polymer membranes can provide diagnostic functions. Recently a blood glucose test strip based on a synthetic membrane has been developed. The membrane separates off the erythrocytes and contains enzymes and reagents. It enables the diabetic a precise and convenient measurement.     

Selective reductions. 56. Exploration of the B-haloisopinocampheylboranes for asymmetric reduction of ketones

A series of diisopinocampheylhaloboranes and monoisopinocampheyldihaloboranes were synthesized by the reaction of the corresponding boranes with the respective HX or X₂ (X = halogen) or by the hydroboration of α-pinene with the corresponding haloboranes. Stabilities of these haloboranes in various solvents were studied. Most of these haloboranes proved capable of reducing prochiral ketones to the alcohols with significant optical induction. When tested against a representative aromatic and aliphatic prochiral ketone, acetophenone and 3-methyl-2-butanone, respectively, α-phenethyl alcohol in 65–98% ee and 3-methyl-2-butanol in 28–59% ee were obtained. Some of them exhibited anomalous behavior.     

Organoboranes. 52. The successful ring enlargement of boracyclanes via sequential one-carbon homologation: The first synthesis of boracyclanes in the strained medium-ring range

Previous attempts to synthesize boracyclanes in the medium-ring range (9-, 10-, 11-, and 12-ring members) via cyclic hydroboration of α,ω-dienes have failed. However, their synthesis via the sequential one-carbon homologation of B-methoxyboracyclanes has been achieved utilizing the successive reaction of B-methoxyboracyclanes with in situ generated (chloromethyl)lithium (LiCH₂Cl): MeOB(CH₂)₅ → MeOB(CH₂)₆ → MeOB(CH₂)₇ → MeOB(CH₂)₈ → MeOB(CH₂)₉ → MeOB(CH₂)₁₀ → MeOB(CH₂)₁₁. The yields achieved are in the range of 75–85%. In each case the products are identified by conversion via the DCME reaction into the known cycloalkanones. This development provides the first entry into boracyclanes of the strained medium ring range.     

Automated Synthesis of 68Ga-Labeled DOTA-MGS8 and Preclinical Characterization of Cholecystokinin-2 Receptor Targeting

The new minigastrin analog DOTA-MGS8 targeting the cholecystokinin-2 receptor (CCK2R) used in this study displays the combination of two site-specific modifications within the C-terminal receptor binding sequence together with an additional N-terminal amino acid substitution preventing fast metabolic degradation. Within this study, the preparation of ⁶⁸Ga-labeled DOTA-MGS8 was validated using an automated synthesis module, describing the specifications and analytical methods for quality control for possible clinical use. In addition, preclinical studies were carried out to characterize the targeting potential. [⁶⁸Ga]Ga-DOTA-MGS8 showed a high receptor-specific cell internalization into AR42J rat pancreatic cells (~40%) with physiological expression of rat CCK2R as well as A431-CCK2R cells transfected to stably express human CCK2R (~47%). A favorable biodistribution profile was observed in BALB/c nude mice xenografted with A431-CCK2R cells and mock-transfected A431 cells as control. The high tumor uptake of ~27% IA/g together with low background activity and limited uptake in non-target tissue confirms the potential for high-sensitivity positron emission tomography of stabilized MG analogs in patients with MTC and other CCK2R-related malignancies.