At the double : DFT studies on the biosynthesis of prostacyclin (PGI2, see scheme) from prostaglandin H2 (PGH2) show two reaction mechanisms through two different oxidation states, an FeIV–porphyrin intermediate and an FeIII–porphyrin π‐cation radical, followed by a proton‐coupled electron‐transfer process.
Super powers! Uranium(VI) ions can be extracted from aqueous solutions into supercritical CO2 (sc‐CO2) via an ionic liquid phase that contained tri‐n‐butyl phosphate (TBP) as a complexing agent (see figure). This process has potential applications in the nuclear industry for removing actinides from nuclear waste.
Resolution through revolution : It is possible to extract 3,5‐dinitrobenzoyl‐protected amino acids enantioselectively with the aid of a table‐top centrifugal contact separator and a catalytic amount of a chiral host compound based on the Cinchona alkaloids. Enantioselectivities of up to 80 % could be reached in a single pass. This allows the development of a process for the continuous separation of racemates.
Chiral pyridoallenophanes! The synthesis and characterization of chiral acetylenic pyridoallenophanes along with 2,4‐ and 2,5‐pyridyl[Re(CO)4LBr] complexes are reported. The relative configurations of the four stereoisomers have been unambiguously assigned. Chromatographic resolution of the racemate of the C4 stereoisomer was accomplished and mirror‐image CD spectra have been obtained (see figure).
Insensitive energetic salts : A series of furazan‐functionalized tetrazolate‐based energetic salts (see figure) were synthesized and characterized. All of the salts exhibit excellent thermal stabilities and high positive heats of formation.
Can phosphinoboranes promote hydrogenation of carbonyl moieties? By means of B3LYP and MPW1K density functional calculations the likelihood of the oxidation of alcohols by phosphinoboranes R2PBR′2 ( 1 ) was explored. As a proof‐of‐principle, a theoretical study that tests the reversibility of the alcohol oxidation is reported. The potential of 1 as a metal‐free hydrogenation mediator is discussed for a series of hydrogen sources such as primary and secondary alcohols.
Polymer, heal thyself! Dynamic polymers formed by a reversible Diels–Alder reaction were formed and studied by using neutron scattering at room temperature. They were used to obtain thin films that displayed self‐healing at room temperature (see figure).
Contrasting magnetic properties : Two isostructural metal‐azido magnetic chains embedded in 3D threefold interpenetrated H‐bonded frameworks and separated by a long bpeado spacer have been assembled (see figure). Incorporation of Mn2+ displays a rarely observed antiferromagnetic Heisenberg chain, while incorporation of Co2+ displays a ferromagnetic Ising chain.
Towards polythiophene polyrotaxanes : The β‐substituted terthiophene [2]rotaxanes have been synthesized (see figure). Basic optical and electrochemical properties of the synthesized [2]rotaxanes are also reported.
Tuning in : The reaction of halocyclopentane organometallic reagents can be tuned by the choice of metal (see scheme). Cyclopentylmagnesium bromide reduces aldehydes and ketones to the corresponding alcohols. However, in the presence of ZnCl2, normal Grignard addition to the ketones gives tertiary alcohols with complete diastereoselectivity. These protocols were used in the asymmetric synthesis of two medicinally important compounds.
