Practical syntheses of a CXCR3 antagonist

Two new, reliable syntheses of a pyrido[2,3-d]-pyrimidine inhibitor of the CXCR3 receptor are described. A nine-step synthesis of the CXCR3 inhibitor (1) from 2-aminonicotinic acid was demonstrated on a multikilogram scale and incorporates a classic resolution to deliver the enantioenriched active pharmaceutical ingredient (API). A second synthesis of the CXCR3 inhibitor starts from (+)-(D)-Boc alanine and 2-chloronicotinic acid and utilizes a Goldberg coupling. This second synthesis, performed on a gram scale, intersects the former route at a common intermediate thereby completing a formal synthesis of the enantioenriched API in higher overall yield without the need for a resolution.     

Solution structure of copper-seamed C-alkylpyrogallol[4]arene nanocapsules with varying chain lengths

The stability of copper-seamed C-alkylpyrogallol[4]arene hexamers with varying chain lengths in solution has been studied using small-angle neutron scattering (SANS). The progression in diameter of spherical capsules with increasing alkyl chain lengths of copper-seamed hexamers in solution suggests both robustness as well as a close correlation between the solid phase and solution phase structures.     

Cucurbit[7]uril: an amorphous molecular material for highly selective carbon dioxide uptake

Cucurbit[7]uril (CB[7]), in its amorphous solid state, shows one of the highest CO(2) sorption capacities among known organic porous materials at 298 K and 0.1 and 1 bar. In addition to the highest CO(2) capacity, CB[7] also shows remarkable selectivity of CO(2) over N(2) and CH(4). These properties, along with the existence of readily available precursors, indicate amorphous CB[7] might find applications in recycling CO(2) particularly considering the easy synthesis and potentially low manufacturing costs.     

Gas-induced solid state transformation of an organic lattice: from nonporous to nanoporous

A well-known organic host, tris-o-phenylenedioxycyclotriphosphazene, exists in two polymorphic guest-free forms: the thermodynamic nonporous high-density phase and the kinetic nanoporous low-density phase. Simple pressurization of the high density phase with CO(2) brings a solid-state transformation to the low density phase, resulting in significant expansion of the crystal volume by 23%.     

Solvent and hydrogen confinement in molecular capsules-Hirshfeld surface and molecular simulation analysis

Hirshfeld surface analysis of the 'ordered' inner phase of the molecular capsule complex, [(chloroform)(6)@C-n-butylpyrogallol[4]arene)(6)], provides insight into the intermolecular contacts and orientation of the solvent molecules. Molecular simulations show that adding two or three hydrogen molecules to the six solvent molecules is energetically favoured, and this correlates with NMR studies.     

First-Order geometrical response equations for state-averaged multiconfigurational self-consistent field (SA-MCSCF) wave functions

The first-order geometrical response equations for a state-averaged multiconfigurational self-consistent field (SA -MCSCF ) calculation are derived. This derivation is carried through from first principles to final working equations suited for computer implementation. The final equations are expressed such that the energies and wave functions must be known only for the internal SA -MCSCF states. In the derivation, the special but important case where two or more internal states have equal weighting factors is treated in a manner fully consistent with all other cases. Except for introducing extra equations that are straightforward to solve, the case where two or more internal states have equal weighting factors introduces no new complications.     

Editorial announcement

Editorial announcement     

Reaction of trimethylaluminum with crown ethers. IV. Crystal structure of (18-crown-6)tetrakis-(trimethylaluminum)·p-xylene solvate

The title compound was prepared by the addition of A1Me₃ to a suspension of 18-crown-6 inp-xylene. The large, colorless, air-sensitive crystals belong to the monoclinic space group P2₁/n witha=14.822(6),b=7.894(4),c=18.805(6) Å,=105.40(4)°, andD _calc=1.03 g cm^–3 forZ=2. The finalR value based on 1758 observed reflections is 0.043. The molecule lies on a crystallographic inversion center and exhibits four strong Al-O bonds. The two independent Al-O distances are 1.978(3) and 2.000(3) Å. The oxygen atoms deviate from the mean plane of the crown, alternating above and below, by 0.13, 0.15, and 0.20 Å, respectively. Thep-xylene molecule is also positioned about a center of inversion.     

The formation and molecular structure of acetylcyclopentadienylsodium-tetrahydrofuranate

Acetylcyclopentadienylsodium has been isolated in crystalline form as a THF adduct from a reaction between cyclopentadienylsodium and methyl acetate in THF solution. The product has been characterized by means of a single-crystal X-ray diffraction study. {[C₅H₄CMeO]Na·THF}_n crystallizes in the monoclinic space group P2₁/c with unit cell parameters a 6.698(3), b 16.095(4), c 10.661(3) Å, β 92.93(3)° and D_c 1.17 g cm^?3 for Z = 4. Least-squares refinement led to a final R value of 0.080 based on 661 independent observed reflections. The coordination sphere around each sodium atom consists of the oxygen atoms from two C₅H₄CMeO ligands, the oxygen atom of the THF molecule, and an ion contact pair between the sodium and the five ring carbon atoms of the C₅H₄CMeO ligand.