Vibsatin A is a new neurotrophic vibsane-type diterpenoid comprising bridged bicyclo[4.2.1]nonane skeleton. Inspired by Sawamura’s works, we generated the bicyclic backbone through Conia-ene-derived 7-exo-dig cyclization from an enantiomerically enriched TIPS-based silyl enol ether. The reaction, catalyzed sensitive gold(I) complex, was efficiently performed on large scale glovebox free techniq...

2014 Proton n.m.r. relaxation time measurements have been made on bicyclo[2.2.2]octane (BCO) and bicyclo[2.2.2]oct-2-ene (BCOE). Measurements for each sample were made throughout the plastic and brittle phases, down to 77 K. The results have been interpreted in terms of the various molecular motions occurring in the solid. Below the plastic-brittle phase transition point anisotropic molecular r...

An asymmetric mechanism for correlated motion occurring in noninteracting pairs of adjacent orthogonal 1,4-bis(carboxyethynyl)bicyclo[1.1.1]pentane (BCP) rotators 1 in the solid state is unraveled and shown to play an important role in understanding the dynamics in the crystalline rotor, Bu4N+[1-]·H2O. Single crystal X-ray diffraction and calculation of rotor-rotor interaction energies combined...

The title compound, C(16)H(20)Cl(2)O(8), contains a central bicyclo-[2.2.2]octane skeleton with slightly twisted conformation. In this structure, the C-C bond lengths are in the range 1.525 (2)-1.552 (2) Å. Two sides of this skeleton have cis,cis acet-oxy substituents and the Cl atoms have a trans arrangement. An extensive network of weak C-H⋯O interactions stabilizes the crystal structure.

The facile preparation of a racemic hydrazine bridged diphosphonium compound possessing a ring system analogous to bicyclo[3.3.2]decane is reported. Although the reaction yield is low, the structure of the compound, which possesses an eight-membered ring, two phosphonium cationic centers, a biimino bridge, molecular chirality and two fused aromatic rings locked into roughly perpendicular planes...

1,6-Enynes with electron-donating substituents at the alkyne undergo gold(I)-catalysed single cleavage skeletal rearrangement, whereas substrates with electron-withdrawing substituents evolve selectively to double cleavage rearrangement. Theoretical calculations provide a qualitative rationale for these effects, and suggest that bicyclo[3.2.0]hept-5-enes are involved as intermediates. We provid...

A flexible approach to construct sterically congested bicyclo-alkenedione frameworks is reported. Under the action of potassium carbonate, α-sulphonyl cycloalkanones are added to functionalized allenyl esters, leading to a lactone intermediate that is subsequently reduced to initiate an intramolecular aldol cyclization to [3.2.1], [3.3.1], and [4.3.1] bicycles. Oxidation then affords bicyclic d...

The structure of the title compound [alternatively called (R)-(-)-1-aza-bicyclo-[2.2.2]octan-3-ol], C7H13NO, at 100 K has hexa-gonal (P61) symmetry. The structure shows a twist along the C-N pseudo-threefold axis. In the crystal, mol-ecules are linked via O-H⋯N hydrogen bonds, forming infinite chains along the c-axis direction. The crystal studied was twinned by merohedry (twin law: 010, 100, 0...