Diverse and Yet Unified: A Comparative Study of the Supramolecular Assemblies of Three Diastereomeric Perhydro‐2,3,4a,6,7,8a‐naphthalenehexols

Abstract

Self-assemblies of three crystalline perhydro-2,3,4a,6,7,8a-naphthalenehexols 3-5, all constructed on a trans-decalin framework, were compared with each other and to that of their diastereomeric all axial hydroxy sibling 2, which was previously reported. The presence of the peripheral equatorial OH groups in 3-5 severs, to varying extents, the end-toend intramolecular O-H···O hydrogen-bonding chain linking the 1,3-diaxial hydroxy groups on both faces of hexol 2. Hence, the crystal packing in 3-5 deviates from the simple qualitative model proposed and observed in 2. Though com-

Synthesis of Anti–-anti (anti–-syn)-3,4:8,9-Tetraacetoxy-11-Oxa-Tricyclo [4.4.1.01,6]Undecanes

“…Shani and Sondheimer studied the bromination reactions of diene after opened of epoxide ring in compound 14. 21 Recently, Mehta et al 22,23 studied the bromination and oxidation reactions of dienes after opened of epoxide ring in compound 14. Additionally, they put forward that oxidation and acetylation of one of two double bonds in sides followed epoxidation with mCPBA gave two isomers as anti and syn in a ratio of 10:1, respectively.…”

A Vicarious One-Pot Transformation of a Fluorocyclitol to a Polycyclitol: Observation of a Formal 4-Fold Axial−Equatorial Epimerization on a Conformationally Locked Scaffold

“…Hence, the molecular packing in crystalline 2 was effected entirely via the agency of strong intermolecular O−H···O hydrogen bonds, with each hexol molecule engaging itself in 12 H-bonds and being linked to 8 nearest neighbors. In fact, the large number of intermolecular O−H···O hydrogen bonds (the highest per molecule in the crystal structure of any of the perhydro-2,3,4a,6,7,8a-naphthalenehexols studied so far) and an efficient close packing (packing index = 72.4%) in the solid-state self-assembly of 2 would probably explain the unique physical properties (melting point and solubility) of the hexol, already alluded to. , …”

“…Although the trans - anti - trans - anti - trans relationship of the hydroxy groups in the C 2 h -symmetric hexol 2 could be discerned from its NMR spectral data, it appeared prudent, given the unconventional nature of its formation, to confirm the stereostructure of 2 through single crystal X-ray diffraction studies. Implicit in this endeavor was also an opportunity to study the solid-state self-assembly of 2 and glean a possible rationale for its unusually high melting point (>300 °C) and near insolubility in most organic solvents as compared to its known diastereomers. , …”