Intramolecular Cyclization of Carbonate and Thiocarbonate Derivatives of myo-Inositol in the Solid State: Implications for Acyl Group Transfer Reactions in Molecular Crystals
| Autor: | Shobhana Krishnaswamy, Mysore S. Shashidhar, Majid I. Tamboli, Rajesh G. Gonnade |
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| Jazyk: | angličtina |
| Rok vydání: | 2015 |
| Předmět: |
Stereochemistry
Carbonates Crystal engineering Crystal structure Radical cyclization Catalysis chemistry.chemical_compound Nucleophile Cyclization reactions Polymer chemistry Molecular crystals Nucleophilic substitution Chemistry Organic Chemistry Intermolecular reactions General Chemistry Intramolecular cyclizations Solid phase synthesis Cyclization Alcohols Synthesis (chemical) Electrophile Nucleophilic substitutions Polyols Chemical stability Thiocarbonate Solid state reactions Sugars Cyclitols Inositols Non-covalent interaction Crystal orientation |
| Zdroj: | IndraStra Global. |
| ISSN: | 2381-3652 |
| DOI: | 10.1002/chem.201501480 |
| Popis: | Racemic 4-O-phenoxycarbonyl and 4-O-phenoxythiocarbonyl derivatives of myo-inositol orthoformate undergo thermal intramolecular cyclization in the solid state to yield the corresponding 4,6-bridged carbonates and thiocarbonates, respectively. The thermal cyclization also occurs in the solution and molten states, but less efficiently, suggesting that these cyclization reactions are aided by molecular pre-organization, although not strictly topochemically controlled. Crystal structures of two carbonates and a thiocarbonate clearly revealed that the relative orientation of the electrophile and the nucleophile in the crystal lattice facilitates the intramolecular cyclization reaction and forbids the intermolecular reaction. The correlation observed between the chemical reactivity and the non-covalent interactions in the crystal of the reactants provides a way to estimate the chemical stability of analogous molecules in the solid state. � 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim. |
| Databáze: | OpenAIRE |
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