Solvent effect in diastereoselective intramolecular Diels–Alder reactions
作者： Anna Tomberg , Stéphane De Cesco , Mitchell Huot , Nicolas Moitessier
DOI: 10.1016/J.TETLET.2015.10.086
关键词: Cycloaddition 、 Intermolecular force 、 Stereoselectivity 、 Stereochemistry 、 Transition state 、 Acylation 、 Solvent effects 、 Diastereomer 、 Intramolecular force 、 Chemistry
摘要: In the process of improving synthesis a novel class chiral drug scaffolds, first reported in 2010, we observed that stereochemical outcome key chemical transformation appeared to be correlated solvophobicity reaction medium. Our mechanistic investigations by NMR monitoring confirmed proposed acylation/intermolecular cycloaddition sequence. The computational studies using DFT methods next predicted exo/endo stereoselectivity (4.3:1 CHCl3, 1.6:1 H2O) agreement with experimental results (3.3:1 1:1 H2O). was related different level asynchronicity diastereomeric transition states. This leads solvent stabilization state one diastereomer more than other.
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