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  • Title: Origins of regio- and stereochemistry in type 2 intramolecular N-acylnitroso Diels-Alder reactions: a computational study of tether length and substituent effects.
    Author: Cleary L, Mak VW, Rychnovsky SD, Shea KJ, Sizemore N.
    Journal: J Org Chem; 2013 Apr 19; 78(8):4090-8. PubMed ID: 23477601.
    Abstract:
    Quantum mechanical calculations have been used to investigate type 2 intramolecular N-acylnitroso Diels-Alder reactions. Experimentally observed regioselectivities and diastereoselectivities of these reactions have been reproduced using B3LYP/6-31+G(d) DFT calculations. The factors that govern selectivity (i.e., tether length, tether substitution and diene substitution) were systematically investigated. Tethers less than 6 carbon atoms lead to 1,3-regioisomers due to conformational restrictions. Substituents on the tether lead to diastereoselective outcomes dictated by transannular interactions in the transition states. The modest diastereoselectivity of diene-substituted substrates is rationalized as arising from reduction of eclipsing interactions in the flattened diene transition states. This method should prove valuable for planning syntheses involving type 2 intramolecular Diels-Alder reactions.
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