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Hierarchical and Programmable One-Pot Oligosaccharide Synthesis
Published on: September 6, 2019
Diastereodivergent Synthesis of Chiral Tetrahydropyrrolodiazepinediones via a One-Pot Intramolecular
Spandan Chennamadhavuni1, James S Panek1, John A Porco1
1Department of Chemistry and Center for Molecular Discovery (BU-CMD) , Boston University , 590 Commonwealth Avenue , Boston , Massachusetts 02215 , United States.
Abstract:
A modular and diastereodivergent synthesis of tetrahydro-1 H-pyrrolo[1,2 d]diazepine-(2,5)-diones is presented. The tetrahydropyrrolodiazepinedione scaffold is obtained via a base-mediated three-step isomerization/tandem cyclization of amino acid-coupled homoallylic amino esters. Diastereoselectivity of the process is mediated by the interplay of a kinetic cyclization event and a propensity for thermodynamic epimerization at two labile chiral centers, giving rise to two distinct major diastereomers dependent on starting material stereochemistry and reaction conditions selected. Herein, we present a synthetic and computational study for this tandem process on a variety of amino ester substrates.
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