Stereoselection in Intramolecular Diels-Alder Reactions of 2-Cyano-1-azadienes: Indolizidine and Quinolizidine Synthesis.
Progress toward understanding the scope and diastereoselectivity of intramolecular Diels-Alder reactions using 2-cyano-1-azadienes is described herein. The resulting cyanoenamine products are underutilized intermediates in organic synthesis. Assembly of the Diels-Alder precursors was achieved using an improved imine condensation/oxidative cyanation protocol. By this method, several highly substituted indolizidine and quinolizidine architectures were constructed. Quantum mechanical DFT calculations at the B3LYP/6-31+G(d) level of theory were performed for these cyclizations and provide insights into the origins of the observed diastereoselectivities.
Department of Chemistry, 1102 Natural Sciences II, University of California , Irvine, California 92697-2025, United States.
Gidget C
GC
Tay
Department of Chemistry, 1102 Natural Sciences II, University of California , Irvine, California 92697-2025, United States.
Nicholas
N
Sizemore
Department of Chemistry, 1102 Natural Sciences II, University of California , Irvine, California 92697-2025, United States.
Scott D
SD
Rychnovsky