[4 + 2] cycloadditions of iminoacetonitriles : synthesis of highly substituted tetrahydropyridines and indolizidine alkaloids

• Main Author: Tumidajski, Stephanie
• Other Authors: Rick L. Danheiser.
• Format: Others
• Language: English
• Published: Massachusetts Institute of Technology 2014
• Subjects: Chemistry.
• Online Access: http://hdl.handle.net/1721.1/84378

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemistry, 2013. === Cataloged from PDF version of thesis. === Includes bibliographical references. === Iminoacetonitriles participate as activated imino dienophiles in intermolecular and intramolecular aza Diels-Alder reactions affording tetrahydropyridines and indolizidines. The [alpha]-amino nitrile cycloadducts are versatile synthetic intermediates that participate in a variety of stereoselective transformations to further elaborate the six-membered ring. This thesis describes the scope of the intermolecular [4 + 2] cycloaddition of N-benzyliminoacetonitrile with unactivated and activated dienes, as well as, the synthetic elaboration of the cycloadducts. This thesis also describes the worked performed to complete the total syntheses of indolizidines (-)- 235B', (-)-235B", and (+)-235B" using the aza Diels-Alder reaction of an iminoacetonitrile as the key step. === by Stephanie Tumidajski. === Ph.D.