Asymmetric Synthesis of Nitrogen Containing Bioactive Compounds via the Utilization of Enantiopure p-Toluenesulfinimines
type: CreativeWork
description: The research objective of this thesis research was to develop new methods for the asymmetric synthesis of amine derivatives using p-toluenesulfinimines. Enantiopure sulfinimines are versatile chiral building blocks for the asymmetric synthesis of alkaloids. Sulfinimines were prepared by the condensation of (S)- or (R)-p-toluenesulfinamide with aldehydes and ketones in good to excellent yields, which were prepared from the commercially available Anderson reagent. The first research project was the development of a new method for the preparation of enantiopure anti-anti- α-lkyl β-amino ketones and was accomplished by the stereoselective α-alkylation of enolates of sulfinimine derived β-amino esters. The anti- α-lkyl β-amino esters were transformed to their corresponding Weinreb amides by reacting with lithium dimethyl hydroxyl amine without epimerization. Reactions of the Weinreb amides with Grignard and organolithium reagents afforded the corresponding anti- α-lkyl β-amino ketones in modest yields and high optical purity. The modest yields are the results of competition between addition and reduction of the Weinreb amide. anti- α-lkyl β-amino ketones are important chiral building blocks for the asymmetric synthesis of nitrogen-containing biologically active molecules, such as pyrrolidines, piperidines and other alkaloids. To further illustrate the utility of sulfinimine -derived enantiopure N-sulfinyl anti- α-lkyl β-amino ketones, they was applied to the asymmetric synthesis of the unknown anti-C5, C6 derivative of 2,3,4,6-tetrasubsituted indolizidine 221-T. The key step in the synthesis was the stereoselective construction of the piperidine ring of the 5,6,8-tri-substituted indolizidine and was realized via the use of an acid-catalyzed intramolecular Mannich cyclization. The indolizidine was readily transformed in to the key intermediate 7-hydroxyl-2,3,4,6-tetrasubsituted indolizidine in high stereoselectivity and yield. Changing the sequence of chemical operation s…
abstract: The research objective of this thesis research was to develop new methods for the asymmetric synthesis of amine derivatives using p-toluenesulfinimines. Enantiopure sulfinimines are versatile chiral building blocks for the asymmetric synthesis of alkaloids. Sulfinimines were prepared by the condensation of (S)- or (R)-p-toluenesulfinamide with aldehydes and ketones in good to excellent yields, which were prepared from the commercially available Anderson reagent. The first research project was the development of a new method for the preparation of enantiopure anti-anti- α-lkyl β-amino ketones and was accomplished by the stereoselective α-alkylation of enolates of sulfinimine derived β-amino esters. The anti- α-lkyl β-amino esters were transformed to their corresponding Weinreb amides by reacting with lithium dimethyl hydroxyl amine without epimerization. Reactions of the Weinreb amides with Grignard and organolithium reagents afforded the corresponding anti- α-lkyl β-amino ketones in modest yields and high optical purity. The modest yields are the results of competition between addition and reduction of the Weinreb amide. anti- α-lkyl β-amino ketones are important chiral building blocks for the asymmetric synthesis of nitrogen-containing biologically active molecules, such as pyrrolidines, piperidines and other alkaloids. To further illustrate the utility of sulfinimine -derived enantiopure N-sulfinyl anti- α-lkyl β-amino ketones, they was applied to the asymmetric synthesis of the unknown anti-C5, C6 derivative of 2,3,4,6-tetrasubsituted indolizidine 221-T. The key step in the synthesis was the stereoselective construction of the piperidine ring of the 5,6,8-tri-substituted indolizidine and was realized via the use of an acid-catalyzed intramolecular Mannich cyclization. The indolizidine was readily transformed in to the key intermediate 7-hydroxyl-2,3,4,6-tetrasubsituted indolizidine in high stereoselectivity and yield. Changing the sequence of chemical operation s…
author: Xu, Peng
language: eng
keywords: Chemistry, Organic, Anti-a-substituted B-amino Ketone, Asymmetric Synthesis, Nitrogen Containing, P-toluenesulfinimine
license: http://rightsstatements.org/vocab/InC/1.0/
date published: 2013
date modified: 2026-07-27T21:20:15Z
provider: Temple University
publisher: Networked Digital Library of Theses and Dissertations
type: WebPage
source organization: Temple University. Libraries

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property ID: Handle
value: http://hdl.handle.net/20.500.12613/3869