Synthesis of N-Containing Compounds: Development of Methodology and its Application in Total Synthesis

Abstract

This thesis aims to develop new synthetic methods and explore the possibilities to apply it in the total synthesis of natural products.
Chapter 2 deals with a mild procedure for the synthesis of a-keto amides by a-oxidation of the corresponding aketo amines mediated by pyrrolidine and TEMPO. The method can also be applied to the synthesis of a-keto thioamides and a-keto amidines.
Chapter 3 deals with a straightforward synthesis of anti-3-alkenyl-2-amido-3-hydroxy esters from the corresponding racemic a-amino-b-keto esters by using ATH/DKR protocol. In order to highlight the versatility of the methodology, it was applied in an efficient asymmetric synthesis of the polyhydroxylated pyrrolizidine alkaloid (+)-alexine.
Chapter 4 describes an asymmetric formal hydroamination of enamines approach using Cu-H catalyst for the synthesis of chiral 1,2-diamines. The method provides a straightforward method for the synthesis of chiral 1,2-dialkyl amines in good yields with high level of enantioselectivities for a broad range of substrates and should
have significant value for the preparation of molecules bearing a 1,2-diamine motif.

Abstract (Swedish)

This thesis aims to develop new synthetic methods and explore the possibilities to apply it in the total synthesis of natural products.
Chapter 2 deals with a mild procedure for the synthesis of a-keto amides by a-oxidation of the corresponding aketo amines mediated by pyrrolidine and TEMPO. The method can also be applied to the synthesis of a-keto thioamides and a-keto amidines.
Chapter 3 deals with a straightforward synthesis of anti-3-alkenyl-2-amido-3-hydroxy esters from the corresponding racemic a-amino-b-keto esters by using ATH/DKR protocol. In order to highlight the versatility of the methodology, it was applied in an efficient asymmetric synthesis of the polyhydroxylated pyrrolizidine alkaloid (+)-alexine.
Chapter 4 describes an asymmetric formal hydroamination of enamines approach using Cu-H catalyst for the synthesis of chiral 1,2-diamines. The method provides a straightforward method for the synthesis of chiral 1,2-dialkyl amines in good yields with high level of enantioselectivities for a broad range of substrates and should
have significant value for the preparation of molecules bearing a 1,2-diamine motif.

• author: Yu, Lu
• supervisor: Peter Somfai; Daniel Strand
• opponent: Professor Pihko, Petri, University of Jyväskylä, Finland
• organization: Centre for Analysis and Synthesis
• publishing date: 2019-08-27
• type: Thesis
• publication status: published
• subject: Organic Chemistry
• keywords: a-keto amides, enamine catalysis, pyrrolidine, TEMPO, a-keto thioamides, a-keto amidines, a-amino-b-hydroxy ester, asymmetric transfer hydrogenation, alexine, dynamic kinetic resolution, hydroamination, 1,2-diamines, enamines, copper
• pages: 142 pages
• defense location: Lecture Hall C, Kemicentrum, Naturvetarvägen 14, Lund
• defense date: 2019-09-20 09:00:00
• ISBN: 978-91-7422-676-8
• ISBN: 978-91-7422-675-1
• language: English
• LU publication?: yes
• id: ccc46933-80cd-4cd5-bbe5-d41fd9b020d6
• date added to LUP: 2019-08-21 17:46:32
• date last changed: 2023-09-07 09:15:58