Ammonium-directed epoxidation in the asymmetric syntheses of dihydroconduramines and conduramines

Thesis

This thesis centres on the asymmetric syntheses of a family of synthetic products: dihydroconduramines and conduramines. The work aims to use the ammonium-directed epoxidation methodology as a key step in all cases.

Chapter 1 introduces a review of literature reports relating to the biological activity and synthetic strategies to access dihydroconduramines and conduramines.

Chapter 2 investigates the olefinic oxidation protocol of racemic N-protected anti- and syn-2-aminocyclohex-3-en-1-ols. Concise syntheses of racemic dihydroconduramines (±)-A-2 and (±)-C-2 are also presented.

Chapter 3 describes the syntheses of enantiopure N-protected anti- and syn-2-aminocyclohex-3-en-1-ols in order to access enantiopure dihydroconduramines. Investigation of the surrogacy of these substrates to the racemate is also undertaken.

Chapter 4 details the asymmetric synthesis of four new enantiopure dihydroconduramines from an appropriate enantiopure anti-2 aminocyclohex-3-en-1-ols.

Chapter 5 details the asymmetric synthesis of six enantiopure dihydroconduramines from an appropriate enantiopure syn-2 aminocyclohex-3-en-1-ols.

Chapter 6 investigates the olefinic oxidation protocol of primary, secondary and tertiary racemic allylic amino alcohols, derived from ring-opening of benzene oxide with primary, secondary and tertiary amines.

Chapter 7 describes concise asymmetric syntheses of six conduramines, including four new, from enantiopure allylic amino alcohols, derived from ring-opening of benzene oxide with (R)-α-methylbenzylamine.

Chapter 8 contains full experimental procedures and characterisation for all compounds synthesised in chapter 2-7.

Authors: Da Silva Pinto, S

• DOI: 10.5287/ora-5rrvwj7de
• Type of award: DPhil
• Level of award: Doctoral
• Awarding institution: University of Oxford
• Language: English
• Keywords: Epoxidation; Conduramines; Asymmetric synthesis; Diastereoselectivity; Ring-opening; Regioselectivity; Chemoselectivity; Stereoselective synthesis; Dihydroconduramines; Amino alcohols
• Subjects: Organic Chemistry