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Development of New Chiral Bicyclic Ligands: Applications in Catalytic Asymmetric Transfer Hydrogenation, Epoxidations, and Epoxide Rearrangements
Uppsala University, Teknisk-naturvetenskapliga vetenskapsområdet, Chemistry, Department of Chemistry, Organic Chemistry.
2005 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis describes the synthesis and application of new chiral bicyclic ligands and their application in asymmetric catalysis. The studies involved: [i] The development of novel chiral bicyclic amino sulfur ligands and their use in transfer hydrogenation. [ii] The development of the kinetic resolution of racemic epoxide through the use of chiral lithium amides. [iii] The synthesis and application of chiral bicyclic amine in the organocatalysed epoxidation of alkenes. [iv] Development and application of new chiral diamine ligands in the rearrangement of epoxides into allylic alcohols.

[i] The preparation of two-series of amino thiol ligands based on the structure of camphor is described, together with their application in the iridium-catalysed asymmetric transfer hydrogenation of acetophenone using isopropanol as the hydrogen source. Excellent activity and good enantioselectivity have been achieved using 2 mol% of chiral ligand in combination with [IrCl(COD)]2.

[ii] The chiral diamines (1S,3R,4R)-3-(pyrrolidine-1-ylmethyl)-2-aza-bicyclo[2.2.1]heptane and its (2R,5R)-dimethylpyrrolidine derivative were applied to the kinetic resolution of a variety of racemic 5-7 membered cycloalkene oxides with lithium diisopropylamide (LDA) as the bulk base. Using 5 mol% of the chiral diamines, both unreacted epoxides and allylic alcohols could be produced in enantiomeric excess up to 99%.

[iii] The synthesis of chiral bicyclic amines and their use in the organocatalysed epoxidation of alkene has been described. Using a substoichiometric amount of the chiral amines and aldehydes as ligands precursors, with Oxone® as oxidant, a good activity but moderate enantioselectivity was observed for the epoxidation of trans-stilbene.

[iv] The preparation of 6-substituted-7-bromo-aza-bicyclo[2.2.1]heptanes via nucleophilic addition of organocopper reagents to 3-bromo-1-azoniatricyclo[2.2.1.0]heptyle bromide has been described. These compounds have been utilised as chiral building blocks in the preparation of novel chiral diamine ligands, which have been successfully applied to the catalysed asymmetric rearrangement of epoxide into the corresponding allylic alcohol.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis , 2005. , p. 61
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 4
Keywords [en]
Organic chemistry, asymmetric catalysis, transfer hydrogenation, epoxide rearrangement, Organocatalysed epoxidation, chiral ligand, allylic alcohol, kinetic resolution, lithium amide
Keywords [sv]
Organisk kemi
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-4753ISBN: 91-554-6131-X (print)OAI: oai:DiVA.org:uu-4753DiVA, id: diva2:165635
Public defence
2005-01-26, B42, BMC, Husargatan 3, Uppsala, 10:15
Opponent
Supervisors
Available from: 2005-01-10 Created: 2005-01-10Bibliographically approved
List of papers
1. Novel Catalytic Kinetic Resolution Of Racemic Epoxides to Allylic alcohols
Open this publication in new window or tab >>Novel Catalytic Kinetic Resolution Of Racemic Epoxides to Allylic alcohols
2002 In: Organic Letters, ISSN 1523-7060, Vol. 4, no 22, p. 3777-3779Article in journal (Refereed) Published
Identifiers
urn:nbn:se:uu:diva-92519 (URN)
Available from: 2005-01-10 Created: 2005-01-10Bibliographically approved
2. Development of new camphor based N,S chiral ligands and their application in transfer hydrogenation
Open this publication in new window or tab >>Development of new camphor based N,S chiral ligands and their application in transfer hydrogenation
2004 In: Organic & Biomolecular Chemistry, ISSN 1477-0520, Vol. 2, no 13, p. 1887-1893Article in journal (Refereed) Published
Identifiers
urn:nbn:se:uu:diva-92520 (URN)
Available from: 2005-01-10 Created: 2005-01-10Bibliographically approved
3. Synthesis of 6-Substituted 7-Bomoazabicyclo[2.2.1]heptanes via Nucleophilic Addition to 3-Bromo-1-azoniatricyclo[2.2.1.0]-heptane Bromide
Open this publication in new window or tab >>Synthesis of 6-Substituted 7-Bomoazabicyclo[2.2.1]heptanes via Nucleophilic Addition to 3-Bromo-1-azoniatricyclo[2.2.1.0]-heptane Bromide
2005 (English)In: Advanced Synthesis and Catalysis, ISSN 1615-4150, E-ISSN 1615-4169, Vol. 347, no 9, p. 1242-1246Article in journal (Refereed) Published
Abstract [en]

We describe herein an efficient method for the preparation of a functionalised bicyclic framework (6-substituted 7-bromo-aza-bicyclo[2.2.1]heptane) through the selective opening of the aziridium 2 with organocuprates in up to 90% yield. These interesting chiral building blocks were then utilised as novel ligands in the rearrangement of epoxides to afford chiral allylic alcohols.

National Category
Organic Chemistry
Identifiers
urn:nbn:se:uu:diva-92521 (URN)10.1002/adsc.200404322 (DOI)
Available from: 2005-01-10 Created: 2005-01-10 Last updated: 2017-12-14Bibliographically approved

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