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Asymmetric Synthesis and Mechanistic Studies on Copper(I)-Catalyzed Substitution of Allylic Substrates
Stockholm University, Faculty of Science, Department of Organic Chemistry.
2006 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis deals with the copper-catalyzed substitution of allylic substrates.

In the first part of this thesis, the synthesis of a series of metallocenethiolates is described. The thiolates were examined as ligands in the enantioselective copper(I)-catalyzed γ-substitution of allylic acetates.

The second part describes a study on copper-catalyzed α-substitution of enantiomerically pure secondary allylic esters. It was observed that the degree of chirality transfer is strongly dependent on the reaction temperature. The loss of chiral information is consistent with an equilibration of the allylCu(III) intermediates prior to product formation, which is essential in order to realize a copper-catalyzed dynamic kinetic asymmetric transformation process.

The third part describes a study on copper-catalyzed stereoselective α-substitution of enantiopure acyclic allylic esters. This method, when combined, with ruthenium and enzyme catalyzed dynamic kinetic resolution of allylic alcohols, provides a straightforward route to pharmaceutically important α-methyl carboxylic acids.

The fourth part is a mechanistic study on the reaction of perfluoroallyl iodide with organocuprates. Experimental studies as well as theoretical calculations were used to explain the contrasting reactivity of perfluoroallyl iodide vs. allyl iodide in cuprate allylation reactions.

In the fifth part, the development of a practical and useful method for the preparation of pentasubstituted acylferrocenes is presented.

Place, publisher, year, edition, pages
Stockholm: Institutionen för organisk kemi , 2006. , 53 p.
Keyword [en]
copper, allylic substitution, ferrocene, DYKAT, cross-coupling, homo-coupling, DFT
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-1031ISBN: 91-7155-280-4 (print)OAI: oai:DiVA.org:su-1031DiVA: diva2:189264
Public defence
2006-06-01, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 13:00
Opponent
Supervisors
Available from: 2006-05-08 Created: 2006-05-08 Last updated: 2017-12-01Bibliographically approved
List of papers
1. Screening of Ligands in the Asymmetric Metallocenethiolatocopper(I)-Catalyzed Allylic Substitution with Grignard Reagents
Open this publication in new window or tab >>Screening of Ligands in the Asymmetric Metallocenethiolatocopper(I)-Catalyzed Allylic Substitution with Grignard Reagents
2006 (English)In: Tetrahedron, ISSN 0040-4020, E-ISSN 1464-5416, Vol. 62, no 24, 5632-5640 p.Article in journal (Refereed) Published
Abstract [en]

Screening of metallocenethiolate ligands for copper(I)-catalyzed substitution of allylic acetates with Grignard reagents has been carried out. The previously used ligand, lithium (R,Sp)-2-(1-dimethylaminoethyl)ferrocenylthiolate (4a), possessing both central and planar chirality, was the starting point for the screening. It was found that the diastereomeric ligand lithium (R,Rp)-2-(1-dimethylaminoethyl)ferrocenylthiolate (4b) exhibiting reversed planar chirality gave increased enantioselectivity in the allylic substitution, at least when cinnamyl acetate was used as a substrate. The ruthenocene-based ligand lithium (R,Sp)-2-(1-dimethylaminoethyl)ruthenocenylthiolate (4c) gave an enhanced reaction rate, but lower chiral induction. The use of disulfide bis[(R,Sp)-2-(1-dimethylaminoethyl)ferrocenyl]disulfide (7a) as a ligand precursor worked well but resulted in lower enantioselectivity.

Place, publisher, year, edition, pages
Elsevier Ltd, 2006
Keyword
Asymmetric induction; Copper catalysis; Allylic substitution; Cross-coupling; Ferrocene ligands
National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-22681 (URN)10.1016/j.tet.2006.03.100 (DOI)
Note
Part of urn:nbn:se:su:diva-1031Available from: 2006-05-08 Created: 2006-05-08 Last updated: 2017-12-13Bibliographically approved
2. Dynamic processes in the copper-catalyzed substitution of chiral allylic acetates leading to loss of chiral information
Open this publication in new window or tab >>Dynamic processes in the copper-catalyzed substitution of chiral allylic acetates leading to loss of chiral information
2007 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 13, 4094-4102 p.Article in journal (Refereed) Published
Abstract [en]

Copper-catalyzed α-substitution of enantiomerically pure secondary allylic esters with Grignard reagents was studied with the aim to find conditions that give racemic products. It was observed that the degree of chiral transfer is strongly dependent on the temperature. The loss of chiral information is consistent with an equilibration of the CuIII(allyl) intermediates prior to product formation. Equilibration of the reaction intermediates is of importance for a possible development of a dynamic kinetic asymmetric transformation (DYKAT) process, in which a chiral catalyst is used to produce an optically active product from a racemic substrate, by means of a dynamic equilibrium of the diastereomeric reaction intermediates.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-22370 (URN)10.1002/chem.200601684 (DOI)000246573200025 ()
Available from: 2007-06-20 Created: 2007-06-20 Last updated: 2017-10-11Bibliographically approved
3. An enantioselective route to alpha-methyl carboxylic acids via metal and enzyme catalysis
Open this publication in new window or tab >>An enantioselective route to alpha-methyl carboxylic acids via metal and enzyme catalysis
2007 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 9, no 24, 5095-5098 p.Article in journal (Refereed) Published
Abstract [en]

Dynamic kinetic resolution of allylic alcohols to allylic acetates followed by copper-catalyzed allylic substitution gave alkenes in high yields and high optical purity. Subsequent oxidative C-C double bond cleavage afforded pharmaceutically important alpha-methyl substituted carboxylic acids in high ee.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-11741 (URN)10.1021/ol702261t (DOI)000250975000042 ()
Available from: 2008-01-14 Created: 2008-01-14 Last updated: 2017-10-16
4. Unusual Homocoupling in the Reaction of Diorganocuprates with an Allylic Halide
Open this publication in new window or tab >>Unusual Homocoupling in the Reaction of Diorganocuprates with an Allylic Halide
2006 In: Organometallics, Vol. 25, no 9, 2129 -2132 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-22684 (URN)
Note
Part of urn:nbn:se:su:diva-1031Available from: 2006-05-08 Created: 2006-05-08Bibliographically approved
5. An Efficient Route to Pentasubstituted Acylferrocenes
Open this publication in new window or tab >>An Efficient Route to Pentasubstituted Acylferrocenes
2002 In: Journal of Organic Chemistry, Vol. 67, no 25, 9096 -9098 p.Article in journal (Refereed) Published
Identifiers
urn:nbn:se:su:diva-22685 (URN)
Note
Part of urn:nbn:se:su:diva-1031Available from: 2006-05-08 Created: 2006-05-08Bibliographically approved

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