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Oxidative Trifluoromethylation and other Functionalization Reactions of Alkenes and Alkynes
Stockholm University, Faculty of Science, Department of Organic Chemistry.
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis concerns the use of various potent oxidants in organic synthesis. The main focus is directed at selectively introducing trifluoromethyl groups into compounds containing double or triple bonds. All reactions proceed under mild conditions and can in most cases be performed on the bench-top.

We have developed three different procedures for transformations of activated alkenes and alkynes as well as quinones. In paper I the selective introduction of a trifluoromethyl group together with an oxygen functionality to double and triple bonds is demonstrated.

Paper II is focused on the related chemoselective cyanotrifluoromethylation in which a cyano group is added instead of the oxygen functionality.

Paper III describes a new procedure for C–H trifluoromethylation of quinones. Our studies on the mechanistic aspects of the above reactions are described in Paper IV. In these studies we investigated the ligand and substituent effects in Cu-catalyzed reactions.

Paper V is focused on a conceptually new palladium-catalyzed allylic C–H acyloxylation of olefins under oxidative conditions. The procedure uses an inexpensive, safe and environmentally benign oxidant, sodium perborate, which is activated with acetic anhydride.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University , 2014. , 63 p.
Keyword [en]
palladium, copper, transition metal, trifluoromethylation, catalysis, acetoxylation, difunctionalization, oxidation, mechanistic study, alkenes, alkynes, quinones
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-103064ISBN: 978-91-7447-930-0 (print)OAI: oai:DiVA.org:su-103064DiVA: diva2:715347
Public defence
2014-06-05, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 13:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 4: Submitted.

Available from: 2014-05-14 Created: 2014-04-30 Last updated: 2017-01-02Bibliographically approved
List of papers
1. Electrophilic Trifluoromethylation by Copper-Catalyzed Addition of CF3-Transfer Reagents to Alkenes and Alkynes
Open this publication in new window or tab >>Electrophilic Trifluoromethylation by Copper-Catalyzed Addition of CF3-Transfer Reagents to Alkenes and Alkynes
2012 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 14, no 11, 2882-2885 p.Article in journal (Refereed) Published
Abstract [en]

Regio- and stereoselective Cu-catalyzed addition of the above hypervalent iodine reagent to alkynes and alkenes was achieved. In the presence of Cul, the reaction is suitable to perform trifluoromethyl-benzoyloxylation and trifluoromethyl-halogenation of alkenes and alkynes. Electron-donating substituents accelerate the process, and alkenes react faster than alkynes emphasizing the electrophilic character of the addition reaction.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-79887 (URN)10.1021/ol3011419 (DOI)000304682700058 ()
Funder
Swedish Research CouncilKnut and Alice Wallenberg Foundation
Note

AuthorCount:4;

Available from: 2012-09-12 Created: 2012-09-11 Last updated: 2017-12-07Bibliographically approved
2. Copper-Mediated Cyanotrifluoromethylation of Styrenes Using the Togni Reagent
Open this publication in new window or tab >>Copper-Mediated Cyanotrifluoromethylation of Styrenes Using the Togni Reagent
2013 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 78, no 21, 11087-11091 p.Article in journal (Refereed) Published
Abstract [en]

Styrenes with an electron-deficient double bond undergo cyanotrifluoromethylation with a trifluoromethylated hypervalent iodine reagent in the presence of CuCN. The reaction proceeds under mild conditions in the presence of bulky phosphines or B(2)pin(2) additives. The process is highly regioselective and involves the consecutive formation of two C-C bonds in a single addition reaction. In the presence of a p-methoxy substituent in the styrene, oxytrifluoromethylation occurs instead of the cyanotrifluoromethylation.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-97375 (URN)10.1021/jo401831t (DOI)000326615300056 ()
Funder
Swedish Research CouncilKnut and Alice Wallenberg Foundation
Note

AuthorCount:3;

Available from: 2013-12-09 Created: 2013-12-09 Last updated: 2017-12-06Bibliographically approved
3. Copper-mediated C-H trifluoromethylation of quinones
Open this publication in new window or tab >>Copper-mediated C-H trifluoromethylation of quinones
2013 (English)In: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, Vol. 49, no 59, 6614-6616 p.Article in journal (Refereed) Published
Abstract [en]

Quinones undergo copper-mediated C-H trifluoromethylation reactions using a hypervalent iodine reagent. The reactions have a broad synthetic scope involving naphtho, alkyl, chloro and methoxy quinones.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-92819 (URN)10.1039/c3cc43357a (DOI)000321012900012 ()
Note

AuthorCount:3;

Available from: 2013-08-21 Created: 2013-08-20 Last updated: 2017-12-06Bibliographically approved
4. Effects of B(2)pin(2) and PCy3 on copper-catalyzed trifluoromethylation of substituted alkenes and alkynes with the Togni reagent
Open this publication in new window or tab >>Effects of B(2)pin(2) and PCy3 on copper-catalyzed trifluoromethylation of substituted alkenes and alkynes with the Togni reagent
2015 (English)In: Tetrahedron, ISSN 0040-4020, E-ISSN 1464-5416, Vol. 71, no 6, 922-931 p.Article in journal (Refereed) Published
Abstract [en]

The copper-catalyzed oxytrifluoromethylation of phenylacetylenes and C-H trifluoromethylation of quinones were studied. It was found that both reactions are accelerated by B(2)pin(2) and PCy3 additives. The two reactions have different substituent effects. The oxytrifluoromethylation is faster in the presence of electron-donating groups, while the C-H trifluoromethylation is faster with electron-withdrawing substituents. The Hammett plot for oxytrifluoromethylation gave a rho value of 0.76 indicating electron demand in the rate determining step of the reaction. According to the absolute value of rho the reaction probably does not proceed through a rate determining formation of a carbocation intermediate. The kinetic isotope effect measurements indicate that in C-H trifluoromethylation of quinones the cleavage of the C-H bond is not the rate determining step of the reaction.

Keyword
Catalysis, Trifluoromethylation, Substituent effects, Hammett plot, Quinones
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-115277 (URN)10.1016/j.tet.2014.12.077 (DOI)000348950300003 ()
Funder
Swedish Research CouncilKnut and Alice Wallenberg Foundation
Note

AuthorCount:4;

Available from: 2015-03-31 Created: 2015-03-18 Last updated: 2017-12-04Bibliographically approved
5. Palladium-Catalyzed Selective Acyloxylation Using Sodium Perborate as Oxidant
Open this publication in new window or tab >>Palladium-Catalyzed Selective Acyloxylation Using Sodium Perborate as Oxidant
2011 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 76, no 5, 1503-1506 p.Article in journal (Refereed) Published
Abstract [en]

Sodium perborate (SPB), a principal component of washing powders, was employed as an inexpensive and eco-friendly oxidant in the palladium-catalyzed C-H acyloxylation of alkenes in excellent regio- and stereochemistry. The reactions used anhydrides as acyloxy sources. The method applies to both terminal and internal alkenes, and even benzylic C-H oxidation.

National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-69434 (URN)10.1021/jo1024199 (DOI)000287636200041 ()
Note
authorCount :3Available from: 2012-01-16 Created: 2012-01-12 Last updated: 2017-12-08Bibliographically approved

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