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Regio- and Stereoselective Allylic Trifluoromethylation and Fluorination using CuCF3 and CuF Reagents
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.ORCID-id: 0000-0002-6536-8506
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.ORCID-id: 0000-0002-9349-7137
2013 (Engelska)Ingår i: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 78, nr 14, s. 7330-7336Artikel i tidskrift (Refereegranskat) Published
Abstract [en]

Copper-mediated trifluoromethylation of allylic chlorides and trifluoroacetates was performed using a convenient Cu-CF3 reagent. The reaction is suitable for selective synthesis of allyl trifluoromethyl species. Mechanistic studies indicate that the reaction proceeds via a nucleophilic substitution mechanism involving allyl copper intermediates. The analogous Cu-F reagent was suitable for fluorination of allyl chlorides. Stereodefined cyclic substrates reacted regio- and stereoselectively.

Ort, förlag, år, upplaga, sidor
2013. Vol. 78, nr 14, s. 7330-7336
Nationell ämneskategori
Organisk kemi
Forskningsämne
organisk kemi
Identifikatorer
URN: urn:nbn:se:su:diva-94192DOI: 10.1021/jo4010074ISI: 000322210700055OAI: oai:DiVA.org:su-94192DiVA, id: diva2:652475
Forskningsfinansiär
VetenskapsrådetKnut och Alice Wallenbergs Stiftelse
Anmärkning

AuthorCount:3;

Tillgänglig från: 2013-09-30 Skapad: 2013-09-30 Senast uppdaterad: 2019-12-17Bibliografiskt granskad
Ingår i avhandling
1. Transition metal-catalyzed allylic and vinylic functionalization: Method development and mechanistic investigations
Öppna denna publikation i ny flik eller fönster >>Transition metal-catalyzed allylic and vinylic functionalization: Method development and mechanistic investigations
2013 (Engelska)Doktorsavhandling, sammanläggning (Övrigt vetenskapligt)
Abstract [en]

The use of small molecule building blocks in, for example, pharmaceutical research and new material development, creates a need for new and improved organic synthesis methods. The use of transition metals as mediators and catalysts opens up new reaction pathways that have made the synthesis of completely new compounds possible as well as greatly improved the synthetic routes to known compounds.

Herein, the development of new metal-mediated and catalyzed reactions for construction of vinylic and allylic carbon-carbon and carbon-heteroatom bonds is described.  The use of iodonium salts as coupling partners in Pd-catalyzed Heck type reactions with alkenes is shown to improve the current substrate scope. Results from a mechanistic study indicate that the reaction proceeds via high oxidation state palladium intermediates.

The use of IIII reagents is also believed to facilitate a PdII/PdIV catalytic cycle in allylic silylation of alkenes using (SiMe3)2, which, to the best of our knowledge, is the first method developed for metal-catalyzed allylic C-H silylation.

The same silyl-source, (SiMe3)2, has previously been used in a Pd-catalyzed allylic substitution reaction in which allylic silanes are formed from allylic alcohols. A detailed mechanistic investigation of this reaction is described in which by-products as well as intermediates, including the resting state of the catalyst, are identified using 1H, 11B, 19F and 29Si NMR spectroscopy. Kinetic experiments are performed that give information about the turn-over limiting step and the mechanism of the analogous borylation using B2pin2 is also investigated. Insights from this study further made it possible to improve the stereoselectivity of this reaction.

Additionally, a new method for Cu-mediated trifluoromethylation of allylic halides is presented in which linear products are formed exclusively from both linear and branched allylic substrates at room temperature.  Identification of allylic fluorides as by-products during the reaction also led to the development of a similar Cu-mediated reaction for the fluorination of allylic halides.

Ort, förlag, år, upplaga, sidor
Stockholm: Department of Organic Chemistry, Stockholm Univeristy, 2013. s. 70
Nyckelord
palladium, copper, catalysis, Heck reaction, C-H functionalization, allylic substitution, silylation, borylation, trifluoromethylation, fluorination, mechanistic study, transition metal, alkene, allylic silane, allylic boronate, allylic fluoride
Nationell ämneskategori
Organisk kemi
Forskningsämne
organisk kemi
Identifikatorer
urn:nbn:se:su:diva-89524 (URN)978-91-7447-668-2 (ISBN)
Disputation
2013-06-14, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 13:00 (Engelska)
Opponent
Handledare
Anmärkning

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

Tillgänglig från: 2013-05-16 Skapad: 2013-04-29 Senast uppdaterad: 2014-03-17Bibliografiskt granskad

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Larsson, Johanna M.Pathipati, Stalin R.Szabó, Kálmán J.
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