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Trifluoromethylation of Propargylic Halides and Trifluoroacetates Using (Ph3P)(3)Cu(CF3) Reagent
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.ORCID-id: 0000-0002-9349-7137
2012 (Engelska)Ingår i: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 14, nr 15, s. 3966-3969Artikel i tidskrift (Refereegranskat) Published
Abstract [en]

A copper-mediated trifluoromethylation of propargylic halides and trifluoroacetates was performed with high allenyl or propargyl selectivity. The reaction proceeds smoothly with aliphatic and aromatic substituents bearing either electron-withdrawing or -supplying groups. Preliminary mechanistic results indicate an ionic mechanism involving nucleophilic transfer of the CF3 group from the Cu complex to the propargylic substrate.

Ort, förlag, år, upplaga, sidor
2012. Vol. 14, nr 15, s. 3966-3969
Nationell ämneskategori
Organisk kemi
Forskningsämne
organisk kemi
Identifikatorer
URN: urn:nbn:se:su:diva-81577DOI: 10.1021/ol3017287ISI: 000307041600040OAI: oai:DiVA.org:su-81577DiVA, id: diva2:563155
Forskningsfinansiär
VetenskapsrådetKnut och Alice Wallenbergs Stiftelse
Anmärkning

AuthorCount:2;

Tillgänglig från: 2012-10-29 Skapad: 2012-10-25 Senast uppdaterad: 2019-12-16Bibliografiskt granskad
Ingår i avhandling
1. Synthesis of functionalized allylic, propargylic and allenylic compounds: Selective formation of C–B, C–C, C–CF3 and C-Si bonds
Öppna denna publikation i ny flik eller fönster >>Synthesis of functionalized allylic, propargylic and allenylic compounds: Selective formation of C–B, C–C, C–CF3 and C-Si bonds
2015 (Engelska)Doktorsavhandling, sammanläggning (Övrigt vetenskapligt)
Abstract [en]

This thesis is focused on the development of new palladium and copper- mediated reactions for functionalization of alkenes and propargylic alcohol derivatives. The synthetic utility of the 1,2-diborylated butadienes synthesized in one of these processes has also been demonstrated.

We have developed an efficient procedure for the synthesis of allenyl boronates from propargylic carbonates and acetates. This was achieved by using a bimetallic system of palladium and copper or silver as co-catalyst. The reactions were performed under mild conditions for the synthesis of a variety of allenyl boronates. Furthermore, the synthesis of 1,2-diborylated butadienes was achieved with high diastereoselectivity from propargylic epoxides. The reactivity of the 1,2-diborylated butadienes with aldehydes was studied. It was found that the initial allylboration reaction proceeds via an allenylboronate intermediate. The allenylboronate reacts readily with an additional aldehyde to construct 2-ethynylbutane-1,4-diols with moderate to high diastereoselectivity.

We have also studied the copper-mediated trifluoromethylation of propargylic halides and trifluoroacetates. It was also shown that a transfer of chirality occurred when an enantioenriched starting material was used.

In the last part of the thesis, we have described a method for palladium-catalyzed functionalization of allylic C-H bonds for the selective synthesis of allylic silanes. The protocol only works under highly oxidative conditions which suggest a mechanism involving high oxidation state palladium intermediates.

Ort, förlag, år, upplaga, sidor
Stockholm: Department of Organic Chemistry, Stockholm University, 2015. s. 73
Nyckelord
palladium catalysis, allylboration, allenylboration, trifluoromethylation, silylation, copper catalysis, borylation, bimetallic catalysis
Nationell ämneskategori
Organisk kemi
Forskningsämne
organisk kemi
Identifikatorer
urn:nbn:se:su:diva-116863 (URN)978-91-7649-189-8 (ISBN)
Disputation
2015-06-10, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (Engelska)
Opponent
Handledare
Forskningsfinansiär
Vetenskapsrådet
Anmärkning

At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 1: Accepted.

Tillgänglig från: 2015-05-19 Skapad: 2015-04-30 Senast uppdaterad: 2020-01-23Bibliografiskt granskad

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Zhao, Tony S. N.Szabó, Kálmán J.
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