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Trifluoromethylthiolation-arylation of diazocarbonyl compounds by modified Hooz multicomponent coupling
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.ORCID-id: 0000-0002-9349-7137
Antal upphovsmän: 32019 (Engelska)Ingår i: Chemical Science, ISSN 2041-6520, E-ISSN 2041-6539, Vol. 10, nr 23, s. 5990-5995Artikel i tidskrift (Refereegranskat) Published
Abstract [en]

A new Zn-mediated trifluoromethylthiolation-based bifunctionalization reaction is developed. In this process, simultaneous C-SCF3 and C-C bond formation takes place in a multicomponent reaction, in which an aryl and a SCF3 group arise from different reagents. Our studies show that the reaction mechanism is similar to the Hooz multicomponent coupling. The process involves in situ generation of BAr3, which reacts with a diazocarbonyl compound, and the reaction is terminated by an electrophilic SCF3 transfer. The reaction can also be extended to fluorination based bifunctionalization which proceeds with somewhat lower yield than the analogous trifluoromethylthiolation reaction.

Ort, förlag, år, upplaga, sidor
2019. Vol. 10, nr 23, s. 5990-5995
Nationell ämneskategori
Organisk kemi
Forskningsämne
organisk kemi
Identifikatorer
URN: urn:nbn:se:su:diva-171109DOI: 10.1039/c9sc00829bISI: 000471133800014OAI: oai:DiVA.org:su-171109DiVA, id: diva2:1342889
Tillgänglig från: 2019-08-14 Skapad: 2019-08-14 Senast uppdaterad: 2020-04-19Bibliografiskt granskad
Ingår i avhandling
1. Bifunctionalization of Small Organic Molecules Based on Fluorine Incorporation
Öppna denna publikation i ny flik eller fönster >>Bifunctionalization of Small Organic Molecules Based on Fluorine Incorporation
2020 (Engelska)Doktorsavhandling, sammanläggning (Övrigt vetenskapligt)
Abstract [en]

The dissertation work that is summarized in this thesis describes novel syntheses of organofluorine compounds with a broad coverage of different fluorine-containing motifs.

Chapter 2.1 covers works on the exploration of new trifluoromethylthiolating reactions of diazocarbonyl compounds. A rhodium-catalyzed oxy-trifluoromethylthiolation reaction enabled the synthesis of densely functionalized carbonyl compounds. Different oxygen nucleophiles, for instance alcohols, ethers and acetals underwent this transformation.

A zinc triflimide mediated three-component reaction established an arylation-trifluoromethylthiolation of diazocarbonyl compounds. In situ generation of triarylboranes was rendered most effective for the arylation event. Both procedures made use of the high reactivity of a recently developed electrophilic trifluoromethylthiolating reagent.

The second chapter (2.2) is dedicated to the late-stage construction of trifluoromethyl motifs. By means of halide exchange, nucleophilic fluoride from a copper(I)-complex could be used to exchange bromide with fluoride in the α-position to carbonyl groups as well as in benzylic positions.

The third chapter (2.3) covers the development of an enantioselective fluorocyclization reaction. In situ generated aryliodine(III)-fluoride species were used as organocatalysts. Through this oxidative olefin difunctionalization reaction, quaternary C-F stereogenic centers could be constructed with high enantiomeric excesses. DFT calculations enabled deeper understanding of the mechanism and the origin of stereoselectivity.

Ort, förlag, år, upplaga, sidor
Stockholm: Department of Organic Chemistry, Stockholm University, 2020. s. 71
Nyckelord
fluorination, fluorocyclization, fluorine chemistry, trifluoromethylthiolation, rhodium-catalysis, organocatalysis, asymmetric synthesis, hypervalent iodine, multicomponent reaction, bifunctionalization, diazo compounds
Nationell ämneskategori
Organisk kemi
Forskningsämne
organisk kemi
Identifikatorer
urn:nbn:se:su:diva-180547 (URN)978-91-7911-138-0 (ISBN)978-91-7911-139-7 (ISBN)
Disputation
2020-06-01, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 14:00 (Engelska)
Opponent
Handledare
Anmärkning

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

Tillgänglig från: 2020-05-07 Skapad: 2020-04-01 Senast uppdaterad: 2020-05-26Bibliografiskt granskad

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Lübcke, MarvinSzabó, Kálmán J.
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