Ändra sökning
RefereraExporteraLänk till posten
Permanent länk

Direktlänk
Referera
Referensformat
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Annat format
Fler format
Språk
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Annat språk
Fler språk
Utmatningsformat
  • html
  • text
  • asciidoc
  • rtf
2,2-Diiododimedone: a mild electrophilic iodinating agent for the selective synthesis of alpha-iodoketones from allylic alcohols
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.ORCID-id: 0000-0001-9774-0731
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.ORCID-id: 0000-0002-1333-7740
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.ORCID-id: 0000-0003-1331-9283
Visa övriga samt affilieringar
2017 (Engelska)Ingår i: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, Vol. 53, nr 71, s. 9842-9845Artikel i tidskrift (Refereegranskat) Published
Abstract [en]

2,2-Diiodo-5,5-dimethylcyclohexane-1,3-dione is reported as a new electrophilic iodinating agent that selectively iodinates electron-rich aromatics. In contrast to other common electrophilic iodinating reagents, its mild nature allows it to be used for the selective synthesis of alpha-iodinated carbonyl compounds from allylic alcohols through a 1,3-hydrogen shift/iodination process catalyzed by iridium(III) complexes.

Ort, förlag, år, upplaga, sidor
2017. Vol. 53, nr 71, s. 9842-9845
Nationell ämneskategori
Organisk kemi
Forskningsämne
organisk kemi
Identifikatorer
URN: urn:nbn:se:su:diva-148095DOI: 10.1039/c7cc04823hISI: 000409481000003PubMedID: 28809976OAI: oai:DiVA.org:su-148095DiVA, id: diva2:1150798
Tillgänglig från: 2017-10-20 Skapad: 2017-10-20 Senast uppdaterad: 2019-10-22Bibliografiskt granskad
Ingår i avhandling
1. Catalytic Methods to Convert Allylic Substrates through Hydride and Proton Shifts: Transition Metal-Catalyzed and Organocatalyzed Approaches
Öppna denna publikation i ny flik eller fönster >>Catalytic Methods to Convert Allylic Substrates through Hydride and Proton Shifts: Transition Metal-Catalyzed and Organocatalyzed Approaches
2019 (Engelska)Doktorsavhandling, sammanläggning (Övrigt vetenskapligt)
Abstract [en]

The present thesis describes the development of new catalytic protocols to transform allylic substrates into a wide variety of versatile carbonyl and vinyl organic compounds. All procedures that are described in this work have in common the existence of one or more hydrogen shifts as key steps in the mechanism of the reactions. The thesis is divided into two mayor sections depending on the strategy employed, metal catalysis or organocatalysis. 

The introductory chapter (Chapter 1) starts with an overview of the different types of catalysis and the importance of allylic substrates in organic chemistry. The chapter continues with an extensive description of the isomerization of allylic alcohols and finishes with a short introduction about hypervalent iodine chemistry. The goals of the thesis are also depicted at the end of this chapter.

Chapters 2, 3 and 4 embody the use of iridium catalysis as an effective tool to synthesize α-functionalized carbonyl compounds selectively as single constitutional isomers from allylic alcohols. The first two chapters of this section describe the employment of several electrophiles to trap enolate derivatives formed from the corresponding allylic alcohols. Chapter 2 shows the development of two new protocols for the preparation of challenging α-iodinated carbonyl compounds. In chapter 3, the synthesis of α-aminooxy and α-hydroxyketones is investigated by employing an N-oxoammonium salt as electrophilic agent. Chapter 4 describes the development of an umpolung strategy that allows the synthesis of α-functionalized carbonyls through the reaction of two formal nucleophiles: enolate derivatives and alcohols. Mechanistic investigations performed in this section point to the presence of an iridium-catalyzed hydride shift operating in the reaction pathways.

The last three chapters (5, 6 and 7) describe the development of metal-free methods for the conversion of allylic substrates into valuable products by means of base catalysis. Chapter 5 and 6 depict the stereospecific isomerization of a large scope of allylic alcohols, ethers and halides. A simple guanidine-type base, TBD (1,5,7-triazabicyclo[4.4.0]dec-5-ene), is an effective catalyst to isomerize allylic substrates with excellent levels of transfer of chirality. The mechanism of this transformation is studied in detail experimentally and computationally and it is suggested to involve a [1,3]-proton shift through the formation of a tight ion-pair. Chapter 7 shows that base-catalysis allows the isomerization of conjugated polyenyl alcohols and ethers which has been proved to be challenging with metal–catalysis. Experimental and computational investigations in this last chapter suggests that the mechanism may proceed through a series of iterative [1,3]-proton shifts or “base-walk”. 

Ort, förlag, år, upplaga, sidor
Stockholm: Department of Organic Chemistry, Stockholm University, 2019. s. 94
Nyckelord
Allylic substrates, Iridium catalysis, Base catalysis, Method development, Isomerization, Hydride shift, Proton shift, Mechanistic studies
Nationell ämneskategori
Organisk kemi
Forskningsämne
organisk kemi
Identifikatorer
urn:nbn:se:su:diva-175359 (URN)978-91-7797-903-6 (ISBN)978-91-7797-904-3 (ISBN)
Disputation
2019-12-06, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (Engelska)
Opponent
Handledare
Anmärkning

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 4: Manuscript. Paper 6: Manuscript.

Tillgänglig från: 2019-11-13 Skapad: 2019-10-22 Senast uppdaterad: 2019-11-11Bibliografiskt granskad

Open Access i DiVA

fulltext(1318 kB)85 nedladdningar
Filinformation
Filnamn FULLTEXT01.pdfFilstorlek 1318 kBChecksumma SHA-512
12a98ee7ce1b96e916b0472f7cd56cb8e4493a8f467500251026739e85867384700ce9a3f3aa38c4ef7834d395fc3281df35605e4c3d083936fb44f825e2b0dd
Typ fulltextMimetyp application/pdf

Övriga länkar

Förlagets fulltextPubMed

Sök vidare i DiVA

Av författaren/redaktören
Martinez-Erro, SamuelBermejo Gómez, AntonioVazquez-Romero, AnaErbing, ElisMartín-Matute, Belén
Av organisationen
Institutionen för organisk kemi
I samma tidskrift
Chemical Communications
Organisk kemi

Sök vidare utanför DiVA

GoogleGoogle Scholar
Totalt: 85 nedladdningar
Antalet nedladdningar är summan av nedladdningar för alla fulltexter. Det kan inkludera t.ex tidigare versioner som nu inte längre är tillgängliga.

doi
pubmed
urn-nbn

Altmetricpoäng

doi
pubmed
urn-nbn
Totalt: 165 träffar
RefereraExporteraLänk till posten
Permanent länk

Direktlänk
Referera
Referensformat
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Annat format
Fler format
Språk
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Annat språk
Fler språk
Utmatningsformat
  • html
  • text
  • asciidoc
  • rtf