Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Borylation of Propargylic Substrates by Bimetallic Catalysis. Synthesis of Allenyl, Propargylic, and Butadienyl Bpin Derivatives
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
2014 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 136, no 21, 7563-7566 p.Article in journal (Refereed) Published
Abstract [en]

Bimetallic Pd/Cu and Pd/Ag catalytic systems were used for borylation of propargylic alcohol derivatives. The substrate scope includes even terminal alkynes. The reactions proceed stererospecifically with formal S(N)2' pathways to give allenyl boronates. Opening of propargyl epoxides leads to 1,2-diborylated butadienes probably via en allenylboronate intermediate.

Place, publisher, year, edition, pages
2014. Vol. 136, no 21, 7563-7566 p.
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-105914DOI: 10.1021/ja502792sISI: 000336635400010OAI: oai:DiVA.org:su-105914DiVA: diva2:733267
Funder
Swedish Research CouncilKnut and Alice Wallenberg Foundation
Note

AuthorCount:4;

Available from: 2014-07-08 Created: 2014-07-08 Last updated: 2017-12-05Bibliographically approved
In thesis
1. Synthesis of functionalized allylic, propargylic and allenylic compounds: Selective formation of C–B, C–C, C–CF3 and C-Si bonds
Open this publication in new window or tab >>Synthesis of functionalized allylic, propargylic and allenylic compounds: Selective formation of C–B, C–C, C–CF3 and C-Si bonds
2015 (English)Doctoral thesis, comprehensive summary (Other academic)
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.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University, 2015. 73 p.
Keyword
palladium catalysis, allylboration, allenylboration, trifluoromethylation, silylation, copper catalysis, borylation, bimetallic catalysis
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-116863 (URN)978-91-7649-189-8 (ISBN)
Public defence
2015-06-10, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Opponent
Supervisors
Funder
Swedish Research Council
Note

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

Available from: 2015-05-19 Created: 2015-04-30 Last updated: 2015-06-29Bibliographically approved

Open Access in DiVA

fulltext(276 kB)69 downloads
File information
File name FULLTEXT01.pdfFile size 276 kBChecksum SHA-512
507dfa508af5db5cfd611b642640d30606e22628711987bf0ac98dbd81f930dd6c6cab447dd6a0e0dcb1a80d4a134447df01864e10049465c96520f841bc6eee
Type fulltextMimetype application/pdf

Other links

Publisher's full text

Search in DiVA

By author/editor
Zhao, Tony S. N.Yang, YuzhuSzabó, Kálmán J.
By organisation
Department of Organic Chemistry
In the same journal
Journal of the American Chemical Society
Organic Chemistry

Search outside of DiVA

GoogleGoogle Scholar
Total: 69 downloads
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

doi
urn-nbn

Altmetric score

doi
urn-nbn
Total: 92 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf