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Stereoselective Synthesis of 1,4-Diols by a Tandem Allylboration–Allenylboration Sequence
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.
2015 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 17, no 9, 2290-2293 p.Article in journal (Refereed) Published
Abstract [en]

The reaction of mono- and dialdehydes with bis-borodienes (incorporating an allylboronate unit) has been studied. It was found that the initial allylboration reaction results in an allenylboronate, which has two stereogenic units: one of them has axial chirality and the other one is a stereogenic carbon center. This reaction proceeds with high diastereoselectivity. The allenylboronate formed in the allylboration reacts with an additional aldehyde with fair to high stereoselectivity depending on the aldehyde substrate. Aromatic dialdehydes react with bis-boro-butadienes creating three new stereocenters with usually high diastereoselectivity.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2015. Vol. 17, no 9, 2290-2293 p.
National Category
Chemical Sciences
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-116860DOI: 10.1021/acs.orglett.5b01048ISI: 000354004400064OAI: oai:DiVA.org:su-116860DiVA: diva2:809027
Funder
Swedish Research CouncilKnut and Alice Wallenberg FoundationWenner-Gren Foundations
Available from: 2015-04-30 Created: 2015-04-30 Last updated: 2017-12-04Bibliographically 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

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