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Synthesis of functionalized allylic, propargylic and allenylic compounds: Selective formation of C–B, C–C, C–CF3 and C-Si bonds
Stockholm University, Faculty of Science, Department of Organic Chemistry.
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 [en]
palladium catalysis, allylboration, allenylboration, trifluoromethylation, silylation, copper catalysis, borylation, bimetallic catalysis
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-116863ISBN: 978-91-7649-189-8 (print)OAI: oai:DiVA.org:su-116863DiVA: diva2:809077
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
List of papers
1. Stereoselective Synthesis of 1,4-Diols by a Tandem Allylboration–Allenylboration Sequence
Open this publication in new window or tab >>Stereoselective Synthesis of 1,4-Diols by a Tandem Allylboration–Allenylboration Sequence
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
National Category
Chemical Sciences
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-116860 (URN)10.1021/acs.orglett.5b01048 (DOI)000354004400064 ()
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
2. Borylation of Propargylic Substrates by Bimetallic Catalysis. Synthesis of Allenyl, Propargylic, and Butadienyl Bpin Derivatives
Open this publication in new window or tab >>Borylation of Propargylic Substrates by Bimetallic Catalysis. Synthesis of Allenyl, Propargylic, and Butadienyl Bpin Derivatives
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.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-105914 (URN)10.1021/ja502792s (DOI)000336635400010 ()
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
3. Trifluoromethylation of Propargylic Halides and Trifluoroacetates Using (Ph3P)(3)Cu(CF3) Reagent
Open this publication in new window or tab >>Trifluoromethylation of Propargylic Halides and Trifluoroacetates Using (Ph3P)(3)Cu(CF3) Reagent
2012 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 14, no 15, 3966-3969 p.Article in journal (Refereed) 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.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-81577 (URN)10.1021/ol3017287 (DOI)000307041600040 ()
Funder
Swedish Research CouncilKnut and Alice Wallenberg Foundation
Note

AuthorCount:2;

Available from: 2012-10-29 Created: 2012-10-25 Last updated: 2017-12-07Bibliographically approved
4. Palladium-Catalyzed Oxidative Allylic C-H Silylation
Open this publication in new window or tab >>Palladium-Catalyzed Oxidative Allylic C-H Silylation
2011 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 13, no 7, 1888-1891 p.Article in journal (Refereed) Published
Abstract [en]

Palladium-catalyzed allylic C−H silylation was performed with use of hexamethyldisilane as the silyl source. These C−H functionalization reactions occur only in the presence of hypervalent iodine reagents or other strong oxidants and proceed with excellent regioselectivity, providing the linear allylic isomer of the allylsilane products. In demonstrating the first oxidative allylic C−H silylation of alkenes, this study marks an important advance for the catalytic C−H functionalization method.

National Category
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-57796 (URN)10.1021/ol200445b (DOI)000288691600081 ()
Funder
Swedish Research Council
Available from: 2011-05-24 Created: 2011-05-19 Last updated: 2017-12-11Bibliographically approved

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