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New Reactions with Allyl- and Allenylboron Reagents: Transition-Metal-Catalyzed and Transition-Metal-Free Carbon-Carbon Bond Formation Processes
Stockholm University, Faculty of Science, Department of Organic Chemistry.ORCID iD: 0000-0002-2435-9179
2018 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Organoboron compounds have been widely used in carbon-carbon bond formation reactions in organic synthesis and catalysis. This thesis is focused on cross-coupling reactions of allyl-, allenylboronic acids and their ester derivatives via transition metal catalysis or transition-metal-free processes.

The first part of the thesis describes Cu-catalyzed C(sp3)-C(sp3) formation reactions involving allylboronic acids and α-diazoketones. This coupling process shows high γ-regioselectivity, resulting in branched allylic products. When stereodefined cyclic allylboronic acids were employed as the substrate, the relative facial configuration was retained in the reaction product.

The second part involves Pd-catalyzed cross-coupling of allylboronic acid and α-diazoketones. The reaction proceeds with high α-regioselectivity, affording linear allylic products. Accordingly, the palladium- and copper-catalyzed cross-coupling of allylboronic acid and α-diazoketones occurs with opposite regioselectivity.

The third part concerns a new transition-metal-free carbon-carbon bond formation between allenylboronic acids and in situ generated diazo compounds. The diazo compounds are generated from tosylhydrazones in the presence of base. The reaction is suitable for synthesis of densely substituted conjugated dienes with high Z-selectivity.

In the final part, the allylation of quinones with allylboronates is presented. The reaction was performed without any catalyst or additive. Various quinones can be employed as substrates, including unsubstituted, monosubstituted benzoquinones and naphthoquinones.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University , 2018. , p. 61
Keywords [en]
carbon-carbon bond formation, cross-coupling, organoboron compound, allylboron reagent, allylation, transition metal, metal carbene, allenylboron reagent, transition metal free, diazo compound, tosylhydrazone, quinone
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-157469ISBN: 978-91-7797-340-9 (print)ISBN: 978-91-7797-341-6 (electronic)OAI: oai:DiVA.org:su-157469DiVA, id: diva2:1221181
Public defence
2018-09-07, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Opponent
Supervisors
Available from: 2018-08-15 Created: 2018-06-19 Last updated: 2018-09-10Bibliographically approved
List of papers
1. Copper-Catalyzed Cross-Coupling of Allylboronic Acids with alpha-Diazoketones
Open this publication in new window or tab >>Copper-Catalyzed Cross-Coupling of Allylboronic Acids with alpha-Diazoketones
2015 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 17, no 19, p. 4754-4757Article in journal (Refereed) Published
Abstract [en]

Copper-catalyzed cross-coupling of substituted allylboronic acids with alpha-diazoketones was studied. This allylation reaction is highly regioselective, providing the branched allylic product. The process involves creation of a new C(sp(3))-C(sp(3)) bond by retaining the keto functional group of the alpha-diazoketone precursor.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-122944 (URN)10.1021/acs.orglett.5b02285 (DOI)000362384700027 ()
Funder
Swedish Research CouncilKnut and Alice Wallenberg Foundation
Available from: 2015-11-11 Created: 2015-11-11 Last updated: 2018-06-21Bibliographically approved
2. Copper-Catalyzed, Stereoselective Cross-Coupling of Cyclic Allyl Boronic Acids with alpha-Diazoketones
Open this publication in new window or tab >>Copper-Catalyzed, Stereoselective Cross-Coupling of Cyclic Allyl Boronic Acids with alpha-Diazoketones
2017 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 19, no 7, p. 1622-1625Article in journal (Refereed) Published
Abstract [en]

In this study; we present the synthesis of new, Stereodefined allylboronic adds employed to investigate the stereochemistry of the Cu-catalyzed cross-coupling of allylboronic acids with alpha-diazoketones. According to our results, this reaction proceeds with retention of the relative configurtion of the allylberonic acid substrate. We suggest that the stereoinduction step involves a syn S(E)2'-type transrnetalation of the allylboronic acid substrate with a Cu-carbene species.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-143602 (URN)10.1021/acs.orglett.7b00433 (DOI)000398985800033 ()28334535 (PubMedID)
Available from: 2017-05-31 Created: 2017-05-31 Last updated: 2018-06-21Bibliographically approved
3. Formation of C(sp(3))-C(sp(3)) Bonds by Palladium Catalyzed Cross-Coupling of alpha-Diazoketones and Allylboronic Acids
Open this publication in new window or tab >>Formation of C(sp(3))-C(sp(3)) Bonds by Palladium Catalyzed Cross-Coupling of alpha-Diazoketones and Allylboronic Acids
2016 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 18, no 10, p. 2503-2506Article in journal (Refereed) Published
Abstract [en]

Palladium catalyzed cross-coupling of allylboronic acids with a-diazoketones was studied. The reaction selectively affords the linear allylic product. The reaction proceeds with formation of a new C(sp(3))-C(sp(3)) bond. The reaction was performed without an external oxidant, likely without the Pd-catalyst undergoing redox reactions.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-132071 (URN)10.1021/acs.orglett.6b01132 (DOI)000376476300045 ()27166509 (PubMedID)
Funder
Swedish Research CouncilKnut and Alice Wallenberg Foundation
Available from: 2016-07-08 Created: 2016-07-06 Last updated: 2019-01-14Bibliographically approved
4. Synthesis of Densely Substituted Conjugated Dienes by Transition-Metal-Free Reductive Coupling of Allenylboronic Acids and Tosylhydrazones
Open this publication in new window or tab >>Synthesis of Densely Substituted Conjugated Dienes by Transition-Metal-Free Reductive Coupling of Allenylboronic Acids and Tosylhydrazones
2018 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 83, no 15, p. 8786-8792Article in journal (Refereed) Published
Abstract [en]

Tosylhydrazones and allenylboronic acids underwent a transition-metal-free reductive coupling reaction. This process is suitable for synthesis of tetra- and pentasubstituted conjugated dienes. The corresponding allenyl-Bpin substrate showed a very poor reactivity. The reaction is suggested to involve coupling of the in situ formed diazo compound and allenylboronic acid. The intermediate formed in this coupling undergoes allenyl migration followed by protodeboronation to furnish a conjugated diene as major product.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-157467 (URN)10.1021/acs.joc.8b01104 (DOI)000441112900119 ()
Available from: 2018-06-19 Created: 2018-06-19 Last updated: 2018-09-12Bibliographically approved
5. Direct Allylation of Quinones with Allylboronates
Open this publication in new window or tab >>Direct Allylation of Quinones with Allylboronates
2015 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 80, no 6, p. 3343-3348Article in journal (Refereed) Published
Abstract [en]

Allylboronates undergo C-H allylation of unsubstituted or monosubstituted benzoquinone and naphthoquinone substrates. In the case of 2,5- or 2,6-disubstituted quinones addition involving the substituted carbon takes place. Allylation with stereodefined allylboronates occurs with retention of the configuration.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2015
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-116999 (URN)10.1021/acs.joc.5b00264 (DOI)000351558400045 ()25728494 (PubMedID)
Funder
Swedish Research CouncilKnut and Alice Wallenberg Foundation
Note

AuthorCount:3;

Available from: 2015-05-13 Created: 2015-05-05 Last updated: 2018-06-21Bibliographically approved

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