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Synthesis of Adjacent Quaternary Stereocenters by Catalytic Asymmetric Allylboration
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 Materials and Environmental Chemistry (MMK).
Stockholm University, Faculty of Science, Department of Organic Chemistry.
2015 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 137, no 35, 11262-11265 p.Article in journal (Refereed) Published
Abstract [en]

Allylboration of ketones with gamma-disubstituted allylboronic acids is performed in the presence of chiral BINOL derivatives. The reaction is suitable for single-step creation of adjacent quaternary stereocenters with high selectivity. We show that, with an appropriate choice of the chiral catalyst and the stereoisomeric prenyl substrate, full control of the stereo- and enantioselectivity is possible in the reaction.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2015. Vol. 137, no 35, 11262-11265 p.
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-121788DOI: 10.1021/jacs.5b07498ISI: 000361251600015PubMedID: 26316158OAI: oai:DiVA.org:su-121788DiVA: diva2:861440
Funder
Swedish Research CouncilKnut and Alice Wallenberg Foundation
Available from: 2015-10-16 Created: 2015-10-16 Last updated: 2017-12-01Bibliographically approved
In thesis
1. Catalytic Regio- and Stereoselective Reactions for the Synthesis of Allylic and Homoallylic Compounds
Open this publication in new window or tab >>Catalytic Regio- and Stereoselective Reactions for the Synthesis of Allylic and Homoallylic Compounds
2015 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis is focused on two main areas of organic synthesis, palladium-catalyzed functionalization of alkenes and allylic alcohols, as well as development of new allylboration reactions.

We have developed a palladium-catalyzed selective allylic trifluoroacetoxylation reaction based on C−H functionalization. Allylic trifluoroacetates were synthesized from functionalized olefins under oxidative conditions. The reactions proceed under mild conditions with a high level of diastereoselectivity. Mechanistic studies of the allylic C−H trifluoroacetoxylation indicate that the reaction proceeds via (η3-allyl)palladium(IV) intermediate.

Palladium-catalyzed regio- and stereoselective synthesis of allylboronic acids from allylic alcohols has been demonstrated. Diboronic acid B2(OH)4 was used as the boron source in this process.

The reactivity of the allylboronic acids were studied in three types of allylboration reactions: allylboration of ketones, imines and acyl hydrazones. All three processes are conducted under mild conditions without any additives. The reactions proceeded with remarkably high regio- and stereoselectivity.

An asymmetric version of the allylboration of ketones was also developed. In this process chiral BINOL derivatives were used as catalysts. The reaction using γ-disubstituted allylboronic acids and various aromatic and aliphatic ketones afforded homoallylic alcohols bearing two adjacent quaternary stereocenters with excellent regio-, diastereo- and enantioselectivity (up to 97:3 er) in high yield. The stereoselectivity in the allylboration reactions could be rationalized on the basis of the Zimmerman-Traxler TS model.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University, 2015. 65 p.
Keyword
palladium catalysis, C−H functionalization, boronic acid, allylboration, asymmetric catalysis, allylic, homoallylic, diastereoselective, enantioselective
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-121757 (URN)978-91-7649-282-6 (ISBN)
Public defence
2015-11-26, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Supervisors
Available from: 2015-11-04 Created: 2015-10-15 Last updated: 2015-10-27Bibliographically approved

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Alam, RaufulEriksson, LarsSzabó, Kálmán J.
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