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Synthesis of Adjacent Quaternary Stereocenters by Catalytic Asymmetric Allylboration
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för material- och miljökemi (MMK).
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.
2015 (engelsk)Inngår i: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 137, nr 35, s. 11262-11265Artikkel i tidsskrift (Fagfellevurdert) 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.

sted, utgiver, år, opplag, sider
American Chemical Society (ACS), 2015. Vol. 137, nr 35, s. 11262-11265
HSV kategori
Forskningsprogram
organisk kemi
Identifikatorer
URN: urn:nbn:se:su:diva-121788DOI: 10.1021/jacs.5b07498ISI: 000361251600015PubMedID: 26316158OAI: oai:DiVA.org:su-121788DiVA, id: diva2:861440
Forskningsfinansiär
Swedish Research CouncilKnut and Alice Wallenberg FoundationTilgjengelig fra: 2015-10-16 Laget: 2015-10-16 Sist oppdatert: 2017-12-01bibliografisk kontrollert
Inngår i avhandling
1. Catalytic Regio- and Stereoselective Reactions for the Synthesis of Allylic and Homoallylic Compounds
Åpne denne publikasjonen i ny fane eller vindu >>Catalytic Regio- and Stereoselective Reactions for the Synthesis of Allylic and Homoallylic Compounds
2015 (engelsk)Doktoravhandling, med artikler (Annet vitenskapelig)
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.

sted, utgiver, år, opplag, sider
Stockholm: Department of Organic Chemistry, Stockholm University, 2015. s. 65
Emneord
palladium catalysis, C−H functionalization, boronic acid, allylboration, asymmetric catalysis, allylic, homoallylic, diastereoselective, enantioselective
HSV kategori
Forskningsprogram
organisk kemi
Identifikatorer
urn:nbn:se:su:diva-121757 (URN)978-91-7649-282-6 (ISBN)
Disputas
2015-11-26, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (engelsk)
Veileder
Tilgjengelig fra: 2015-11-04 Laget: 2015-10-15 Sist oppdatert: 2015-10-27bibliografisk kontrollert

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