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Selective Formation of Adjacent Stereocenters by Allylboration of Ketones under Mild Neutral Conditions
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), Avdelningen för oorganisk kemi och strukturkemi.
Stockholms universitet, Naturvetenskapliga fakulteten, Institutionen för organisk kemi.
2013 (engelsk)Inngår i: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 15, nr 10, s. 2546-2549Artikkel i tidsskrift (Fagfellevurdert) Published
Abstract [en]

Allylboronic acids readily react with a broad variety of ketones, affording homoallylic alcohols with adjacent quaternary and tertiary stereocenters. The reaction proceeds with very high anti stereoselectivity even if the substituents of the keto group have a similar size. a-Keto acids react with syn stereoselectivity probably due to the formation of acyl boronate intermediates. The allylation reactions proceed without added acids/bases under mild conditions. Because of this, many functionalities are tolerated even with in situ generated allylboronic acids.

sted, utgiver, år, opplag, sider
2013. Vol. 15, nr 10, s. 2546-2549
HSV kategori
Forskningsprogram
organisk kemi
Identifikatorer
URN: urn:nbn:se:su:diva-91841DOI: 10.1021/ol401055mISI: 000319720900056OAI: oai:DiVA.org:su-91841DiVA: diva2:636002
Forskningsfinansiär
The Wenner-Gren FoundationSwedish Research CouncilKnut and Alice Wallenberg Foundation
Merknad

AuthorCount:4

Tilgjengelig fra: 2013-07-08 Laget: 2013-07-04 Sist oppdatert: 2017-12-06bibliografisk 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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