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Domino Carbopalladation-Carbonylation: Investigation of Substrate Scope
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry. (Peter Somfai)
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
2012 (English)In: Advanced Synthesis and Catalysis, ISSN 1615-4150, E-ISSN 1615-4169, Vol. 354, no 1, 205-216 p.Article in journal (Refereed) Published
Abstract [en]

This work gives an in depth account of our domino carbopalladation-carbonylation method for substrates possessing beta-hydrogens. The scope of the method is examined for allylic amines containing trisubstituted olefins and we detail our attempts toward the diastereospecific synthesis of contiguous quaternary centers using this technology. The results give key insights into the relative rates of the competing reactions of the alkyl palladium intermediates, which is crucial for the understanding and development of new domino processes.

Place, publisher, year, edition, pages
2012. Vol. 354, no 1, 205-216 p.
Keyword [en]
carbonylation, domino reactions, Heck reaction, oxindoles, quaternary stereocenters
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-90663DOI: 10.1002/adsc.201100678ISI: 000299331300020Scopus ID: 2-s2.0-84856833104OAI: oai:DiVA.org:kth-90663DiVA: diva2:506209
Funder
Knut and Alice Wallenberg FoundationSwedish Research Council
Note
QC 20120228Available from: 2012-02-28 Created: 2012-02-27 Last updated: 2017-12-07Bibliographically approved
In thesis
1. New Methods for the Synthesis of Vicinal Stereocenters: Palladium-Catalyzed Domino Reactions and Asymmetric Transfer Hydrogenation
Open this publication in new window or tab >>New Methods for the Synthesis of Vicinal Stereocenters: Palladium-Catalyzed Domino Reactions and Asymmetric Transfer Hydrogenation
2012 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

In this thesis the synthesis of vicinal stereocenters is investigated in two distinct contexts, namely the construction of 3,3-disubstituted oxindoles and the synthesis of b-hydroxy-a-amino acids. Both scaffolds are prevalent in a range of natural products and biologically relevant compounds and, therefore, methods for their synthesis are of great import.

First, the construction of 3,3-disubstituted oxindoles using palladium-catalyzed domino reactions is described.  This covers two stereospecific methods for the construction of the desired oxindoles based on domino carbopalladation sequences.  The termination events for these domino reactions are carbonylation or cross-coupling.  In the carbopalladation-carbonylation reaction, we studied the possibilty of suppressing b-hydride elimination for substrates possessing pendant b-hydrogens.  In the carbopalladation-cross-coupling sequence, we examined the role of the boron source and substrate scaffold in the outcome of the reaction.  In both of these methods, an intricate balance of rates needs to be attained in order to achieve the desired domino sequences.  Thus, these investigations offer insight into the rates of the competing reactions, and the factors that influence these processes.

Secondly, the stereoselective synthesis of b-hydroxy-a-amino acids is explored.  This has lead to two separate methods for the construction of this scaffold.  We first examined a 1,3-dipolar cycloaddition of azomethine ylides to aldehydes for the construction of syn-b-hydroxy-a-amino esters.  It was found that one set of azomethine ylides reacted through a 1,3-dipolar cycloaddition, while the other set reacted via a direct aldol reaction.  Finally, we studied an asymmetric transfer hydrogenation reaction to provide anti-b-hydroxy-a-amido esters from the corresponding a-amido-b-ketoesters.  Two protocols were developed for the reduction of these substrates, one using triethylammonium formate and the other using sodium formate in an emulsion.  The latter method gives high yields, diastereoselectivities and enantioselectivities for a broad range of substrates.

 

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2012. 75 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2012:27
Keyword
asymmetric synthesis, domino reactions, palladium-catalyzed reactions, oxindoles, amino alcohols
National Category
Natural Sciences Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-95327 (URN)978-91-7501-374-9 (ISBN)
Public defence
2012-08-17, F3, Linstedtsvägen 26, KTH, Stockholm, 10:00 (English)
Opponent
Supervisors
Note
QC 20120605Available from: 2012-06-05 Created: 2012-05-22 Last updated: 2012-06-05Bibliographically approved
2. Stereoselective Nucleophilic Additions to Aldehydes and Synthesis of α-Amino-β- Hydroxy-Esters
Open this publication in new window or tab >>Stereoselective Nucleophilic Additions to Aldehydes and Synthesis of α-Amino-β- Hydroxy-Esters
2012 (English)Licentiate thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis deals with the development of new reaction methodology as well as stereochemical investigations.

The first part concerns the investigation of 1,2- and merged 1,2- and 1,3- asymmetric induction in Mukaiyama aldol additions to α-heteroatom and α,β- heteroatom substituted aldehydes respectively. In particular, the unexpected 1,2-syn selectivity obtained in the addition of sterically hindered nucleophiles to α-chloroaldehydes is examined, and an explanation for the observed stereochemical trends is proposed.

The second part describes the development of a novel entry to α-amino-β- hydroxy esters by a 1,3-dipolar cycloaddition reaction of aldehydes and azomethine ylides, generated by thermolysis of aziridines.

The third part deals with our efforts to develop a novel entry to vicinal all- carbon quaternary centers, based on an intramolecular domino Heck- carbonylation reaction using tetrasubstituted olefins.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2012. 60 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2012:32
Keyword
Asymmetric induction, stereochemical models, Mukaiyama, polar Felkin-Anh, Cornforth-Evans, 1, 3-dipole, aziridine, cycloaddition, amino alcohol, carbonylation, Heck reaction, quaternary stereocenter
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-95467 (URN)978-91-7501-396-1 (ISBN)
Presentation
2012-08-16, F3, KTH, Lindstedtsvägen 3, entréplan, Stockholm, 10:00 (English)
Opponent
Supervisors
Note
QC 20120611Available from: 2012-06-11 Created: 2012-05-25 Last updated: 2012-06-12Bibliographically approved

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