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Stereoselective Nucleophilic Additions to Aldehydes and Synthesis of α-Amino-β- Hydroxy-Esters
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry. (Peter Somfai)
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 [en]
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: urn:nbn:se:kth:diva-95467ISBN: 978-91-7501-396-1 (print)OAI: oai:DiVA.org:kth-95467DiVA: diva2:528536
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
List of papers
1. Diastereoselective Nucleophilic Addition to Aldehydes with Polar alpha- and alpha,beta-Substituents
Open this publication in new window or tab >>Diastereoselective Nucleophilic Addition to Aldehydes with Polar alpha- and alpha,beta-Substituents
Show others...
2011 (English)In: Advanced Synthesis and Catalysis, ISSN 1615-4150, E-ISSN 1615-4169, Vol. 353, no 11-12, 2022-2036 p.Article in journal (Refereed) Published
Abstract [en]

The stereoselectivities obtained in Lewis acid-promoted Mukaiyama aldol additions and Sakurai allylations of mono-, and syn- and anti-disubstituted aldehydes possessing various polar alpha- and beta-substituents under non-chelating conditions are presented. The stereochemical outcome in the nucleophilic addition to alpha-substituted aldehydes containing an alpha-benzyloxy, alpha-fluoro or alpha-sulfonamide substituent are accurately predicted by current stereoinduction models. In contrast, the selectivitites obtained from addition of sterically demanding nucleophiles to alpha-chloro-substituted aldehydes cannot be rationalized by the same models and an alternative is discussed. The stereochemichal outcome in the additions to alpha, beta-disubstituted aldehydes is more complex and cannot be predicted using current models.

Keyword
aldol reaction, allylation, diastereoselectivity, induction model
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-39526 (URN)10.1002/adsc.201100173 (DOI)000294179400027 ()2-s2.0-80052019661 (Scopus ID)
Note

QC 20110916

Available from: 2011-09-16 Created: 2011-09-12 Last updated: 2017-12-08Bibliographically approved
2. Mukaiyama aldol addition to α-chloro-substituted aldehydes. Origin of the unexpected syn selectivity.
Open this publication in new window or tab >>Mukaiyama aldol addition to α-chloro-substituted aldehydes. Origin of the unexpected syn selectivity.
2010 (English)In: Chemical Communications, ISSN 1359-7345, E-ISSN 1364-548X, Vol. 46, no 8, 1281-1283 p.Article in journal (Refereed) Published
Abstract [en]

The addition of sterically demanding enolsilanes to alpha-chloro aldehydes results unexpectedly in preferential formation of the anti-PFA product (1,2-syn), while the addition of the corresponding boron enolate furnishes the expected polar Felkin-Anh product (1,2-anti). A stereoinduction model explaining these observations is proposed.

Keyword
ASYMMETRIC INDUCTION, 1, 3-ASYMMETRIC INDUCTION, ACYCLIC STEREOSELECTION, FELKIN-ANH, MODEL, ENOL, CONDENSATION, CORNFORTH, ENOLSILANES, GEOMETRY
National Category
Natural Sciences Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-50172 (URN)10.1039/b922954j (DOI)000274396700028 ()2-s2.0-76349096927 (Scopus ID)
Available from: 2011-12-02 Created: 2011-12-02 Last updated: 2017-12-08Bibliographically approved
3. 1,3-Dipolar Cycloaddition of Azomethine Ylides to Aldehydes: Synthesis of anti alpha-Amino-beta-Hydroxy Esters
Open this publication in new window or tab >>1,3-Dipolar Cycloaddition of Azomethine Ylides to Aldehydes: Synthesis of anti alpha-Amino-beta-Hydroxy Esters
2011 (English)In: European Journal of Organic Chemistry, ISSN 1434-193X, E-ISSN 1099-0690, no 3, 607-613 p.Article in journal (Refereed) Published
Abstract [en]

A 1,3-dipolar cycloaddition reaction of azomethine ylides to aldehydes is described. The azomethine ylides, generated by thermal electrocyclic ring opening of aziridines, adds to aldehydes in good yields with moderate to good selectivities to furnish oxazolidines. The oxazolidines were subsequently hydrolyzed to the corresponding amino alcohols, giving the anti diastereomer as the major product.

Keyword
Cycloaddition, Azomethine ylides, Aldehydes, Amino alcohols
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-30958 (URN)10.1002/ejoc.201001274 (DOI)000287162700019 ()2-s2.0-78651330597 (Scopus ID)
Funder
Knut and Alice Wallenberg FoundationSwedish Research Council
Note
QC 20110307Available from: 2011-03-07 Created: 2011-03-07 Last updated: 2017-12-11Bibliographically approved
4. Domino Carbopalladation-Carbonylation: Investigation of Substrate Scope
Open this publication in new window or tab >>Domino Carbopalladation-Carbonylation: Investigation of Substrate Scope
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.

Keyword
carbonylation, domino reactions, Heck reaction, oxindoles, quaternary stereocenters
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-90663 (URN)10.1002/adsc.201100678 (DOI)000299331300020 ()2-s2.0-84856833104 (Scopus ID)
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

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