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Stereoselective Nucleophilic Additions to Aldehydes and Development of New Methodology in Organic Synthesis
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry. (Somfai)
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis is divided into four separate parts with nucleophilic addition to aldehydes as the common feature in three of them.

The first part deals with the investigation of the stereochemical induction and elucidation of the factors that dictate the p-facial selectivities in Mukaiyama aldol addition to a- and a,b-heteroatom substituted aldehydes. An explanation for the unexpected shift from 1,2-anti to 1,2-syn selectivity seen in the reaction when applying nucleophiles of different sizes in the addition to a-chloro aldehydes is offered.

The next two parts describes the addition of 1,3-bis(silyl)propenes and C3 substituted 1,3-bis(silyl)propenes to aldehydes and the development of two highly stereoselective new methodologies for the construction of 1,3-dienes and 2,3,4,5-tetrasubstituted tetrahydrofuranes, respectively.

The last part describes the attempts made towards the total synthesis of (±)-aspidophylline A, where the intention was to apply a domino carbopalladation-carbonylation reaction as the key step in the synthetic route.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2013. , 62 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2013:8
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-121172ISBN: 978-91-7501-690-0 (print)OAI: oai:DiVA.org:kth-121172DiVA: diva2:619332
Public defence
2013-05-08, Kollegiesalen, Brinellvägen 8, KTH, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

QC 20130503

Available from: 2013-05-03 Created: 2013-04-22 Last updated: 2013-05-03Bibliographically 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. Lewis Acid-Promoted Addition of 1,3-Bis(silyl)propenes to Aldehydes: A Route to 1,3-Dienes
Open this publication in new window or tab >>Lewis Acid-Promoted Addition of 1,3-Bis(silyl)propenes to Aldehydes: A Route to 1,3-Dienes
2011 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 76, no 19, 8070-8075 p.Article in journal (Refereed) Published
Abstract [en]

The Lewis acid-promoted addition of 1,3-bis(silyl)-propenes to aldehydes to provide the corresponding (E)-1,3-dienes in excellent stereoselectivity and good to excellent yields is reported. The procedure is mild, base-free, and operationally straightforward.

Keyword
diels-alder reaction, olefination reaction, wittig olefination, conjugated dienes, stereochemistry, allylsilanes, elimination, mechanism, oxidation, alcohols
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-46847 (URN)10.1021/jo2013466 (DOI)000295302300049 ()2-s2.0-80054119264 (Scopus ID)
Funder
Swedish Research CouncilKnut and Alice Wallenberg Foundation
Note
QC 20111107Available from: 2011-11-07 Created: 2011-11-07 Last updated: 2017-12-08Bibliographically approved
4. Diastereoselective formation of 2,3,4,5-tetrasubstituted tetrahydrofurans by a Lewis acid promoted addition of C3-substituted 1,3-bis(silyl)propenes to aldehydes
Open this publication in new window or tab >>Diastereoselective formation of 2,3,4,5-tetrasubstituted tetrahydrofurans by a Lewis acid promoted addition of C3-substituted 1,3-bis(silyl)propenes to aldehydes
2010 (English)Manuscript (preprint) (Other academic)
National Category
Natural Sciences Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-121636 (URN)
Note

QC 20170807

Available from: 2013-05-03 Created: 2013-05-03 Last updated: 2017-08-07Bibliographically approved

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