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Mukaiyama aldol addition to α-chloro-substituted aldehydes. Origin of the unexpected syn selectivity.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry. (Peter Somfai)
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry. (Peter Somfai)
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
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.

Place, publisher, year, edition, pages
2010. Vol. 46, no 8, 1281-1283 p.
Keyword [en]
ASYMMETRIC INDUCTION, 1, 3-ASYMMETRIC INDUCTION, ACYCLIC STEREOSELECTION, FELKIN-ANH, MODEL, ENOL, CONDENSATION, CORNFORTH, ENOLSILANES, GEOMETRY
National Category
Natural Sciences Organic Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-50172DOI: 10.1039/b922954jISI: 000274396700028Scopus ID: 2-s2.0-76349096927OAI: oai:DiVA.org:kth-50172DiVA: diva2:461189
Available from: 2011-12-02 Created: 2011-12-02 Last updated: 2017-12-08Bibliographically approved
In thesis
1. 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
2. Stereoselective Nucleophilic Additions to Aldehydes and Development of New Methodology in Organic Synthesis
Open this publication in new window or tab >>Stereoselective Nucleophilic Additions to Aldehydes and Development of New Methodology in Organic Synthesis
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:nbn:se:kth:diva-121172 (URN)978-91-7501-690-0 (ISBN)
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

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