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1,3-Dipolar Cycloadditions of Carbonyl Ylides to Aldimines: A Three Component Approach to syn-α-Hydroxy-β-amino Esters
KTH, School of Chemical Science and Engineering (CHE), Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry.
2005 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 44, no 20, 3096-3099 p.Article in journal (Refereed) Published
Abstract [en]

(Chemical Equation Presented) A highly diastereoselective Rh II-catalyzed 1,3-dipolar cycloaddition leads to the formation of syn-β-amino alcohols and syn-α-hydroxy-β-amino acids in high yields (see scheme; p-TSA = poro-toluenesulfonic acid, Bn = benzyl). This three-component approach to the addition of metal-associated carbonyl ylides to aldimines was applied to a short enantioselective synthesis of the C13 side chain of taxol.

Place, publisher, year, edition, pages
2005. Vol. 44, no 20, 3096-3099 p.
Keyword [en]
amino alcohols; carbenoids; cycloaddition; multicomponent reactions; ylides
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:kth:diva-7403DOI: 10.1002/anie.200500296ISI: 000229342600020Scopus ID: 2-s2.0-18944380156OAI: oai:DiVA.org:kth-7403DiVA: diva2:12421
Note
QC 20100817Available from: 2007-08-23 Created: 2007-08-23 Last updated: 2017-12-14Bibliographically approved
In thesis
1. Stereoselective Synthesis of Amino Alcohols: Applications to Natural Product Synthesis
Open this publication in new window or tab >>Stereoselective Synthesis of Amino Alcohols: Applications to Natural Product Synthesis
2007 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [en]

This thesis is divided into four separate parts with amino alcohols as the common feature.

The first part of the thesis describes the development of an efficient three-component approach to the synthesis of α-hydroxy-β-amino esters. Utilizing a highly diastereoselective Rh(II)-catalyzed 1,3-dipolar cycloaddition of carbonyl ylides to various aldimines, syn-α-hydroxy-β-amino esters are formed in high yields and excellent diastereoselectivities. An asymmetric version was also developed by employing chiral α-methylbenzyl imines as dipolarophiles yielding enantiomerically pure syn-α-hydroxy-β-amino esters. This methodology was also applied on a short asymmetric synthesis of the paclitaxel side-chain as well as in an asymmetric synthetic approach towards the proteasome inhibitor omuralide. Furthermore, the use of chiral Rh(II) carboxylates furnishes the syn-α-hydroxy-β-amino esters in moderate enantioselectivity (er up to 82:18), which indicates that the reaction proceeds via a metal-associated carbonyl ylide.

The second part describes the development of a 1,3-dipolar cycloaddition reaction of azomethine ylides to aldehydes for the synthesis of α-amino-β-hydroxy esters. Different methods for the generation of the ylides, including Vedejs’ oxazole methology and an Ag(I)/phosphine-catalyzed approach have been evaluated. The best results were obtained with the Ag(I)/phosphine approach, which yielded the desired α-amino-β-hydroxy ester in 68% yield and 3.4:1 syn:anti-selectivity.

The last two parts deals with the total synthesis of the amino alcohol-containing natural products D-erythro-sphingosine and (−)-stemoamide. The key transformation in the sphingosine synthesis is a cross-metathesis reaction for the assembly of the polar head group and the aliphatic chain. In the stemoamide synthesis, the key feature is an iodoboration/Negishi/RCM-sequence for the construction of the β,γ-unsaturated azepine core of stemoamide followed by a stereoselective bromolactonization/1,4-reduction strategy for the installation of the requisite C8-C9 trans-stereochemistry.

Place, publisher, year, edition, pages
Stockholm: KTH, 2007. 71 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2007:52
Keyword
Amino alcohol, asymmetric 1.3-dipolar cycloaddition, azomethine ylide, carbenoid, carbonyl ylide, cross-metathesis, omuralide, oxazolidine, rhodium, sphingosine, stemoamide, stereoselective synthesis, total synthesis.
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-4472 (URN)978-91-7178-734-7 (ISBN)
Public defence
2007-09-14, F3, Lindstedtsvägen 26, Stockholm, 10:00
Opponent
Supervisors
Note
QC 20100820Available from: 2007-08-23 Created: 2007-08-23 Last updated: 2010-08-20Bibliographically approved
2. Amino Aacohols: stereoselective synthesis and applications in diversity-oriented synthesis
Open this publication in new window or tab >>Amino Aacohols: stereoselective synthesis and applications in diversity-oriented synthesis
2005 (English)Licentiate thesis, comprehensive summary (Other scientific)
Abstract [en]

This thesis is divided into three separate parts with amino alcohols as the common feature. The first part describes the development of a novel three-component approach to the synthesis of α-hydroxy-β-amino esters. Utilizing a highly diastereoselective Rh(II)-catalyzed 1,3-dipolar cycloaddition of carbonyl ylides to various aldimines, syn-α-hydroxy-β-amino esters formed in high yields and excellent diastereoselectivities. This methodology was also applied in a short enantioselective synthesis of the C-13 side-chain of Taxol.

The second part of the thesis describes a total synthesis of D-erythro- Sphingosine based on a cross-metathesis approach to assemble the polar head group and the aliphatic chain.

The last part deals with the application of amino alcohols as scaffolds in a diversity-oriented protocol for the development of libraries of small polycyclic molecules. The design of the libraries is based on the iterative use of two powerful ring-forming reactions; a ring-closing metathesis and an intramolecular Diels-Alder reaction, to simultaneously introduce structural complexity and diversity.

Place, publisher, year, edition, pages
Stockholm: KTH, 2005. 41 p.
Series
Trita-IOK, ISSN 1100-7974 ; 05.95
Keyword
Organic chemistry, amino alcohol, carbenoid, carbonyl ylide, cross-metathesis, diastereoselective, 1, 3-dipolar cycloaddition, sphingosine, Organisk kemi
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-315 (URN)91-7178-006-8 (ISBN)
Presentation
2005-05-09, Sal D41, Lindstedtsvägen 17, Stockholm, 10:00
Supervisors
Note
QC 20101222Available from: 2005-07-18 Created: 2005-07-18 Last updated: 2010-12-22Bibliographically approved

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