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New Methodologies in Organic Chemistry: Applications to the Synthesis of α-Amino Acids and Natural Products
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry. (Peter Somfai)
2009 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis deals with the development and application of new synthetic methodology in organic chemistry.

The first part describes the development of a new protocol for the synthesis of 3-pyrrolines by means of a microwave-assisted ring-expansion reaction of 2-vinylaziridines. In addition, this methodology is implemented as a key-step in a formal total synthesis of the antibiotic (-)-anisomycin.

In the second part, a new methodology for the synthesis of arylglycines from Weinreb amides is described. In this procedure, a Grignard reagent is added to the iminium ion formed from the Weinreb amide upon treatment with a base. When a chiral amide is used, the nucleophilic addition proceeds with high diastereoselectivity.

Finally, an easy and straightforward synthesis of α-amino amides via a base-mediated rearrangement of modified Weinreb amides into N,O-acetals is presented. Subsequent arylation, alkylation, alkenylation or alkynylation of this intermediate affords the corresponding α-amino amides in excellent yields. Furthermore, a more generalized protocol for the α-arylation of Weinreb amides lacking an α-amino moiety is also discussed.

Place, publisher, year, edition, pages
Stockholm: Kemi , 2009. , 64 p.
Series
Trita-CHE-Report, ISSN 1654-1081 ; 2009:46
Keyword [en]
Organic synthesis, 2-Vinylaziridines, 3-Pyrrolines, Ringexpansion, Rearrangement, Anisomycin, Total synthesis, α-Amino acids, Arylglycines, Weinreb amides, α-Arylation, Grignard reagents, Umpolung
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-11112ISBN: 978-91-7415-404-7 (print)OAI: oai:DiVA.org:kth-11112DiVA: diva2:236033
Public defence
2009-10-09, F3, Lindstedtsvägen 26, KTH, Stockholm, 10:00 (English)
Opponent
Supervisors
Note
QC 20100719Available from: 2009-09-22 Created: 2009-09-20 Last updated: 2011-09-06Bibliographically approved
List of papers
1. Microwave-Assisted Rearrangement of Vinylaziridines to 3-Pyrrolines: Formal Synthesis of (-)-Anisomycin
Open this publication in new window or tab >>Microwave-Assisted Rearrangement of Vinylaziridines to 3-Pyrrolines: Formal Synthesis of (-)-Anisomycin
2005 (English)In: Synlett: Accounts and Rapid Communications in Synthetic Organic Chemistry, ISSN 0936-5214, E-ISSN 1437-2096, no 20, 3099-3102 p.Article in journal (Refereed) Published
Abstract [en]

An efficient microwave-assisted rearrangement of activated vinylaziridines to 3-pyrrolines is described. The rearrangement proceeds in good to excellent yields and is mediated by NaI or LiI in MeCN at elevated temperatures. The synthetic utility of this reaction is shown in an efficient formal total synthesis of the antibiotic (-)-anisomycin.

Keyword
vinylaziridines, pyrrolines, rearrangement, ring expansion, total synthesis
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-11126 (URN)10.1055/s-2005-921934 (DOI)000235012400017 ()2-s2.0-29744467990 (Scopus ID)
Note
QC 20100719Available from: 2009-09-22 Created: 2009-09-22 Last updated: 2017-12-13Bibliographically approved
2. Synthesis of aryl glycines by the alpha arylation of Weinreb amides
Open this publication in new window or tab >>Synthesis of aryl glycines by the alpha arylation of Weinreb amides
2008 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 47, no 10, 1907-1909 p.Article in journal (Refereed) Published
Keyword
amino acids, aryl glycines, arylation, Grignard reaction, Weinreb amides
National Category
Chemical Sciences
Identifiers
urn:nbn:se:kth:diva-33383 (URN)10.1002/anie.200704689 (DOI)000253594300023 ()2-s2.0-41949119899 (Scopus ID)
Note

QC 20110505

Available from: 2011-05-05 Created: 2011-05-05 Last updated: 2017-12-11Bibliographically approved
3. Synthesis of alpha-Amino Acids by Umpolung of Weinreb Amide Enolates
Open this publication in new window or tab >>Synthesis of alpha-Amino Acids by Umpolung of Weinreb Amide Enolates
2008 (English)In: European Journal of Organic Chemistry, ISSN 1434-193X, E-ISSN 1099-0690, no 33, 5583-5589 p.Article in journal (Refereed) Published
Abstract [en]

An efficient and diastereoselective synthesis of alpha-amino acids from readily available starting materials has been developed. The key feature of this reaction is an umpolung of a glycine-derived enolate, providing an alternative approach for the synthesis of alpha-amino acids.

Keyword
Amino acids, Umpolung, Arylglycines, Grignard reaction, Weinreb amides
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-11128 (URN)10.1002/ejoc.200800683 (DOI)000261553700011 ()2-s2.0-56049091042 (Scopus ID)
Funder
Swedish Research CouncilKnut and Alice Wallenberg Foundation
Note
QC 20100719Available from: 2009-09-22 Created: 2009-09-22 Last updated: 2017-12-13Bibliographically approved
4. Synthesis of alpha-Amino Amides via N,O-Acetals Derived from Weinreb Amides
Open this publication in new window or tab >>Synthesis of alpha-Amino Amides via N,O-Acetals Derived from Weinreb Amides
2009 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 74, no 20, 7798-7803 p.Article in journal (Refereed) Published
Abstract [en]

An easy and straightforward synthesis of alpha-amino amides via a base-mediated rearrangement of modified Weinreb amides into N,O-acetals is presented. Subsequent arylation, alkylation, alkenylation, or alkynylation of this intermediate affords the corresponding alpha-amino amides in excellent yields. Furthermore, a more generalized protocol for the alpha-arylation of Weinreb amides lacking an alpha-amino moiety is also discussed.

Keyword
phase-transfer catalysis; acid-derivatives; enantioselective synthesis; asymmetric-synthesis; efficient synthesis; imino esters; rearrangement; clopidogrel; peptides; glycines
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-14142 (URN)10.1021/jo9015166 (DOI)000270504900025 ()2-s2.0-70349871066 (Scopus ID)
Note
QC 20100719Available from: 2010-07-19 Created: 2010-07-19 Last updated: 2017-12-12Bibliographically approved

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