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Tetrazolic Acid Functionalized Dihydroindol: Rational Design of a Highly Selective Cyclopropanation Organocatalyst
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Biochemistry and Organic Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Biochemistry and Organic Chemistry.
2007 (English)In: Journal of Organic Chemistry, ISSN 0022-3263, E-ISSN 1520-6904, Vol. 72, no 15, 5874-5877 p.Article in journal (Refereed) Published
Abstract [en]

Herein we wish to report our development of an improved catalyst (S)-(-)-indoline-2-yl-1H-tetrazole (1) for the enantioselective organocatalyzed cyclopropanation of α,β-unsaturated aldehydes with sulfur ylides. The new organocatalyst readily facilitates the enantioselective organocatalytic cyclopropanation, providing cyclized product in excellent diastereoselectivities ranging from 96% to 98% along with enantioselectivities exceeding 99% enantiomeric excess for all reacted α,β-unsaturated aldehydes. The new catalyst provides the best results so far reported for intermolecular enantioselective organocatalyzed cyclopropanation.

Place, publisher, year, edition, pages
2007. Vol. 72, no 15, 5874-5877 p.
Keyword [en]
Nitrogen heterocycle, Diastereoselectivity, Cyclization, Ylide, Organic sulfide, Aldehyde, Unsaturated compound, Enantioselectivity, Tetrazole derivatives, Enantiomeric excess, Catalyst, Cyclopropanation, Selectivity, Indole derivatives, Functionalization
National Category
Chemical Sciences
URN: urn:nbn:se:uu:diva-95940DOI: 10.1021/jo070519eISI: 000247992800059OAI: oai:DiVA.org:uu-95940DiVA: diva2:170327
Available from: 2007-05-11 Created: 2007-05-11 Last updated: 2011-02-01Bibliographically approved
In thesis
1. Towards Rational Design of Asymmetric Catalyst for Organometallic and Organocatalytic Reactions
Open this publication in new window or tab >>Towards Rational Design of Asymmetric Catalyst for Organometallic and Organocatalytic Reactions
2007 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis deals with synthetically modified chiral molecules and their application in asymmetric catalysis. The first part of the thesis describes the use of commercially available chiral diamine ligands in the iridium catalyzed transfer hydrogenation of aromatic ketones. The chiral diamine ligands were mixed with an appropriate transition-metal complex, which after addition of suitable base provided a chiral transition metal complex capable of reducing a range of different aromatic ketones in high yields and enantioselectivities. The developed methodology constitutes a cost effective and readily available procedure for transfer hydrogenation reactions. The following chapters in the thesis are completely devoted to rational design of small organic molecules acting as catalyst in various organocatalytic transformations. Organocatalytic methodology, represent a new and complementary approach to asymmetric organic synthesis, as compared to e.g. transition metal based methodology. Advantages of this methodology typically include mild and less stringent reaction conditions. This, in combination with the lack of toxic transition metal by-products, makes the process more environmentally benign; the organocatalytic methodology, therefore represent a promising approach towards implementation of green chemistry in organic synthesis. Despite this promise, typical drawbacks of the current methodology are long reaction times and the need for high catalyst loadings. Thus, a large demand exists for enhancing reactivity and increasing selectivity in organocatalytic reactions. The present thesis describes several efforts where we have tried to rationally design improved catalysts for various enantioselective organocata-lytic reactions. First, a structurally modified L-proline, incorporating a 1H-tetrazolic acid, was synthesized and evaluated in the direct asymmetric organocatalytic aldol reaction. As shown in Paper II, the catalyst displayed very high reactivity and subsequent studies were initiated in order to rationalize the reactivity enhancement (Paper III). Delightfully, the design principle of a 1H-tetrazolic acid as replacement for a carboxylic acid has since been widely used in the community, including our own efforts in organocatalytic asymmetric cyclopropanations (Paper V)and Diels-Alder reactions (Paper VII). Novel catalysts, including other functionalizations, were also designed for organocatalytic asymmetric addition of nitroalkanes to α,β-unsaturated aldehydes (Paper IV) and for cyclopropanations (Paper VI).

Place, publisher, year, edition, pages
Uppsala: Universitetsbiblioteket, 2007. 65 p.
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 313
Organocatalysis, Transition Metal Complex, Asymmetric, Aldol Reaction, Cyclopropanation, Diels-Alder, Reduction, Conjugate Addition
National Category
Organic Chemistry
urn:nbn:se:uu:diva-7905 (URN)978-91-554-6905-4 (ISBN)
Public defence
2007-06-02, B41, BMC, Husargatan 3, Uppsala, 10:15
Available from: 2007-05-11 Created: 2007-05-11Bibliographically approved

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Hartikka, AnttiArvidsson, Per. I
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