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Catalytic Regio- and Stereoselective Reactions for the Synthesis of Allylic and Homoallylic Compounds
Stockholm University, Faculty of Science, Department of Organic Chemistry. (Professor Kalman J Szabo)
2015 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis is focused on two main areas of organic synthesis, palladium-catalyzed functionalization of alkenes and allylic alcohols, as well as development of new allylboration reactions.

We have developed a palladium-catalyzed selective allylic trifluoroacetoxylation reaction based on C−H functionalization. Allylic trifluoroacetates were synthesized from functionalized olefins under oxidative conditions. The reactions proceed under mild conditions with a high level of diastereoselectivity. Mechanistic studies of the allylic C−H trifluoroacetoxylation indicate that the reaction proceeds via (η3-allyl)palladium(IV) intermediate.

Palladium-catalyzed regio- and stereoselective synthesis of allylboronic acids from allylic alcohols has been demonstrated. Diboronic acid B2(OH)4 was used as the boron source in this process.

The reactivity of the allylboronic acids were studied in three types of allylboration reactions: allylboration of ketones, imines and acyl hydrazones. All three processes are conducted under mild conditions without any additives. The reactions proceeded with remarkably high regio- and stereoselectivity.

An asymmetric version of the allylboration of ketones was also developed. In this process chiral BINOL derivatives were used as catalysts. The reaction using γ-disubstituted allylboronic acids and various aromatic and aliphatic ketones afforded homoallylic alcohols bearing two adjacent quaternary stereocenters with excellent regio-, diastereo- and enantioselectivity (up to 97:3 er) in high yield. The stereoselectivity in the allylboration reactions could be rationalized on the basis of the Zimmerman-Traxler TS model.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University , 2015. , 65 p.
Keyword [en]
palladium catalysis, C−H functionalization, boronic acid, allylboration, asymmetric catalysis, allylic, homoallylic, diastereoselective, enantioselective
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-121757ISBN: 978-91-7649-282-6 (print)OAI: oai:DiVA.org:su-121757DiVA: diva2:861175
Public defence
2015-11-26, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Supervisors
Available from: 2015-11-04 Created: 2015-10-15 Last updated: 2015-10-27Bibliographically approved
List of papers
1. Stereoselective intermolecular allylic C-H trifluoroacetoxylation of functionalized alkenes
Open this publication in new window or tab >>Stereoselective intermolecular allylic C-H trifluoroacetoxylation of functionalized alkenes
2012 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 134, no 21, 8778-8781 p.Article in journal (Refereed) Published
Abstract [en]

Pd-catalyzed allylic C-H trifluoroacetoxylation of substituted alkenes was performed using PhI(OCOCF3)(2) as the oxidant and acyloxy source. Trifluoroacetoxylation of monosubstituted cyclopentenes and cyclohexenes proceeds with excellent regio- and diastereoselectivity. Studies with one of the possible (eta(3)-allyl)Pd(II) intermediates suggest that the reaction proceeds via stereoselective formation of Pd(IV) intermediates and subsequent stereo- and regioselective reductive elimination of the product.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-79767 (URN)10.1021/ja302457p (DOI)000304570700013 ()
Funder
Swedish Research CouncilKnut and Alice Wallenberg Foundation
Note

AuthorCount:4;

Available from: 2012-09-12 Created: 2012-09-11 Last updated: 2017-12-07Bibliographically approved
2. Palladium-Catalyzed Synthesis and Isolation of Functionalized Allylboronic Acids: Selective, Direct Allylboration of Ketones
Open this publication in new window or tab >>Palladium-Catalyzed Synthesis and Isolation of Functionalized Allylboronic Acids: Selective, Direct Allylboration of Ketones
2012 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 51, no 52, 13050-13053 p.Article in journal (Refereed) Published
Keyword
allylic compounds, boron, homogeneous catalysis, ketones, palladium
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-87125 (URN)10.1002/anie.201207951 (DOI)000312552900026 ()
Note

AuthorCount:3;

Available from: 2013-01-29 Created: 2013-01-28 Last updated: 2017-12-06Bibliographically approved
3. Selective Formation of Adjacent Stereocenters by Allylboration of Ketones under Mild Neutral Conditions
Open this publication in new window or tab >>Selective Formation of Adjacent Stereocenters by Allylboration of Ketones under Mild Neutral Conditions
2013 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 15, no 10, 2546-2549 p.Article in journal (Refereed) Published
Abstract [en]

Allylboronic acids readily react with a broad variety of ketones, affording homoallylic alcohols with adjacent quaternary and tertiary stereocenters. The reaction proceeds with very high anti stereoselectivity even if the substituents of the keto group have a similar size. a-Keto acids react with syn stereoselectivity probably due to the formation of acyl boronate intermediates. The allylation reactions proceed without added acids/bases under mild conditions. Because of this, many functionalities are tolerated even with in situ generated allylboronic acids.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-91841 (URN)10.1021/ol401055m (DOI)000319720900056 ()
Funder
The Wenner-Gren FoundationSwedish Research CouncilKnut and Alice Wallenberg Foundation
Note

AuthorCount:4

Available from: 2013-07-08 Created: 2013-07-04 Last updated: 2017-12-06Bibliographically approved
4. Synthesis of Adjacent Quaternary Stereocenters by Catalytic Asymmetric Allylboration
Open this publication in new window or tab >>Synthesis of Adjacent Quaternary Stereocenters by Catalytic Asymmetric Allylboration
2015 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 137, no 35, 11262-11265 p.Article in journal (Refereed) Published
Abstract [en]

Allylboration of ketones with gamma-disubstituted allylboronic acids is performed in the presence of chiral BINOL derivatives. The reaction is suitable for single-step creation of adjacent quaternary stereocenters with high selectivity. We show that, with an appropriate choice of the chiral catalyst and the stereoisomeric prenyl substrate, full control of the stereo- and enantioselectivity is possible in the reaction.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2015
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-121788 (URN)10.1021/jacs.5b07498 (DOI)000361251600015 ()26316158 (PubMedID)
Funder
Swedish Research CouncilKnut and Alice Wallenberg Foundation
Available from: 2015-10-16 Created: 2015-10-16 Last updated: 2017-12-01Bibliographically approved
5. Stereoselective allylboration of imines and indoles under mild conditions. An in situ E/Z isomerization of imines by allylboroxines
Open this publication in new window or tab >>Stereoselective allylboration of imines and indoles under mild conditions. An in situ E/Z isomerization of imines by allylboroxines
Show others...
2014 (English)In: Chemical Science, ISSN 2041-6520, E-ISSN 2041-6539, Vol. 5, no 7, 2732-2738 p.Article in journal (Refereed) Published
Abstract [en]

Direct allylboration of various acyclic and cyclic aldimine, ketimine and indole substrates was performed using allylboronic acids. The reaction proceeds with very high anti-stereoselectivity for both E and Z imines. The allylboroxines formed by dehydration of allylboronic acids have a dual effect: promoting E/Z isomerization of aldimines and triggering the allylation by efficient electron withdrawal from the imine substrate.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-106118 (URN)10.1039/c4sc00415a (DOI)000337108200016 ()
Funder
Swedish Research CouncilKnut and Alice Wallenberg Foundation
Note

AuthorCount:6;

Available from: 2014-07-22 Created: 2014-07-21 Last updated: 2017-12-05Bibliographically approved
6. Stereocontrol in Synthesis of Homoallylic Amines. Syn Selective Direct Allylation of Hydrazones with Allylboronic Acids
Open this publication in new window or tab >>Stereocontrol in Synthesis of Homoallylic Amines. Syn Selective Direct Allylation of Hydrazones with Allylboronic Acids
2014 (English)In: Organic Letters, ISSN 1523-7060, E-ISSN 1523-7052, Vol. 16, no 14, 3808-3811 p.Article in journal (Refereed) Published
Abstract [en]

Allylboronic acids directly react with acyl hydrazones, affording homoallylic amine derivatives. The reaction proceeds with very high syn selectivity, which is the opposite of the stereochemistry observed for allylboration of imines. The reaction can be carried out with both aromatic and aliphatic acyl hydrazones. Based on our studies the excellent syn stereochemistry can be explained by chelation control of the acyl hydrazone and the B(OH)(2) moiety.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-106905 (URN)10.1021/ol501699x (DOI)000339367300050 ()
Funder
Swedish Research CouncilKnut and Alice Wallenberg Foundation
Note

AuthorCount:4;

Available from: 2014-08-27 Created: 2014-08-26 Last updated: 2017-12-05Bibliographically approved

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