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Catalytic Stereoselective Formation of C–O, C–C and C–B Bonds: A Voyage from Asymmetric Reactions Enabled by Lipases to Stereoselective Palladium-Catalyzed Oxidative Transformations of Enallenes
Stockholm University, Faculty of Science, Department of Organic Chemistry. (Prof. Jan -E. Bäckvall's Group)
2017 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis has been focused on enzymatic kinetic resolutions and stereoselective oxidative transformations of enallenes catalyzed by PdII.

In the first part of the thesis, a detailed discussion on Candida antarctica lipase B (CALB)-catalyzed kinetic resolution (KR) of δ-functionalized alkan-2-acetates is shown. We gained a deeper insight into the mechanism of enzyme-substrate recognition. Changing from an anhydrous solvent to water or a water-containing organic solvent enhanced the enantioselectivity. The effect of –OH was also confirmed by a lipase mutant suggesting that the water molecule mentioned above can be partly mimicked.

In the second part of the thesis, we developed an efficient KR for allenic alcohols. On this basis, a novel synthesis of optically pure 2-substituted 2,3-dihydrofurans from allenic alcohols via a Ru-catalyzed cycloisomerization was reported. The developed protocol enabled us to assemble an optically pure precursor for total synthesis with three chiral centers from readily available allenol in 2 days.

In the third part, we reported a class of reactions involving C–H cleavage under mild conditions: PdII-catalyzed oxidative transformations of enallenes. These reactions are particularly attractive since a number of meticulous structures have been achieved from readily accessible starting materials. The directing effect of an unsaturated hydrocarbon was found to be key for these transformations.

In the final part, we developed the carbonylative insertion reaction discussed in the third part of the thesis into an asymmetric version. By using this methodology, a number of cyclopentenone compounds were obtained in good to excellent enantioselectivity.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University , 2017. , p. 76
Keywords [en]
Synthesis, Enzymatic kinetic resolution, Palladium, Allenes, Oxidative Transformations, Ruthenium
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-141519ISBN: 978-91-7649-823-1 (print)ISBN: 978-91-7649-824-8 (electronic)OAI: oai:DiVA.org:su-141519DiVA, id: diva2:1087080
Public defence
2017-05-17, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 13:00 (English)
Opponent
Supervisors
Available from: 2017-04-24 Created: 2017-04-05 Last updated: 2017-05-23Bibliographically approved
List of papers
1. Investigation of the Impact of Water on the Enantioselectivity Displayed by CALB in the Kinetic Resolution of δ-Functionalized Alkan-2-ol Derivatives
Open this publication in new window or tab >>Investigation of the Impact of Water on the Enantioselectivity Displayed by CALB in the Kinetic Resolution of δ-Functionalized Alkan-2-ol Derivatives
2014 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 20, no 42, p. 13517-13521Article in journal (Refereed) Published
Abstract [en]

It is shown that the low enantioselectivity of Candida antarctica lipase B (CALB)-catalyzed transesterification of a δ-functionalized alkan-2-ol to its acetate does not correlate at all with the high enantioselectivity of the CALB-catalyzed hydrolysis of the corresponding acetate in water. This lack of correlation is unusual and for unfunctionalized alkan-2-ol derivatives there is a very good correlation between the enantioselectivity of transesterification of the alcohol and hydrolysis of the corresponding acetate (E>200 in both cases). The results confirm previous predictions from molecular modeling. The water effect was mimicked by CALB variant Ala281Ser, which showed an enhanced enantioselectivity in transesterification of δ-functionalized alkan-2-ols compared to wild-type CALB.

Keywords
CALB, enantioselectivity, hydrolysis, lipase, transesterification
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-108352 (URN)10.1002/chem.201404233 (DOI)000342797500010 ()
Funder
Knut and Alice Wallenberg Foundation
Available from: 2014-10-22 Created: 2014-10-22 Last updated: 2017-04-18Bibliographically approved
2. Enzyme- and Ruthenium-Catalyzed Enantioselective Transformation of alpha-Allenic Alcohols into 2,3-Dihydrofurans
Open this publication in new window or tab >>Enzyme- and Ruthenium-Catalyzed Enantioselective Transformation of alpha-Allenic Alcohols into 2,3-Dihydrofurans
2016 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 55, no 18, p. 5568-5572Article in journal (Refereed) Published
Abstract [en]

An efficient one-pot method for the enzyme- and ruthenium-catalyzed enantioselective transformation of alpha-allenic alcohols into 2,3-dihydrofurans has been developed. The method involves an enzymatic kinetic resolution and a subsequent ruthenium-catalyzed cycloisomerization, which provides 2,3-dihydrofurans with excellent enantioselectivity (up to >99%ee). A ruthenium carbene species was proposed as a key intermediate in the cycloisomerization.

Keywords
allenic alcohols, asymmetric catalysis, cycloisomerization, kinetic resolution, ruthenium
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-130865 (URN)10.1002/anie.201601505 (DOI)000375113300030 ()27061624 (PubMedID)
Available from: 2016-06-08 Created: 2016-06-07 Last updated: 2017-04-18Bibliographically approved
3. Olefin-Directed Palladium-Catalyzed Regio- and Stereoselective Oxidative Arylation of Allenes
Open this publication in new window or tab >>Olefin-Directed Palladium-Catalyzed Regio- and Stereoselective Oxidative Arylation of Allenes
2015 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 54, no 31, p. 9066-9069Article in journal (Refereed) Published
Abstract [en]

An olefin-directed palladium-catalyzed oxidative regio- and stereoselective arylation of allenes to afford 1,3,6-trienes has been established. A number of functionalized allenes, including 2,3- and 3,4-dienoates and 3,4-dienol derivatives, have been investigated and found to undergo the olefin-directed allene arylation. The olefin moiety has been proven to be a crucial element for the arylating transformation.

Keywords
allenes, arylation, directing groups, oxidation, palladium
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-120087 (URN)10.1002/anie.201502924 (DOI)000358501500035 ()
Funder
EU, European Research CouncilSwedish Research CouncilBerzelii Centre EXSELENTKnut and Alice Wallenberg Foundation
Available from: 2015-09-07 Created: 2015-09-01 Last updated: 2017-04-18Bibliographically approved
4. Highly Selective Cascade C-C Bond Formation via Palladium-Catalyzed Oxidative Carbonylation-Carbocyclization-Carbonylation-Alkynylation of Enallenes
Open this publication in new window or tab >>Highly Selective Cascade C-C Bond Formation via Palladium-Catalyzed Oxidative Carbonylation-Carbocyclization-Carbonylation-Alkynylation of Enallenes
2015 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 137, no 37, p. 11868-11871Article in journal (Refereed) Published
Abstract [en]

A highly efficient palladium-catalyzed oxidative cascade reaction of enallenes undergoing overall four C-C bond formations has been developed. The insertion cascade proceeds via carbonylation carbocyclization carbonylation alkynylation involving sequential insertion of carbon monoxide, olefin, and carbon monoxide. Furthermore, different types of terminal alkynes and functionalized enallenes have been investigated and found to undergo the cascade reaction under mild reaction conditions.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2015
National Category
Chemical Sciences
Identifiers
urn:nbn:se:su:diva-122320 (URN)10.1021/jacs.5b06828 (DOI)000361930000004 ()
Funder
EU, European Research CouncilBerzelii Centre EXSELENTKnut and Alice Wallenberg Foundation
Available from: 2015-12-02 Created: 2015-10-29 Last updated: 2017-12-01Bibliographically approved
5. Palladium-Catalyzed Oxidative Carbocyclization–Borylation of Enallenes to Cyclobutenes
Open this publication in new window or tab >>Palladium-Catalyzed Oxidative Carbocyclization–Borylation of Enallenes to Cyclobutenes
2016 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 55, no 22, p. 6520-6524Article in journal (Refereed) Published
Abstract [en]

A highly efficient palladium-catalyzed oxidative borylation of enallenes was developed for the selective formation of cyclobutene derivatives and fully-substituted alkenylboron compounds. Cyclobutenes are formed as the exclusive products in MeOH in the presence of H2O and Et3N, whereas the use of AcOH leads to alkenylboron compounds. Both reactions showed a broad substrate scope and good tolerance for various functional groups, including carboxylic acid ester, free hydroxy, imide, and alkyl groups. Furthermore, transformations of the borylated products were conducted to show their potential applications.

Keywords
allenes, borylation, cyclobutenes, oxidation, palladium
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-141525 (URN)10.1002/anie.201601613 (DOI)000377921200029 ()
Funder
EU, European Research Council
Available from: 2017-04-05 Created: 2017-04-05 Last updated: 2017-05-03Bibliographically approved
6. Highly selective olefin-assisted palladium-catalyzed oxidative carbocyclization via remote olefin insertion
Open this publication in new window or tab >>Highly selective olefin-assisted palladium-catalyzed oxidative carbocyclization via remote olefin insertion
2017 (English)In: Chemical Science, ISSN 2041-6520, E-ISSN 2041-6539, Vol. 8, no 1, p. 616-620Article in journal (Refereed) Published
Abstract [en]

A highly selective olefin-assisted palladium-catalyzed oxidative carbocyclization via remote olefin insertion to afford cyclohexenes has been developed. It was shown that the assisting olefin moiety was indispensable for the formation of the cyclohexene product. Furthermore, preliminary studies on chiral anion-induced asymmetrical carbocyclization-borylation of enallenes have been carried out.

National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-140405 (URN)10.1039/c6sc02660e (DOI)000391454500074 ()
Available from: 2017-03-13 Created: 2017-03-13 Last updated: 2017-04-18Bibliographically approved
7. Highly Selective Construction of Seven-Membered Carbocycles by Olefin-Assisted Palladium-Catalyzed Oxidative Carbocyclization-Alkoxycarbonylation of Bisallenes
Open this publication in new window or tab >>Highly Selective Construction of Seven-Membered Carbocycles by Olefin-Assisted Palladium-Catalyzed Oxidative Carbocyclization-Alkoxycarbonylation of Bisallenes
2016 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 55, no 46, p. 14403-14406Article in journal (Refereed) Published
Abstract [en]

An olefin-assisted palladium-catalyzed oxidative carbocyclization-alkoxycarbonylation of bisallenes to afford seven-membered carbocycles has been established. This dehydrogenative coupling reaction showed excellent substrate scope and functional group compatibility. The reaction exhibited high chemo-and regioselectivity, and ester 3 was the only product obtained. The olefin unit has been proven to be indispensable during the reaction. Moreover, intramolecular oxidative coupling suggests that the reaction proceeds via a (pallyl)palladium intermediate.

Keywords
bisallene, carbocyclization, olefins, palladium, seven-membered carbocycles
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-136145 (URN)10.1002/anie.201608247 (DOI)000387028000037 ()
Available from: 2016-11-30 Created: 2016-11-29 Last updated: 2017-04-18Bibliographically approved
8. Enantioselective Palladium-Catalyzed Carbonylative Carbocyclization of Enallenes via Cross-Dehydrogenative Coupling with Terminal Alkyne: Efficient Construction of a-Chirality of Ketones
Open this publication in new window or tab >>Enantioselective Palladium-Catalyzed Carbonylative Carbocyclization of Enallenes via Cross-Dehydrogenative Coupling with Terminal Alkyne: Efficient Construction of a-Chirality of Ketones
Show others...
2017 (English)In: Angewandte Chemie International Edition, ISSN 1433-7851, E-ISSN 1521-3773, Vol. 56, no 16, p. 4535-4539Article in journal (Refereed) Published
Abstract [en]

An enantioselective PdII/Brønsted acid-catalyzed carbonylative carbocyclization of enallenes ending with a cross-dehydrogenative coupling (CDC) with a terminal alkyne was developed. VAPOL phosphoric acid was found as the best co-catalyst among the examined 28 chiral acids, for inducing the enantioselectivity of α-chiral ketones. As a result, a number of chiral cyclopentenones were easily synthesized in good to excellent enantiomeric ratio with good yields.

Keywords
asymmetric carbocyclization, enallenes, homogeneous catalysis, oxidation, palladium
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-141526 (URN)10.1002/anie.201612385 (DOI)000398154000023 ()
Funder
EU, European Research Council
Available from: 2017-04-05 Created: 2017-04-05 Last updated: 2017-05-02Bibliographically approved

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