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A Stereodivergent Strategy for the Preparation of Corynantheine and Ipecac Alkaloids, Their Epimers, and Analogues: Efficient Total Synthesis of ()- Dihydrocorynantheol, ()-Corynantheol, ()-Protoemetinol, ()- Corynantheal, ()-Protoemetine, and Related Natural and Nonnatural Compound
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Organic Chemistry.ORCID iD: 0000-0003-1933-4193
2011 (English)In: Chemistry - A European Journal, ISSN 0947-6539, E-ISSN 1521-3765, Vol. 17, no 49, 13814-13824 p.Article in journal (Refereed) Published
Abstract [en]

Abstract: Here we present a general and common catalytic asymmetric strategy for the total and formal synthesis of a broad number of optically active natural products from the corynantheine and ipecac alkaloid families, for example, indoloACHTUNGTRENUNG[2,3-a]- and benzo[a]quinolizidines. Construction of the core alkaloid skeletons with the correct absolute and relative stereochemistry relies on an enantioselective and diastereodivergent one-pot cascade sequence followed by an additional diastereodivergent reaction step. This allows for enantio- and diastereoselective synthesis of three out of four possible epimers of the quinolizidine alkaloids that begin from common and easily accessible starting materials by using a common synthetic route. Focus has been made on excluding protecting groups and limiting isolation and purification of synthetic intermediates. This methodology is applied in the total synthesis of the natural products ()-dihydrocorynantheol, ()-hirsutinol, ()-corynantheol, ()-protometinol, ()-dihydrocorynantheal, ()-corynantheal, ()-protoemetine, ()-(15S)-hydroxydihydrocorynantheol, and an array of their nonnatural epimers. The potential of this strategy is also demonstrated in the synthesis of biologically interesting natural product analogues not accessible through synthetic elaboration of alkaloid precursors available from nature, for example, thieno[3,2-a]quinolizidine derivatives. We also report the formal synthesis of (+)-dihydrocorynantheine, ()-emetine, ()-cephaeline, ()-tubulosine, and ()-deoxytubulosine.

Place, publisher, year, edition, pages
2011. Vol. 17, no 49, 13814-13824 p.
Keyword [en]
alkaloids · asymmetric catalysis · diastereodivergency · natural products · total synthesis
National Category
Organic Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-79167DOI: 10.1002/chem.201102012ISI: 000298060800028Scopus ID: 2-s2.0-82455192855OAI: oai:DiVA.org:kth-79167DiVA: diva2:495193
Funder
Swedish Research Council
Note

QC 20120209

Available from: 2012-02-08 Created: 2012-02-08 Last updated: 2017-12-07Bibliographically approved
In thesis
1. Metal-Free Catalysis for Efficient Synthesis
Open this publication in new window or tab >>Metal-Free Catalysis for Efficient Synthesis
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The strength of efficient metal-free catalysis will be examined in this thesis. Efforts towards more sustainable processes will be demonstrated through implementation of strategies that meet several of the 12 principles of Green Chemistry.In the first part, a stereoselective total synthesis of multiple alkaloids from the Corynantheine and Ipecac families together with their non-natural analogues will be disclosed. A highly efficient, common synthetic strategy is applied leading to high overall yields starting from easily available starting material. Overall operational simplicity and sustainability have been the main focus. Time-consuming and waste-generating isolations and purifications of intermediates have been minimized, as well as the introduction of protection-group chemistry. Moreover, the first example of the total synthesis of Hydroxydihydrocorynantheol together with its non-natural epimer has been accomplished in multi-gram scale without protection groups and without a single isolation or purification step in high overall yield and diastereoselectivity.In the second part, carbocations will be presented as highly effective and versatile non-metal Lewis acid catalysts. Lewis acidity-tuning of carbocations will be introduced and applied in several reactions to suppress competing reactions. Finally, the broad scope of carbocation catalyzed transformations will be exposed.At large, evident progress has been made towards more sustainable chemistry.

Place, publisher, year, edition, pages
KTH Royal Institute of Technology, 2014. 69 p.
Series
TRITA-CHE-Report, ISSN 1654-1081 ; 2014:15
Keyword
Homogeneous c atalysi s, O rga nocatalysis, Green C hemistry, T o tal S ynthesis, A lkaloids, A symmetric S ynthesis, N on - metal Lewis acid s, C arbocations, Sustainability
National Category
Organic Chemistry
Research subject
Chemistry
Identifiers
urn:nbn:se:kth:diva-144577 (URN)978-91-7595-110-2 (ISBN)
Public defence
2014-05-08, E3, Osquars Backe 14, 5 tr, Stockholm, 13:00 (English)
Opponent
Supervisors
Note

QC 20140425

Available from: 2014-04-25 Created: 2014-04-24 Last updated: 2014-04-25Bibliographically approved

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