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Petasis borono-Mannich reaction and allylation of carbonyl compounds via transient allyl boronates generated by palladium-catalyzed substitution of allyl alcohols: An efficient one-pot route to stereodefined alpha-amino acids and homoallyl alcohols
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
Stockholm University, Faculty of Science, Department of Organic Chemistry.
2007 (English)In: Journal of the American Chemical Society, ISSN 0002-7863, E-ISSN 1520-5126, Vol. 129, no 44, 13723-13731 p.Article in journal (Refereed) Published
Abstract [en]

An efficient one-pot procedure was designed by integration of the pincer-complex-catalyzed borylation of allyl alcohols in the Petasis borono-Mannich reaction and in allylation of aldehydes and ketones. These procedures are suitable for one-pot synthesis of α-amino acids and homoallyl alcohols from easily available allyl alcohol, amine, aldehyde, or ketone substrates. In the presented transformations, the active allylating agents are in situ generated allyl boronic acid derivatives. These transient intermediates are proved to be reasonably acid-, base-, alcohol-, water-, and air-stable species, which allows a high level of compatibility with the reaction conditions of the allylation of various aldehyde/ketone and imine electrophiles. The boronate source of the reaction is diboronic acid or in situ hydrolyzed diboronate ester ensuring that the waste product of the reaction is nontoxic boric acid. The regio- and stereoselectivity of the reaction is excellent, as almost all products form as single regio- and stereoisomers. The described procedure is suitable to create quaternary carbon centers in branched allylic products without formation of the corresponding linear allylic isomers. Furthermore, products comprising three stereocenters were formed as single products without formation of other diastereomers. Because of the highly disciplined consecutive processes, up to four-step, four-component transformations could be performed selectively as a one-pot sequence. For example, stereodefined pyroglutamic acid could be prepared from a simple allyl alcohol, a commercially available amine, and glyoxylic acid in a one-step procedure. The presented method also grants an easy access to stereodefined 1,7-dienes that are useful substrates for Grubbs ring-closing metathesis.

Place, publisher, year, edition, pages
2007. Vol. 129, no 44, 13723-13731 p.
Identifiers
URN: urn:nbn:se:su:diva-19692DOI: 10.1021/ja074917aISI: 000250819200060OAI: oai:DiVA.org:su-19692DiVA: diva2:186216
Available from: 2007-11-15 Created: 2007-11-15 Last updated: 2017-12-13Bibliographically approved
In thesis
1. Catalytic Functionalization of Allylic Substrates by Palladium Pincer Complexes
Open this publication in new window or tab >>Catalytic Functionalization of Allylic Substrates by Palladium Pincer Complexes
2010 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis is based on the development of novel catalytic reactions for the synthesis and application of organometallic reagents. The main focus is directed towards organoboronate derivatives. We developed an efficient procedure for converting allylic alcohols to the corresponding allylboronates using palladium pincer complexes as catalysts. The reactions were performed under mild conditions with high selectivity, allowing further one-pot transformations. Using this approach, a variety of stereodefined homoallylic alcohols and amino acid derivatives were synthesized via trapping of the in situ generated allylboronate derivatives with an appropriate electrophile. The synthetic scope of these types of multi-component reactions is broad as many different substrate allylic alcohols may be used together with various electrophiles. Several aspects of these reactions were studied, including different reagents, catalysts and electrophiles.

Furthermore, we studied the possibility to use oxidizing reagents as an essential component in the functionalization of olefins. Two main strategies were utilized for these catalytic methods using palladium pincer complexes. The functional group was either transferred from the oxidizing reagent, or introduced via an oxidation-transmetallation route. We propose that both methods involve palladium(IV) intermediates thus expanding both the coordination sphere of palladium and the synthetic scope of pincer complex catalysis.

Place, publisher, year, edition, pages
Stockholm: Department of Organic Chemistry, Stockholm University, 2010. 65 p.
Keyword
Catalysis, Palladium, Pincer Complex, Boron, Multicomponent Reaction
National Category
Organic Chemistry
Research subject
Organic Chemistry
Identifiers
urn:nbn:se:su:diva-39065 (URN)978-91-7447-090-1 (ISBN)
Public defence
2010-06-22, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 13:00 (English)
Opponent
Supervisors
Note
At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 11: In press.Available from: 2010-05-24 Created: 2010-05-06 Last updated: 2010-05-21Bibliographically approved

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