A1 Journal article (refereed)
Stereoselective Synthesis and Catalytical Application of Perillaldehyde-Based 3-Amino-1,2-diol Regioisomers (2024)


Háznagy, M. B., Csámpai, A., Ugrai, I., Molnár, B., Haukka, M., & Szakonyi, Z. (2024). Stereoselective Synthesis and Catalytical Application of Perillaldehyde-Based 3-Amino-1,2-diol Regioisomers. International Journal of Molecular Sciences, 25(8), Article 4325. https://doi.org/10.3390/ijms25084325


JYU authors or editors


Publication details

All authors or editorsHáznagy, Márton Benedek; Csámpai, Antal; Ugrai, Imre; Molnár, Barnabás; Haukka, Matti; Szakonyi, Zsolt

Journal or seriesInternational Journal of Molecular Sciences

ISSN1661-6596

eISSN1422-0067

Publication year2024

Publication date13/04/2024

Volume25

Issue number8

Article number4325

PublisherMDPI AG

Publication countrySwitzerland

Publication languageEnglish

DOIhttps://doi.org/10.3390/ijms25084325

Publication open accessOpenly available

Publication channel open accessOpen Access channel

Publication is parallel published (JYX)https://jyx.jyu.fi/handle/123456789/94454


Abstract

A library of regioisomeric monoterpene-based aminodiols was synthesised and applied as chiral catalysts in the addition of diethylzinc to benzaldehyde. The synthesis of the first type of aminodiols was achieved starting from (−)-8,9-dihydroperillaldehyde via reductive amination, followed by Boc protection and dihydroxylation with the OsO4/NMO system. Separation of formed stereoisomers resulted in a library of aminodiol diastereoisomers. The library of regioisomeric analogues was obtained starting from (−)-8,9-dihydroperillic alcohol, which was transformed into a mixture of allylic trichloroacetamides via Overman rearrangement. Changing the protecting group to a Boc function, the protected enamines were subjected to dihydroxylation with the OsO4/NMO system, leading to a 71:16:13 mixture of diastereoisomers, which were separated, affording the three isomers in isolated form. The obtained primary aminodiols were transformed into secondary derivatives. The regioselectivity of the ring closure of the N-benzyl-substituted aminodiols with formaldehyde was also investigated, resulting in 1,3-oxazines in an exclusive manner. To explain the stability difference between diastereoisomeric 1,3-oxazines, a series of comparative theoretical modelling studies was carried out. The obtained potential catalysts were applied in the reaction of aromatic aldehydes and diethylzinc with moderate to good enantioselectivities (up to 94% ee), whereas the opposite chiral selectivity was observed between secondary aminodiols and their ring-closed 1,3-oxazine analogues.


Keywordscatalystsmonoterpenes

Free keywordsmonoterpene; chiral; aminodiol; enantioselective; regioselective; catalyst; diethylzinc


Contributing organizations


Ministry reportingYes

Reporting Year2024

Preliminary JUFO rating1


Last updated on 2024-15-06 at 00:05