Acylative Dynamic Kinetic Resolution of Secondary Alcohols: Tandem Catalysis by HyperBTM and Bäckvall's Ruthenium Complex

Journal of Organic Chemistry 2021
Artis Kinēns, S Balkaitis, O.K Ahmad, D.W Piotrowski, Edgars Sūna

Non-enzymatic dynamic kinetic resolution (DKR) of secondary alcohols by enantioselective acylation using an isothiourea-derived HyperBTM catalyst and racemization of slowly reacting alcohol by Bäckvall's ruthenium complex is reported. The DKR approach features high enantioselectivities (up to 99:1), employs easy-to-handle crystalline 4-nitrophenyl isobutyrate as the acylating reagent, and proceeds at room temperature and under an ambient atmosphere. The stereoinduction model featuring cation-πsystem interactions between the acylated HyperBTM catalyst and πelectrons of an alcohol aryl subunit has been elaborated by DFT calculations.

Keywords
Enantioselective Synthesis, Transfer Hydrogenation, Benzotetramisole, Derivatives, Selectivity
DOI
10.1021/acs.joc.1c00545
Hyperlink
https://pubs.acs.org/doi/10.1021/acs.joc.1c00545

Kinēns, A., Balkaitis, S., Ahmad, O., Piotrowski, D., Sūna, E. Acylative Dynamic Kinetic Resolution of Secondary Alcohols: Tandem Catalysis by HyperBTM and Bäckvall's Ruthenium Complex. Journal of Organic Chemistry, 2021, Vol. 86, No. 10, pp.7189-7202. ISSN 0022-3263. e-ISSN 1520-6904. Available from: doi:10.1021/acs.joc.1c00545

Publication language
English (en)