Continuous flow synthesis of aryl aldehydes by Pd-catalyzed formylation of phenol-derived aryl fluorosulfonates using syngas.

Autor: Köckinger M; Center for Continuous Flow Synthesis and Processing (CCFLOW), Research Center Pharmaceutical Engineering GmbH (RCPE) Inffeldgasse 13 8010 Graz Austria.; Institute of Chemistry, University of Graz, NAWI Graz Heinrichstrasse 28 8010 Graz Austria christopher.hone@rcpe.at oliver.kappe@uni-graz.at., Hanselmann P; R&D Chemistry, LPBN, Lonza AG CH-3930 Visp Switzerland., Hu G; R&D Chemistry, LPBN, Lonza AG CH-3930 Visp Switzerland., Hone CA; Center for Continuous Flow Synthesis and Processing (CCFLOW), Research Center Pharmaceutical Engineering GmbH (RCPE) Inffeldgasse 13 8010 Graz Austria.; Institute of Chemistry, University of Graz, NAWI Graz Heinrichstrasse 28 8010 Graz Austria christopher.hone@rcpe.at oliver.kappe@uni-graz.at., Kappe CO; Center for Continuous Flow Synthesis and Processing (CCFLOW), Research Center Pharmaceutical Engineering GmbH (RCPE) Inffeldgasse 13 8010 Graz Austria.; Institute of Chemistry, University of Graz, NAWI Graz Heinrichstrasse 28 8010 Graz Austria christopher.hone@rcpe.at oliver.kappe@uni-graz.at.
Jazyk: angličtina
Zdroj: RSC advances [RSC Adv] 2020 Jun 11; Vol. 10 (38), pp. 22449-22453. Date of Electronic Publication: 2020 Jun 11 (Print Publication: 2020).
DOI: 10.1039/d0ra04629a
Abstrakt: This communication describes the palladium-catalyzed reductive carbonylation of aryl fluorosulfonates (ArOSO 2 F) using syngas as an inexpensive and sustainable source of carbon monoxide and hydrogen. The conversion of phenols to aryl fluorosulfonates can be conveniently achieved by employing the inexpensive commodity chemical sulfuryl fluoride (SO 2 F 2 ) and base. The developed continuous flow formylation protocol requires relatively low loadings for palladium acetate (1.25 mol%) and ligand (2.5 mol%). Good to excellent yields of aryl aldehydes were obtained within 45 min for substrates containing electron withdrawing substituents, and 2 h for substrates containing electron donating substituents. The optimal reaction conditions were identified as 120 °C temperature and 20 bar pressure in dimethyl sulfoxide (DMSO) as solvent. DMSO was crucial in suppressing Pd black formation and enhancing reaction rate and selectivity.
Competing Interests: The authors declare no competing financial interest.
(This journal is © The Royal Society of Chemistry.)
Databáze: MEDLINE
Externí odkaz: