Continuous flow preparation of enantiomerically pure BINOL(s) by acylative kinetic resolution
MetadataShow full item record
A polystyrene‐immobilized isothiourea has been applied to the enantioselective acylative kinetic resolution (KR) of monoacylated BINOL(s) with inexpensive isobutyric anhydride in batch and flow. High selectivity values (s=29 at 0 °C) and a remarkable stability of the catalytic system in the operation conditions have been recorded for unsubstituted BINOL. No significant loss of activity/selectivity is recorded after 10 consecutive KR cycles in batch. A continuous flow process has been implemented and operated with a 100 mmol (32.8 g) sample of racemic monoacetylated BINOL in dichloromethane solution in an 84 hours experiment with a packed bed reactor containing 1 g (f=0.37 mmol.g−1) of the functional resin (s=17–21). Residence time can be decreased to 10 min with the same reactor to achieve a conversion of 58% with a selectivity factor s=17 when a more highly functionalized catalyst (f=0.88 mmol.g−1) is used. This translates into a remarkable combined productivity of 5.5 mmolprod ⋅ mmolcat−1 ⋅ h−1.
Lai , J , Neyyappadath , R M , Smith , A D & Pericàs , M A 2020 , ' Continuous flow preparation of enantiomerically pure BINOL(s) by acylative kinetic resolution ' , Advanced Synthesis & Catalysis , vol. Early View . https://doi.org/10.1002/adsc.201901420
Advanced Synthesis & Catalysis
Copyright © 2020 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim. This work has been made available online in accordance with publisher policies or with permission. Permission for further reuse of this content should be sought from the publisher or the rights holder. This is the author created accepted manuscript following peer review and may differ slightly from the final published version. The final published version of this work is available at https://doi.org/10.1002/adsc.201901420
DescriptionFinancial support from CERCA Programme/Generalitat de Catalunya, MINECO (CTQ2015-69136-R) and AGAUR/Generalitat de Catalunya (2017 SGR 1139) is gratefully acknowledged.
Items in the St Andrews Research Repository are protected by copyright, with all rights reserved, unless otherwise indicated.