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Asymmetric Nucleophilic Monofluorobenzylation of Carbonyl Compounds: Synthesis of Enantiopure vic ‐Fluorohydrins and α‐Fluorobenzylketones
Author(s) -
Arroyo Yolanda,
SanzTejedor M. Ascensión,
Parra Alejandro,
García Ruano José Luis
Publication year - 2012
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201103919
Subject(s) - carbanion , enantiopure drug , chemistry , nucleophile , pyridinium , nucleophilic addition , selectivity , carbonyl group , medicinal chemistry , organic chemistry , stereochemistry , enantioselective synthesis , catalysis
Asymmetric nucleophilic monofluoroalkylation of a broad range of aldehydes with an α‐fluoro‐γ‐sulfinylbenzyl carbanion takes place with complete control of the facial selectivity at the carbanion and good to high anti ‐diastereoselectivity to give easily separable mixtures of two optically pure 1,2‐fluorohydrin derivatives (up to 24:1 anti / syn ). Separation and removal of the p ‐tolylsulfinyl group with t BuLi provides enantiomerically pure anti ‐1,2‐disubstituted‐1,2‐fluorohydrins, whereas α‐fluorobenzylketones can be obtained by desulfinylation of the mixture followed by pyridinium chlorochromate oxidation (one‐pot process).