Dianionic Phase-Transfer Catalyst for Asymmetric Fluoro-cyclization.
J Am Chem Soc
; 140(8): 2785-2788, 2018 02 28.
Article
em En
| MEDLINE
| ID: mdl-29424534
ABSTRACT
Inspired by the dicationic nature of the electrophilic fluorinating reagent, Selectfluor (1), we rationally designed a series of dicarboxylic acid precatalysts (2), which, when deprotonated, act as anionic phase-transfer catalysts for asymmetric fluorination of alkenes. Among them, 2a having the shortest linker moiety efficiently catalyzed unprecedented 6-endo-fluoro-cyclization of various allylic amides, affording fluorinated dihydrooxazine compounds with high enantioselectivity (up to 99% ee). In addition to cyclic substrates, acyclic trisubstituted alkenes underwent the reaction with good diastereoselectivity, whereas low diastereoselectivity was observed for linear disubstituted alkenes. Results suggest that the reaction proceeds via a fluoro-carbocation intermediate.
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MEDLINE
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En
Ano de publicação:
2018
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Article