A combination of directing groups and chiral anion phase-transfer catalysis for enantioselective fluorination of alkenes

作者：Wu Jeffrey; Wang Yi Ming; Drljevic Amela; Rauniyar Vivek; Phipps Robert J; Toste F Dean^*

来源：Proceedings of the National Academy of Sciences of the United States of America, 2013, 110(34): 13729-13733.

DOI：10.1073/pnas.1304346110

• asymmetric
• organocatalysis
• hydrogen-bonding

We report a catalytic enantioselective electrophilic fluorination of alkenes to form tertiary and quaternary C(sp3)-F bonds and generate beta-amino- and beta-aryl-allylic fluorides. The reaction takes advantage of the ability of chiral phosphate anions to serve as solid-liquid phase transfer catalysts and hydrogen bond with directing groups on the substrate. A variety of heterocyclic, carbocyclic, and acyclic alkenes react with good to excellent yields and high enantioselectivities. Further, we demonstrate a one-pot, tandem dihalogenation-cyclization reaction, using the same catalytic system twice in series, with an analogous electrophilic brominating reagent in the second step.

• 出版日期2013-8-20