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Organocatalytic Enantioselective Vinylogous Pinacol Rearrangement Enabled by Chiral Ion Pairing
Author(s) -
Wu Hua,
Wang Qian,
Zhu Jieping
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201609911
Subject(s) - enantioselective synthesis , allylic rearrangement , pinacol , chemistry , chirality (physics) , ion , catalysis , tetrahydrofuran , organic chemistry , chiral anomaly , physics , fermion , quantum mechanics , nambu–jona lasinio model , solvent
An enantioselective pinacol rearrangement of functionalized ( E )‐2‐butene‐1,4‐diols was developed. In the presence of a catalytic amount of a chiral BINOL‐derived N ‐triflyl phosphoramide, these 1,4‐diols rearranged to β,γ‐unsaturated ketones in excellent yields and enantioselectivities. The formation of a chiral ion pair between the intermediary allylic cation and the chiral phosphoramide anion was postulated to be responsible for the highly efficient chirality transfer. These chiral building blocks were further converted into enantioenriched polysubstituted tetrahydrofuran and tetrahydronaphthalene derivatives.