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Generation and Application of Homoenolate Equivalents Utilizing [1,2]‐Phospha‐Brook Rearrangement under Brønsted Base Catalysis
Author(s) -
Kondoh Azusa,
Aoki Takuma,
Terada Masahiro
Publication year - 2017
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.201605673
Subject(s) - electrophile , chemistry , catalysis , phosphazene , base (topology) , adduct , brønsted–lowry acid–base theory , medicinal chemistry , equivalent , organic base , organic chemistry , mathematical analysis , mathematics , polymer , biochemistry
A new method for catalytic generation of a homoenolate equivalent and its application to carbon−carbon bond formation was developed by utilizing the [1,2]‐phospha‐Brook rearrangement under Brønsted base catalysis. The α‐oxygenated allyl anions, which can serve as homoenolate equivalents, were catalytically generated in situ by treating readily available chalcones with diethyl phosphite or the pre‐formed 1,2‐adducts of diethyl phosphite with chalcones in the presence of a catalytic amount of a phosphazene base, P2‐ t Bu. The resulting allyl anions were subsequently trapped by various electrophiles, including Michael acceptors, imines, and aldehydes, providing the corresponding adducts in good yields with moderate to good diastereoselectivities.