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Stereoselective Synthesis of Phosphoryl‐Substituted Phenols
Author(s) -
Xiong Biquan,
Li Mei,
Liu Yanxi,
Zhou Yongbo,
Zhao Changqiu,
Goto Midori,
Yin ShuangFeng,
Han LiBiao
Publication year - 2014
Publication title -
advanced synthesis and catalysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.541
H-Index - 155
eISSN - 1615-4169
pISSN - 1615-4150
DOI - 10.1002/adsc.201300913
Subject(s) - chemistry , lithium diisopropylamide , reagent , phosphorus , phosphorylation , walden inversion , aryl , phenols , ligand (biochemistry) , optically active , stereochemistry , stereoselectivity , catalysis , medicinal chemistry , organic chemistry , receptor , biochemistry , ion , alkyl , deprotonation
Abstract Copper‐catalyzed CX activation‐phosphorylation of aryls bearing different groups has been achieved using P(O)H compounds as efficient phosphorylation reagents without the assistance of any ligand. Optically active H ‐phosphinates can also act as good substrates in the reaction, giving the ( S p)‐phosphoryl substituted phenolic compounds stereospecifically with retention of configuration at the phosphorus center. Furthermore, it is shown that the migration of phosphorus on O‐aryl phosphonates from oxygen to carbon also proceeds stereospecifically to produce the corresponding optically active ( R p)‐phosphoryl‐substituted phenolic compounds with retention of configuration at phosphorus via treatment with lithium diisopropylamide (LDA). Plausible mechanisms have been proposed for these reactions.