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Preparation of Solid, Substituted Allylic Zinc Reagents and Their Reactions with Electrophiles
Author(s) -
Ellwart Mario,
Knochel Paul
Publication year - 2015
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.201504354
Subject(s) - allylic rearrangement , reagent , chemistry , zinc , regioselectivity , electrophile , aryl , magnesium , organic chemistry , acylation , medicinal chemistry , combinatorial chemistry , catalysis , alkyl
The treatment of various allylic chlorides or bromides with zinc dust in the presence of lithium chloride and magnesium pivalate (Mg(OCO t Bu) 2 ) in THF affords allylic zinc reagents which, after evaporation of the solvent, produce solid zinc reagents that display excellent thermal stability. These allylic reagents undergo Pd‐catalyzed cross‐coupling reactions with PEPPSI‐IPent, as well as highly regioselective and diastereoselective additions to aryl ketones and aldehydes. Acylation with various acid chlorides regioselectively produces the corresponding homoallylic ketones, with the new CC bond always being formed on the most hindered carbon of the allylic system.