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Highly Regioselective Addition of Allylic Zinc Halides and Various Zinc Enolates to [1.1.1]Propellane
Author(s) -
Schwärzer Kuno,
Zipse Hendrik,
Karaghiosoff Konstantin,
Knochel Paul
Publication year - 2020
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.202009340
Subject(s) - regioselectivity , chemistry , allylic rearrangement , zinc , metalation , electrophile , propellane , aryl , medicinal chemistry , bioisostere , organic chemistry , chemical synthesis , alkyl , bicyclic molecule , catalysis , biochemistry , in vitro
We report a range of highly regioselective openings of [1.1.1]propellane with various allylic zinc halides, as well as zinc enolates of ketones, esters and nitriles. The resulting zincated bicyclopentanes (BCPs) were trapped with a range of electrophiles including acyl chlorides, sulfonothioates, hydroxylamino benzoates, tosyl cyanide as well as aryl and allyl halides, generating highly functionalized BCP‐derivatives. The unusually high regioselectivity of these reactions has been rationalized using DFT calculations. A bioisostere of the synthetic opioid pethidine was prepared in 95 % yield in one step using this method.