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Enantiospecific Synthesis of ortho ‐Substituted 1,1‐Diarylalkanes by a 1,2‐Metalate Rearrangement/ anti ‐S N 2′ Elimination/Rearomatizing Allylic Suzuki–Miyaura Reaction Sequence
Author(s) -
Rubial Belén,
Collins Beatrice S. L.,
Bigler Raphael,
Aichhorn Stefan,
Noble Adam,
Aggarwal Varinder K.
Publication year - 2019
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.201811343
Subject(s) - chemistry , allylic rearrangement , benzylamine , aryl , stereospecificity , iodide , medicinal chemistry , boronic acid , phenylboronic acid , palladium , catalysis , organic chemistry , combinatorial chemistry , alkyl
The one‐pot sequential coupling of benzylamines, boronic esters, and aryl iodides has been investigated. In the presence of an N‐activator, the boronate complex formed from an ortho ‐lithiated benzylamine and a boronic ester undergoes stereospecific 1,2‐metalate rearrangement/anti‐S N 2′ elimination to form a dearomatized tertiary boronic ester. Treatment with an aryl iodide under palladium catalysis leads to rearomatizing γ‐selective allylic Suzuki–Miyaura cross‐coupling to generate 1,1‐diarylalkanes. When enantioenriched α‐substituted benzylamines are employed, the corresponding 1,1‐diarylalkanes are formed with high stereospecificity.