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Stereoselective Retentive Domino Transmetalations of Secondary Alkyllithium Compounds to Functionalized Secondary Alkylcopper Reagents
Author(s) -
Moriya Kohei,
Simon Meike,
Mose Rasmus,
Karaghiosoff Konstantin,
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.201505740
Subject(s) - domino , stereoselectivity , reagent , chemistry , combinatorial chemistry , organic chemistry , catalysis
Functionalized secondary alkyllithium reagents obtained by I/Li exchange from the corresponding secondary alkyl iodides undergo two successive transmetalations with Me 3 SiCH 2 ZnBr⋅LiBr and CuBr⋅2 LiCl⋅Me 2 S to provide functionalized secondary alkylcopper compounds with high retention of configuration. These alkylcopper derivatives react further with electrophiles such as alkynyl esters, acid chlorides, allylic chlorides, ketals, ethylene oxide, and 3‐iodocyclopentanone with high retention of configuration. A related sequence of transmetalations with MeMgI and LaCl 3 ⋅2 LiCl allows a retentive addition of secondary alkyllithium reagents to acetone. The influence of the solvent on the configurational stability of secondary alkylzinc reagents is described.