Stereoselective Retentive Domino Transmetalations of Secondary Alkyllithium Compounds to Functionalized Secondary Alkylcopper Reagents. Issue 37 (14th August 2015)

• Record Type: Journal Article
• Authors: Moriya, Kohei; Simon, Meike; Mose, Rasmus; Karaghiosoff, Konstantin; Knochel, Paul
• Is Part Of: Angewandte Chemie international edition. Volume 54:Issue 37(2015)
• Page Start: 10963
• Page End: 10967
• Publication Date: 2015-08-14
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201505740
• Languages: English
• ISSNs: 1433-7851

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Functionalized secondary alkyllithium reagents obtained by I/Li exchange from the corresponding secondary alkyl iodides undergo two successive transmetalations with Me₃SiCH₂ZnBr⋅LiBr and CuBr⋅2 LiCl⋅Me₂S 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 LaCl₃⋅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.</p> </abstract>