Sulfur‐Directed Construction of Vinyl Cyclopropanes from 1,3‐Dienes
Abstract
ABSTRACT The stereoselective cyclopropanation of 1,3‐dienes remains a long‐standing challenge in the preparation of vinyl cyclopropanes (VCPs) due to the intrinsic electronic and steric bias of the diene scaffold. We report a sulfur‐directed strategy that enables highly site‐ and diastereoselective cyclopropanation of S ‐substituted 1,3‐dienes with diazo reagents under Cu‐catalyzed reaction conditions. This unprecedented approach overrides the innate reactivity of the 1,3‐diene through a thioether‐directed reaction mode, providing rapid access to a broad library of highly functionalized S ‐VCPs obtained as single regio‐ and diastereomers. Preliminary mechanistic studies indicate a pericyclic cascade involving a 6π‐electrocyclization and a [2,3]‐sigmatropic rearrangement and postmodifications permit streamlined access to complex VCPs that remain inaccessible through conventional cyclopropanation techniques.
Article Details
Authors (7)
Anna Keimer
Institute of Chemistry and Biochemistry Freie Universität Berlin Berlin Germany
Jonas Rettig
Institute of Chemistry and Biochemistry Freie Universität Berlin Berlin Germany
Tim‐Niclas Streit
Institute of Chemistry and Biochemistry Freie Universität Berlin Berlin Germany
Bob Barthel
Institute of Chemistry and Biochemistry Freie Universität Berlin Berlin Germany
Mélissa Calmels
Institute of Chemistry and Biochemistry Freie Universität Berlin Berlin Germany
Moritz Malischewski
Institut für Chemie und Biochemie − Anorganische Chemie, Freie Universität Berlin, Fabeckstr. 34-36, Berlin 14195, Germany
Franz‐Lucas Haut
Institute of Chemistry and Biochemistry Freie Universität Berlin Berlin Germany