Novel Chiral 1,3‐Diamines by a Highly Modular Umpolung Strategy Employing a Diastereoselective Fluorination–Nucleophilic Aromatic Substitution Sequence

Abstract

A new highly modular synthesis for the rare class of chiral 1,3-diamines has been devised. It is accessible through nucleophilic aromatic ipso-substitution of fluorine in [(R,R)-1-fluoro-2-{(1-dimethylamino)ethyl}benzene]tricarbonylchromium and related complexes by secondary as well as primary amines. The precursor is accessible by a new diastereoselective electrophilic fluorination using N-fluorobenzenesulfonimide (NFSI), and the method is of potential interest for the synthesis of fluorinated pharmaceuticals. The protocol allows for the straightforward, modular synthesis of a broad library of diamines. A stock of 21 diamines has been synthesized. Primary amines bearing a stereogenic α-center can be intro-

N-Heterocyclic Olefin Catalysis for the Ring Opening of Cyclic Amidine Compounds: A Pathway to the Synthesis of ε-Caprolactam- and γ-Lactam-Derived Amines

“…Diamines, specially 1,2-diamines or 1,4-diamines, the majority of which display C2-symmetry, have a special role in coordination chemistry. − The 1,3-diamine family has not been used so often in coordination chemistry − due to the limited methods documented for its synthesis. Furthermore, 1,3-diamines are important structural motifs existing in many natural products with an increasing importance in the pharmaceutical chemistry .…”