Cyclic cis-1,3-Diamines Derived from Bicyclic Hydrazines: Synthesis and Applications

AbstractCyclic cis-1,3-diamines are versatile building blocks frequently found in natural molecules or biologically active compounds. In comparison with widely studied 1,2-diamines, and despite their chemical similarity, 1,3-diamines have been investigated less intensively probably because of a lack of general synthetic procedures giving access to these compounds with good levels of chemo-, regio-, and stereocontrol. In this Account we will give a general overview of the biological interest of cyclic cis-1,3-diamines. We will then describe the synthesis and potential applications of these compounds with a particular focus on the work realized in our laboratory.1 Introduction2 Biological Relevance of the cis-1,3-Diamine Motif3 Classical Synthetic Strategies towards cis-1,3-Diamines4 N–N Bond Cleavage of Bicyclic Hydrazines: A Versatile Method to Access cis-1,3-Diamines4.1 Preparation of Five-Membered Cyclic cis-1,3-Diamino Alcohols4.2 Access to Fluorinated 1,3-cis-Diaminocyclopentanes4.3 Synthesis of cis-1,3-Diaminocyclohexitols4.4 Formation of Cyclic cis-3,5-Diaminopiperidines5 Applications of Cyclic cis-1,3-Diamines5.1 Small-Molecular RNA Binders5.2 Fluorinated 1,3-Diamino Cyclopentanes as NMR Probes6 Concluding Remarks