Palladium and Platinum 2,4-cis-amino Azetidine and Related Complexes.

Akina Yoshizawa,Louise Male,Antonio Feula,John S Fossey,Andrew G Leach

doi:10.3389/fchem.2018.00211

Akina Yoshizawa, Louise Male + Show 3 more

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https://doi.org/10.3389/fchem.2018.00211

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Abstract

Seven N,N'-palladium(II) chloride complexes, one N,N'-palladium(II) acetate complex of 2,4-cis-azetidines where prepared and analyzed by single crystal XRD. Two platinum(II) chloride N,N'-complexes of 2,4-cis-azetidines where prepared and analyzed by single crystal XRD. Computational analysis and determination of the %Vbur was examined conducted. A CNN' metallocyclic complex was prepared by oxidative addition of palladium(0) to an ortho bromo 2,4-cis-disubstituted azetidine and its crystal structure displays a slightly pyramidalized metal-ligand orientation.

Highlights

Complexes of group 10 metals coordinated by N,N’-ligands have found wide use from therapeutics (Graham et al, 2004) through to catalysis (Fossey et al, 2005; Saito and Fu, 2007; Binder et al, 2012; Martínez-Olid et al, 2014; Álvarez-Casao et al, 2015)
Successful attempts to prepare crystals of metal complexes suitable for single crystal X-ray diffraction structure determination are reported along with crystal structures of unexpected by-products, a complex formed from a pyrrolidine ligand as well as an observation pertaining to diastereoisomer differentiation upon complexation and sample preparation under slightly different conditions
Our previously documented interest in the synthesis of 2,4-cisdisubstituted azetidines (Fossey et al.; Feula et al, 2010, 2013; Feula and Fossey, 2013; Hama Salih et al, 2015), and our recent use of the same family of azetidines as chiral ligands in asymmetric copper-catalyzed Henry reactions afforded us the opportunity to probe the complexation of these ligands and related compounds with various metal sources, in this report examples leading to samples suitable for analysis by X-ray single crystal diffraction studies are collected and compared

Summary

Introduction

Complexes of group 10 metals coordinated by N,N’-ligands have found wide use from therapeutics (Graham et al, 2004) through to catalysis (Fossey et al, 2005; Saito and Fu, 2007; Binder et al, 2012; Martínez-Olid et al, 2014; Álvarez-Casao et al, 2015). Our previously documented interest in the synthesis of 2,4-cisdisubstituted azetidines (Fossey et al.; Feula et al, 2010, 2013; Feula and Fossey, 2013; Hama Salih et al, 2015), and our recent use of the same family of azetidines as chiral ligands in asymmetric copper-catalyzed Henry reactions afforded us the opportunity to probe the complexation of these ligands and related compounds with various metal sources, in this report examples leading to samples suitable for analysis by X-ray single crystal diffraction studies are collected and compared.

Results

Conclusion