Synthesis, Structure, and Metal Complexation Behavior of a New Type of Functionalized Chiral Phenanthroline Derivative

Plummer, Jacob M.; Weitgenant, Jeremy A.; Noll, Bruce C.; Lauher, Joseph W.; Wiest, Olaf; Helquist, Paul

doi:10.1021/jo702566m

Cited by 23 publications

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References 42 publications

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“…32 The ligand L1 in Fig. 1 has been reported 118 along with the structures of its Cu(II) and Zn(II) complexes. The two hydroxyalkyl groups at the 2 and 9 positions of the phen part of the ligand form 6-membered chelate rings, unlike PDALC, where 5-membered chelate rings are formed.…”

Section: +mentioning

confidence: 99%

The pyridyl group in ligand design for selective metal ion complexation and sensing

2013

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Factors in polypyridyl ligands that control their thermodynamic metal ion selectivity in aqueous solution, and their use in selective fluorescent sensing, are examined. Preorganization of polypyridyl ligands ranging from bidentate to tetradentate by bridging benzo groups, as are present in 1,10-phenanthroline (phen) compared to 2,2'-bipyridyl (bpy), is discussed. The role of solvation is considered in relation to the relative affinity of ligands containing pyridyl groups for divalent and trivalent metal ions in aqueous solution. The effects of steric clashes between H atoms on polypyridyl ligands in decreasing complex stability are evaluated, as well as the effect of chelate ring size on metal ion selectivity. Phen ligands with other donor groups present at the 2 and 9 positions, such as alcohols, amides, carboxylates, and oximes are discussed. The design of pyridyl-based ligands for the separation of Am(III) from lanthanide(III) ions is considered, as well as ligands for the removal of metal ions such as Cu(II) or Zn(II) in neurological diseases such as Alzheimer's. The design of pyridyl-based fluorescent sensors for selective sensing of metal ions is examined in terms of the role of spin-orbit coupling constants (ζ), paramagnetism, and steric effects in the development of selective fluorescent sensors that operate via chelation enhanced fluorescence (CHEF). It is concluded that for lighter metal ions with smaller ζ values such as Zn(II) and Ca(II), and to a lesser extent Cd(II), that the CHEF effect can be achieved with pyridyl-containing fluorophores that coordinate directly to the metal ion. The way in which steric effects can be used to decrease the CHEF effect in Zn(II) relative to Cd(II) to enable selective sensing of the latter is analyzed. For heavier metal ions such as Hg(II) and Pb(II), because of their large ζ values which quench fluorescence, it is concluded that the fluorophore should be tethered to the metal-binding part of the sensor, and prevented from binding to the metal ion by steric and electronic factors. How Hg(II) can quench the CHEF effect by π-contact with fluorophores such as the anthracenyl group, which at first sight might not seem able to bond with metal ions, is examined.

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Section: +mentioning

confidence: 99%

The pyridyl group in ligand design for selective metal ion complexation and sensing

2013

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“…Many types of supporting ligands may be used in these reactions, and although 1,10-phenanthrolines have broad utility, their use in hydroaminations has not been demonstrated . This fact, as well as our previous development of methods for the synthesis of functionalized phenanthrolines, has prompted us to investigate the use of this ligand class in these reactions. We wish to report the results of these studies whereby silver−1,10-phenanthroline complexes function as efficient and recyclable catalysts for the intramolecular hydroamination of aminoalkynes.…”

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confidence: 99%

Intramolecular Hydroamination of Aminoalkynes with Silver−Phenanthroline Catalysts

et al. 2008

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Intramolecular hydroamination of several aminoalkynes catalyzed by silver-phenanthroline complexes is reported. This catalyst system complements previous protocols by employing air- and moisture-stable complexes without compromising activity or reaction control. Some of the hydroamination products are subject to a useful aerobic oxidation. Silver-phenanthroline complexes have successfully demonstrated efficacy in the desymmetrization of a prochiral diyne.

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“…Some of the important applications of chiral phenanthroline derivatives in asymmetric catalysis, which have mainly come from the Chelucci group, include Pd‐catalyzed allylic alkylation of allylic acetates,12 Cu‐catalyzed cyclopropanation of styrenes,13 Rh‐catalyzed asymmetric hydrosilylation14 and transfer hydrogenation of ketones,15 and Cu‐catalyzed allylic oxidation of alkenes 16. In addition, Helquist and co‐workers recently reported the synthesis of a functionalized chiral phenanthroline in 17–42 % yield through SmI 2 ‐mediated coupling of the parent 1,10‐phenanthroline with ( R )‐1,2‐epoxybutane 11j. However, no application of this ligand in asymmetric catalysis has yet been reported in the literature.…”

Section: Introductionmentioning

confidence: 91%

Enantioselective Synthesis of a Novel Chiral 2,9‐Disubstituted 1,10‐Phenanthroline and First Applications in Asymmetric Catalysis

2009

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The asymmetric synthesis of a novel, C2‐symmetric, tetradentate 1,10‐phenanthroline is described; it is based on the stereoselective preparation of two functionalized pyridine subunits, which were subsequently joined through two consecutive carbon–carbon bond‐forming reactions to assemble the heteroaromatic system. Some initial applications of this new chiral ligand in metal‐catalyzed, enantioselective ring‐opening reactions of meso‐epoxides and aminations of β‐keto esters are presented.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

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Synthesis, Structure, and Metal Complexation Behavior of a New Type of Functionalized Chiral Phenanthroline Derivative

Cited by 23 publications

References 42 publications

The pyridyl group in ligand design for selective metal ion complexation and sensing

The pyridyl group in ligand design for selective metal ion complexation and sensing

Intramolecular Hydroamination of Aminoalkynes with Silver−Phenanthroline Catalysts

Enantioselective Synthesis of a Novel Chiral 2,9‐Disubstituted 1,10‐Phenanthroline and First Applications in Asymmetric Catalysis

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