Side chain functionalized η5-tetramethyl cyclopentadienyl complexes of Rh and Ir with a pendant primary amine group

Reiner, Thomas; Jantke, Dominik; Raba, Andreas; Marziale, Alexander N.; Eppinger, Jörg

doi:10.1016/j.jorganchem.2009.01.056

Cited by 24 publications

(14 citation statements)

References 52 publications

(33 reference statements)

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“…[12,19,28,29] The dimeric precursor was reacted in situ with a selection of commercially available bidentate ligands (Scheme 2). To identify suitable coordination conditions, the chiral ligand l-ProNH 2 was complexed in situ with the dinuclear catalyst precursors [MCp* biotin Cl 2 ] 2 (M = Ir, Rh) at different pH values within the buffer range of 3-(N-morpholino)propanesulfonic acid (MOPS) or 2-(N-morpholino)ethanesulfonic acid.…”

Section: Resultsmentioning

confidence: 99%

Expanding the Chemical Diversity in Artificial Imine Reductases Based on the Biotin–Streptavidin Technology

Quinto¹,

Schwizer²,

Zimbron³

et al. 2014

ChemCatChem

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We report on the optimization of an artificial imine reductase based on the biotin‐streptavidin technology. With the aim of rapidly generating chemical diversity, a novel strategy for the formation and evaluation of biotinylated complexes is disclosed. Tethering the biotin‐anchor to the Cp* moiety leaves three free coordination sites on a d6 metal for the introduction of chemical diversity by coordination of a variety of ligands. To test the concept, 34 bidentate ligands were screened and a selection of the 6 best was tested in the presence of 21 streptavidin (Sav) isoforms for the asymmetric imine reduction by the resulting three legged piano stool complexes. Enantiopure α‐amino amides were identified as promising bidentate ligands: up to 63 % ee and 190 turnovers were obtained in the formation of 1‐phenyl‐1,2,3,4‐tetrahydroisoquinoline with [IrCp*biotin(L‐ThrNH2)Cl]⊂SavWT as a catalyst.

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Section: Resultsmentioning

confidence: 99%

Expanding the Chemical Diversity in Artificial Imine Reductases Based on the Biotin–Streptavidin Technology

Quinto¹,

Schwizer²,

Zimbron³

et al. 2014

ChemCatChem

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“…Although this reaction is typically performed in MeOH or EtOH, ( 22, 23 ) we were pleased to find that the reaction proceeds to completion in a 4:1 mixture of H 2 O/MeOH under basic conditions (200 mol % CsOAc), despite the sparing solubility of the substrates in this solvent mixture. Next, we designed a biotinylated analog [RhCp* biotin Cl 2 ] 2 ( 26 ) for incorporation within streptavidin ( Sav hereafter, Fig. 1).…”

mentioning

confidence: 99%

Biotinylated Rh(III) Complexes in Engineered Streptavidin for Accelerated Asymmetric C–H Activation

Hyster

Knörr

Ward

et al. 2012

Science

745

371

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Enzymes provide an exquisitely tailored chiral environment to foster high catalytic activities and selectivities, but their native structures are optimized for very specific biochemical transformations. Designing a protein to accommodate a non-native transition metal complex can broaden the scope of enzymatic transformations while raising the activity and selectivity of small molecule catalysis. Herein, we report the creation of a bifunctional artificial metalloenzyme in which a glutamic acid or aspartic acid residue engineered into streptavidin acts in concert with a docked biotinylated rhodium(III) complex to enable catalytic asymmetric C–H activation. The coupling of benzamides and alkenes to access dihydroisoquinolones proceeds with up to nearly a hundredfold rate acceleration compared to the activity of the isolated Rh complex and enantiomeric ratios as high as 93: 7.

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“…Some reports about functionalized h 6 -arene ruthenium(II) complexes exist in literature [13]. For example, h 6 -arenes with pendant carboxylate groups [14,15], alcohols [16], or even amino acids [17e20] have been synthesized (A, Fig. 1).…”

Section: Introductionmentioning

confidence: 99%

“…1). Several examples of h 6 :h 1 -arenes which include an additional tether at the metal centre are known, comprising functional groups such as alcohols [21], amides [22,15] or carbenes [23e25]. Solubility in aqueous solutions is crucial for bioavailability of organometallic systems, hence studies were reported targeting improved uptake, biomolecular interactions and efficacy of h 6 -arene ruthenium(II) systems via side chain functionalization of the arene ligand [12].…”

Section: Introductionmentioning

confidence: 99%

“…While the half-sandwich architecture of such complexes is particularly important to generate the desired reactivity profile, the labile coordination sphere at the metal center may complicate synthetic access due to additional coordination of the side chain [15]. We herein report the synthesis of three new m-chloro-bridged h 6 -arene ruthenium(II) complexes as well as the first examples of functionalized h 6 -arene osmium(II) species providing a pendant reactive donor moiety.…”

Section: Introductionmentioning

confidence: 99%

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η6-Arene complexes of ruthenium and osmium with pendant donor functionalities

Reiner

Waibel

Marziale

et al. 2010

Journal of Organometallic Chemistry

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Side chain functionalized η5-tetramethyl cyclopentadienyl complexes of Rh and Ir with a pendant primary amine group

Cited by 24 publications

References 52 publications

Expanding the Chemical Diversity in Artificial Imine Reductases Based on the Biotin–Streptavidin Technology

Expanding the Chemical Diversity in Artificial Imine Reductases Based on the Biotin–Streptavidin Technology

Biotinylated Rh(III) Complexes in Engineered Streptavidin for Accelerated Asymmetric C–H Activation

η6-Arene complexes of ruthenium and osmium with pendant donor functionalities

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