19350-64-2Relevant academic research and scientific papers
Wrapping Rhodium in a Borane Canopy: Implications for Hydride Formation and Transfer
Zurakowski, Joseph A.,Austen, Brady J. H.,Drover, Marcus W.
, p. 2450 - 2457 (2021)
The unique reactivity of metal hydrides has encouraged considerable advances in both synthesis and catalysis. In this arena, ligand optimization has played a significant role, wherein metal-ligand cooperativity can be employed to guide reactivity. Of the
Octaboraneyl [Ni(H)(diphosphine)2]+Complexes: Exploiting Phosphine Ligand Lability for Hydride Transfer to an [NAD]+Model
Zurakowski, Joseph A.,Bhattacharyya, Moulika,Spasyuk, Denis M.,Drover, Marcus W.
, p. 37 - 41 (2021)
Ligand design represents a central tenet of synthetic chemistry, wherein simple modification can lead to major differences in reactivity. Herein, we describe the preparation of two bis(diphosphino)nickel(II) hydride complexes that contain eight pendant boranes in their secondary coordination sphere, [Ni(H)(P2BR4)2]+ (R = Cy or Mes; Mes = 2,4,6-trimethylphenyl). Divergent reactivity of the cyclohexyl analogue toward the [NAD]+ model, 3-acetyl-N-benzylpyridinium bromide ([BNAcP]Br), is underscored. While [Ni(H)(P2BCy4)2]+ undergoes rapid hydride transfer, the related species [Ni(H)(dnppe)2]+ [dnppe = 1,2-bis(di-n-propylphosphino)ethane] and adduct [Ni(H)(P2BCy4)2(DMAP)8]+ (DMAP = 4-N,N-dimethylaminopyridine) exhibit no such reactivity. This borane-appended nickel(II) hydride distinguishes itself from its "all-alkyl"cousins and provides future opportunities for the design of [Ni(H)(diphosphine)2]+ reagents for hydride transfer.
Straightforward Regeneration of Reduced Flavin Adenine Dinucleotide Required for Enzymatic Tryptophan Halogenation
Ismail, Mohamed,Schroeder, Lea,Frese, Marcel,Kottke, Tilman,Hollmann, Frank,Paul, Caroline E.,Sewald, Norbert
, p. 1389 - 1395 (2019/02/10)
Flavin-dependent halogenases are known to regioselectively introduce halide substituents into aromatic moieties, for example, the indole ring of tryptophan. The process requires halide salts and oxygen instead of molecular halogen in the chemical halogena
Mimicking nature: Synthetic nicotinamide cofactors for C=C bioreduction using enoate reductases
Paul, Caroline E.,Gargiulo, Serena,Opperman, Diederik J.,Lavandera, Iván,Gotor-Fernández, Vicente,Gotor, Vicente,Taglieber, Andreas,Arends, Isabel W. C. E.,Hollmann, Frank
supporting information, p. 180 - 183 (2013/04/24)
A series of synthetic nicotinamide cofactors were synthesized to replace natural nicotinamide cofactors and promote enoate reductase (ER) catalyzed reactions without compromising the activity or stereoselectivity of the bioreduction process. Conversions and enantioselectivities of >99% were obtained for C=C bioreductions, and the process was successfully upscaled. Furthermore, high chemoselectivity was observed when employing these nicotinamide cofactor mimics (mNADs) with crude extracts in ER-catalyzed reactions.
Structure Sensitivity of the Marcus λ for Hydride Transfer between NAD+ Analogues
Kreevoy, Maurice M.,Ostovic, Drazen,Lee, In-Sook Han,Binder, David A.,King, Gary W.
, p. 524 - 530 (2007/10/02)
Thirty-five rate constants, kij, for transfer of hydride between various pyridinium, quinilinium, acridinium, and phenantridinium ions spanning a range of over 10E11 in their equilibrium constants Kij and over 10E6 in kij
Photosensitized Hydride Transfer. Highly Regioselective 1,4-Photoreduction of NAD(P)+ Models under Visible Light with an Organometallic Rhodium(III) Porphyrin as Sensitizer
Aoyama, Yasuhiro,Midorikawa, Koji,Toi, Hiroo,Ogoshi, Hisanobu
, p. 1651 - 1654 (2007/10/02)
An organometallic acetyl-Rh complex of octaethylporphyrin catalyzes under the visible light the photoreduction of 1-benzylnicotinamide (BNA+) or 1-benzyl-3-acetylpyridinium ion (BAP+) as NAD(P)+ model with tetraphenylborate as a reductant and an alcohol as a proton source to give the corresponding 1,4-dihydro derivative (BNAH or BAPH) as the sole reduction product and biphenyl as the oxidation product of B(C6H5)4-.
Hydride Transfer and Oxyanion Addition Equilibria of NAD+ Analogues
Ostovic, Drazen,Lee, In-Sook Han,Roberts, Roger M. G.,Kreevoy, Maurice M.
, p. 4206 - 4211 (2007/10/02)
Equilibrium constants, K, have been determined for the reduction of 10-methylacridinium ion by 15 N-heterocyclic hydride donors: acridine, quinoline, pyridine, and phenanthridine derivatives.The solvent was a mixture of 2-propanol and water in the ratio 4 : 1 by volume.Reduction potentials have been estimated for the corresponding cations in aqueous solution by assuming that the K's would be the same and accepting -361 mV as the reduction potential of the 3-(aminocarbonyl)-1-benzylpyridinium ion.These reduction potentials span 430 mV.Values of pKR have also been determined for six of the cations in the same solvent.For derivatives of the same ring system, -ΔlogK is approximately equal to ΔpKR, but a 4 log unit discrepancy appears when phenanthridine derivatives are compared with the 9-methylacridinium ion.
