16183-83-8Relevant academic research and scientific papers
Interaction of Sulfur Dioxide with 1-Benzyl-1,4-dihydronicotinamide
Jarvis, William F.,Dittmer, Donald C.
, p. 2784 - 2786 (1983)
Anhydrous sulfur dioxide reacts rapidly with 1-benzyl-1,4-dihydronicotinamide to give a reduced species of sulfur dioxide, possibly HSO2(1-),which can be trapped by reaction with Michael acceptors to give sulfones.
Long-Lived C60Radical Anion Stabilized Inside an Electron-Deficient Coordination Cage
Baksi, Ananya,Clever, Guido H.,Hasegawa, Shota,Holstein, Julian J.,Kasanmascheff, Müge,Meichsner, Shari L.
, p. 9718 - 9723 (2021)
Fullerene C60 and its derivatives are widely used in molecular electronics, photovoltaics, and battery materials, because of their exceptional suitability as electron acceptors. In this context, single-electron transfer on C60 generates the C60???- radical anion. However, the short lifetime of free C60???- hampers its investigation and application. In this work, we dramatically stabilize the usually short-lived C60???- species within a self-assembled M2L4 coordination cage consisting of a triptycene-based ligand and Pd(II) cations. The electron-deficient cage strongly binds C60 by providing a curved inner ?-surface complementary to the fullerene's globular shape. Cyclic voltammetry revealed a positive potential shift for the first reduction of encapsulated C60, which is indicative of a strong interaction between confined C60???- and the cationic cage. Photochemical one-electron reduction with 1-benzyl-1,4-dihydronicotinamide allows selective and quantitative conversion of the confined C60 molecule in millimolar acetonitrile solution at room temperature. Radical generation was confirmed by nuclear magnetic resonance, electron paramagnetic resonance, ultraviolet-visible-near-infrared spectroscopy and electrospray ionization mass spectrometry. The lifetime of C60???- within the cage was determined to be so large that it could still be detected after one month under an inert atmosphere.
Cupric superoxo-mediated intermolecular C-H activation chemistry
Peterson, Ryan L.,Himes, Richard A.,Kotani, Hiroaki,Suenobu, Tomoyoshi,Tian, Li,Siegler, Maxime A.,Solomon, Edward I.,Fukuzumi, Shunichi,Karlin, Kenneth D.
, p. 1702 - 1705 (2011)
The new cupric superoxo complex [LCuII(O2 -)]+, which possesses particularly strong O-O and Cu-O bonding, is capable of intermolecular C-H activation of the NADH analogue 1-benzyl-1,4-dihydronicotinamide (BNAH).
A Chromium(III)-Superoxo Complex as a Three-Electron Oxidant with a Large Tunneling Effect in Multi-Electron Oxidation of NADH Analogues
Devi, Tarali,Lee, Yong-Min,Jung, Jieun,Sankaralingam, Muniyandi,Nam, Wonwoo,Fukuzumi, Shunichi
, p. 3510 - 3515 (2017)
Metal-superoxo species are involved in a variety of enzymatic oxidation reactions, and multi-electron oxidation of substrates is frequently observed in those enzymatic reactions. A CrIII-superoxo complex, [CrIII(O2)(TMC)(Cl)]+ (1; TMC=1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), is described that acts as a novel three-electron oxidant in the oxidation of dihydronicotinamide adenine dinucleotide (NADH) analogues. In the reactions of 1 with NADH analogues, a CrIV-oxo complex, [CrIV(O)(TMC)(Cl)]+ (2), is formed by a heterolytic O?O bond cleavage of a putative CrII-hydroperoxo complex, [CrII(OOH)(TMC)(Cl)], which is generated by hydride transfer from NADH analogues to 1. The comparison of the reactivity of NADH analogues with 1 and p-chloranil (Cl4Q) indicates that oxidation of NADH analogues by 1 proceeds by proton-coupled electron transfer with a very large tunneling effect (for example, with a kinetic isotope effect of 470 at 233 K), followed by rapid electron transfer.
Metal ion-catalyzed cycloaddition vs hydride transfer reactions of NADH analogues with p-benzoquinones
Fukuzumi,Fujii,Suenobu
, p. 10191 - 10199 (2001)
1-Benzyl-4-tert-butyl-1,4-dihydronicotinamide (t-BuBNAH) reacts efficiently with p-benzoquinone (Q) to yield a [2+3] cycloadduct (1) in the presence of Sc(OTf)3 (OTf = OSO2CF3) in deaerated acetonitrile (MeCN) at room temperature, while no reaction occurs in the absence of Sc3+. The crystal structure of 1 has been determined by the X-ray crystal analysis. When t-BuBNAH is replaced by 1-benzyl-1,4-dihydronicotinamide (BNAH), the Sc3+-catalyzed cycloaddition reaction of BNAH with Q also occurs to yield the [2+3] cycloadduct. Sc3+ forms 1:4 complexes with t-BuBNAH and BNAH in MeCN, whereas there is no interaction between Sc3+ and Q. The observed second-order rate constant (kobs) shows a first-order dependence on [Sc3+] at low concentrations and a second-order dependence at higher concentrations. The first-order and the second-order dependence of the rate constant (ket) on [Sc3+] was also observed for the Sc3+-promoted electron transfer from CoTPP (TPP = tetraphenylporphyrin dianion) to Q. Such dependence of ket on [Sc3+] is ascribed to formation of 1:1 and 1:2 complexes between Q?- and Sc3+ at the low and high concentrations of Sc3+, respectively, which results in acceleration of the rate of electron transfer. The formation constants for the 1:2 complex (K2) between the radical anions of a series of p-benzoquinone derivatives (X - Q?-) and Sc3+ are determined from the dependence of ket on [Sc3+]. The K2 values agree well with those determined from the dependence of kobs on [Sc3+] for the Sc3+-catalyzed addition reaction of t-BuBNAH and BNAH with X - Q. Such an agreement together with the absence of the deuterium kinetic isotope effects indicates that the addition proceeds via the Sc3+-promoted electron transfer from t-BuBNAH and BNAH to Q. When Sc(OTf)3 is replaced by weaker Lewis acids such as Lu(OTf)3, Y(OTf)3, and Mg(ClO4)2, the hydride transfer reaction from BNAH to Q also occurs besides the cycloaddition reaction and the kobs value decreases with decreasing the Lewis acidity of the metal ion. Such a change in the type of reaction from a cycloaddition to a hydride transfer depending on the Lewis acidity of metal ions employed as a catalyst is well accommodated by the common reaction mechanism featuring the metal-ion promoted electron transfer from BNAH to Q.
Mechanisms of the oxidations of NAD(P)H model Hantzsch 1,4-dihydropyridines by nitric oxide and its donor N-methyl-N-nitrosotoluene-p-sulfonamide
Zhu,Zhao,Cheng
, p. 8158 - 8163 (2000)
4-Substituted derivatives of Hantzsch 1,4-dihydropyridine were treated by nitric oxide (NO) or its donor N-methyl-N-nitrosotoluene-p-sulfonamide (MNTS) to give the corresponding pyridine derivatives. When the 4-substituted group was methyl, ethyl, n-propy
Coenzyme Models. Part 24. Micellar Catalysis of Flavin-mediated Reactions. Influence of the Flavin Structure on the Reactivity
Shinkai, Seiji,Kusano, Yumiko,Manabe, Osamu,Yoneda, Fumio
, p. 1111 - 1115 (1980)
The catalytic effect of a cationic (CTAB) micelle on the flavin-mediated oxidation of 1-benzyl-1,4-dihydronicotinamide (6), nitroethane carbanion (7), and thiophenol (8) is reported.The oxidation of (6) was subject to a small extent to micellar catalysis, whereas the oxidation of (7) and (8) which does not proceed in a simple aqueous solution was efficiently catalysed by the CTAB micelle.The rate of oxidation of (7) was profoundly dependent upon the structure of the flavin: flavins which have either a long alkyl group or a carboxy-group gave rate constants greater by 103-104 fold than unmodified flavin, and the rate constant for flavin (5) which has both groups was further enhanced (>106 fold).On the other hand, the oxidation of (8) was less affected by the change in the flavin structure.The reactivity order for the oxidation of (7) was (1) (unmodified neutral flavin) (2) (neutral flavin with a hexadecyl group) (4) (anionic flavin with a carboxy-group) (5) (anionic flavin with carboxy- and tetradecanoyl groups), whereas that for the oxidation of (8) was (1) (4) (2).The results indicate that the reactivity of flavins is variable, depending not only on the type of reaction but also on the environment.The results provide useful information on the versatile reactivity of flavin coenzymes bound to apoenzymes.
Selective one-electron and two-electron reduction of C60 with NADH and NAD dimer analogues via photoinduced electron transfer
Fukuzumi, Shunichi,Suenobu, Tomoyoshi,Patz, Matthias,Hirasaka, Takeomi,Itoh, Shinobu,Fujitsuka, Mamoru,Ito, Osamu
, p. 8060 - 8068 (1998)
The selective one-electron reduction of C60 to C60.- is attained through photoinduced electron transfer from an NADH analogue, 1-benzyl-1,4- dihydronicotinamide (BNAH), and the dimer analogue [(BNA)2] to the tri
Bis-1,4-dihydronicotinamides. Intramolecular Electronic Interaction and Its Consequence in the Reduction of a Carbonyl Substrate in Aprotic Solvents
Murakami, Yukito,Aoyama, Yasuhiro,Kikuchi, Jun-ichi
, p. 444 - 446 (1981)
The reduction of hexachloroacetone in CH2Cl2 or CHCl3 was much enhanced in the presence of 1,6-bis(1-benzyl-1,4-dihydronicotinamido)hexane owing to an intramolecular electronic interaction of charge transfer character.
Hydricities of BzNADH, CH5Mo(PMe3)(CO)2H, and C5Me5Mo(PMe3)(CO)2H in acetonitrile.
Ellis, William W,Raebiger, James W,Curtis, Calvin J,Bruno, Joseph W,DuBois, Daniel L
, p. 2738 - 2743 (2004)
The thermodynamic hydride donor abilities of 1-benzyl-1,4-dihydronicotinamide (BzNADH, 59 +/- 2 kcal/mol), C(5)H(5)Mo(PMe(3))(CO)(2)H (55 +/- 3 kcal/mol), and C(5)Me(5)Mo(PMe(3))(CO)(2)H (58 +/- 2 kcal/mol) have been measured in acetonitrile by calorimetr
