scholarly journals Synthesis, Structure, and Catalytic Reactivity of Pd(II) Complexes of Proline and Proline Homologs

Catalysts ◽  
2019 ◽  
Vol 9 (6) ◽  
pp. 515 ◽  
Author(s):  
David B. Hobart ◽  
Joseph S. Merola ◽  
Hannah M. Rogers ◽  
Sonia Sahgal ◽  
James Mitchell ◽  
...  
Keyword(s):  
Hydrogen Bonding ◽  
Amino Acid ◽  
Oxidative Coupling ◽  
Lattice Structures ◽  
Single Crystal Xrd ◽  
Acetone Water ◽  
Square Planar ◽  
Catalytically Active ◽  
Catalytic Reactivity ◽  
Phenylboronic Acids

Palladium(II) acetate reacts with proline and proline homologs in acetone/water to yield square planar bis-chelated palladium amino acid complexes. These compounds are all catalytically active with respect to oxidative coupling of olefins and phenylboronic acids. Some enantioselectivity is observed and formation of products not reported in other Pd(II) oxidative couplings is seen. The crystal structures of nine catalyst complexes were obtained. Extended lattice structures arise from N-H••O or O••(HOH)••O hydrogen bonding. NMR, HRMS, and single-crystal XRD data obtained on all are evaluated.

scholarly journals Synthesis, Characterization, and Non-Covalent Interactions of Palladium(II)-Amino Acid Complexes

Molecules ◽  
2021 ◽  
Vol 26 (14) ◽  
pp. 4331
Author(s):  
David B. Hobart ◽  
Michael A. G. Berg ◽  
Hannah M. Rogers ◽  
Joseph S. Merola
Keyword(s):  
Amino Acid ◽  
High Resolution Mass Spectrometry ◽  
Resonance Spectroscopy ◽  
Spectroscopic Techniques ◽  
X Ray Diffraction ◽  
Amino Acid Complexes ◽  
Acetone Water ◽  
Square Planar ◽  
Non Covalent Interactions ◽  
Covalent Interactions

The reaction of palladium(II) acetate with acyclic amino acids in acetone/water yields square planar bis-chelated palladium amino acid complexes that exhibit interesting non-covalent interactions. In all cases, complexes were examined by multiple spectroscopic techniques, especially HRMS (high resolution mass spectrometry), IR (infrared spectroscopy), and 1H NMR (nuclear magnetic resonance) spectroscopy. In some cases, suitable crystals for single crystal X-ray diffraction were able to be grown and the molecular structure was obtained. The molecular geometries of the products are discussed. Except for the alanine complex, all complexes incorporate water molecules into the extended lattice and exhibit N-H···O and/or O···(HOH)···O hydrogen bonding interactions. The non-covalent interactions are discussed in terms of the extended lattice structures exhibited by the structures.

Amino acid derived CuII compounds as catalysts for asymmetric oxidative coupling of 2-naphthol

2015 ◽  
Vol 44 (4) ◽  
pp. 1612-1626 ◽  
Author(s):  
Pedro Adão ◽  
Sónia Barroso ◽  
M. Fernanda N. N. Carvalho ◽  
Carlos M. Teixeira ◽  
Maxim L. Kuznetsov ◽  
...  
Keyword(s):  
Amino Acid ◽  
Oxidative Coupling ◽  
Product Yields ◽  
Aqueous Conditions

Several chiral amino acid-derived CuII complexes were prepared and used as catalysts in the aerobic oxidative coupling of 2-naphthol. Moderate homocoupling product yields and enantiomeric excesses were obtained under mild, aqueous conditions.

Enantioselective Nucleophilic Aromatic Substitution Reaction of Azlactones to Synthesize Quaternary α-Amino Acid Derivatives

Synlett ◽  
2020 ◽  
Author(s):  
Xiaohua Liu ◽  
Yi Li ◽  
Hao Pan ◽  
Wang-Yuren Li ◽  
Xiaoming Feng
Keyword(s):  
Hydrogen Bonding ◽  
Charge Transfer ◽  
Amino Acid ◽  
Substitution Reaction ◽  
Nucleophilic Aromatic Substitution ◽  
Amino Acid Derivatives ◽  
Amino Acid Esters ◽  
Aromatic Substitution ◽  
Charge Transfer Interaction ◽  
Acid Esters

AbstractAn asymmetric organocatalytic nucleophilic aromatic substitution reaction of azlactones with electron-deficient aryls was established. A variety of α-aryl α-alkyl α-amino acid esters and peptides were obtained in decent yields and stereoselectivities. A new bifunctional catalytic mode involving charge-transfer interaction and hydrogen bonding is proposed to explain the enantioselectivity.

Synthesis, characterisation and activity in catalytic epoxidation of olefins of new dinuclear nickel(ll) complexes

2009 ◽  
Vol 2009 (8) ◽  
pp. 527-532
Author(s):  
Manindranath Bera
Keyword(s):  
Visible Region ◽  
Chemical Oxidation ◽  
Cyclic Voltammetric ◽  
Catalytic Epoxidation ◽  
Redox Couples ◽  
Square Planar ◽  
Catalytically Active ◽  
Mecn Solution ◽  
Voltammetric Measurements ◽  
Epoxidation Of Olefins

Two new dinuclear nickel(ll) compounds of formula [Nill2(μ-L1)2](CIO4)2·MeCN (1·MeCN) and [NiII2(μ-L2)2](CIO4)2 (2) where HL1 and HL2 stand for 3-(2-(dimethylamino)ethylimino)butan-2-one oxime and 1-(2-(dimethylamino)ethyl-imino)-1-phenylpropan-2-one oxime respectively, have been synthesised. Single crystal X-ray analyses of the complexes reveal that the nickel(ll) ions are in square-planar N3O environments and form six-membered (NiNO)2 metallacycles. Cyclic voltammetric measurements of 1·MeCN and 2 in MeCN solution show quasirreversible one-electron oxidations at E1/2 = 0.566 V and 0.603 V ( vs Fc+/Fc), respectively, attributed to NiIIINiII/NiII2 redox couples. Additional reversible NiIII2/NiIIINiII redox responses were observed at relatively higher potential near E1/2 = 0.832 V and 0.850 V ( vs Fc+/Fc), respectively, for 1·MeCN and 2. Complexes 1·MeCN and 2 display intense charge-transfer bands at ∼390 and ∼345 nm in the visible region. Chemical oxidation of complex 1·MeCN by sodium hexachloroiridate(IV) hexahydrate generates red Ni2III species with characteristic new bands at ∼520 and 427 nm in the visible region as well as the characteristic EPR signals at 77 K with g⊥ > gII. Similar phenomena were observed for complex 2 upon chemical oxidation. The dinickel(ll) complexes are catalytically active for epoxidation of olefins using iodosylbenzene as the terminal oxidant.

scholarly journals Terminal deoxynucleotidyltransferase. Alignment of α- and β-subunits of the core enzyme along the primary translation product

1985 ◽  
Vol 227 (3) ◽  
pp. 1003-1007 ◽  
Author(s):  
C M Beach ◽  
S K Chan ◽  
T C Vanaman ◽  
M S Coleman
Keyword(s):  
Amino Acid ◽  
Nucleotide Sequence ◽  
Amino Acid Sequence ◽  
Beta Subunits ◽  
Isolation And Purification ◽  
C Terminus ◽  
Human Lymphoblast ◽  
Catalytically Active ◽  
Single Polypeptide ◽  
Dna Nucleotide Sequence

Terminal deoxynucleotidyltransferase exists in multiple Mr forms, all apparently generated from a single polypeptide of 62kDa. On isolation and purification, the smallest catalytically active protein of this enzyme consists of two subunits, alpha (12kDa) and beta (30kDa). Recently a complementary-DNA nucleotide sequence has been reported for a portion of the enzyme from human lymphoblast. We have pinpointed the locations of the alpha- and beta-subunits within the elucidated nucleotide sequence. From these data, the portions of the nucleotide sequence coding for the catalytically important area of the transferase can be estimated. Here the amino acid sequence of a number of tryptic peptides from calf alpha- and beta-subunits is presented. Because of the striking homology between the amino acid sequence of the calf enzyme and that predicted for human lymphoblast enzyme, it is possible for us to conclude that the alpha-subunit was generated from the C-terminus of the precursor protein and the beta-subunit was non-overlapping and proximal.

CAN SEMIEMPIRICAL QUANTUM MODELS CALCULATE THE BINDING ENERGY OF HYDROGEN BONDING FOR BIOLOGICAL SYSTEMS?

2009 ◽  
Vol 08 (04) ◽  
pp. 691-711 ◽  
Author(s):  
FENG FENG ◽  
HUAN WANG ◽  
WEI-HAI FANG ◽  
JIAN-GUO YU
Keyword(s):  
Hydrogen Bonding ◽  
Amino Acid ◽  
Amino Acid Residue ◽  
Density Functional ◽  
Biological Systems ◽  
Binding Energies ◽  
Semiempirical Model ◽  
Hydrogen Bonded Systems ◽  
High Level ◽  
Hydrogen Bonded

A modified semiempirical model named RM1BH, which is based on RM1 parameterizations, is proposed to simulate varied biological hydrogen-bonded systems. The RM1BH is formulated by adding Gaussian functions to the core–core repulsion items in original RM1 formula to reproduce the binding energies of hydrogen bonding of experimental and high-level computational results. In the parameterizations of our new model, 35 base-pair dimers, 18 amino acid residue dimers, 14 dimers between a base and an amino acid residue, and 20 other multimers were included. The results performed with RM1BH were compared with experimental values and the benchmark density-functional (B3LYP/6-31G**/BSSE) and Möller–Plesset perturbation (MP2/6-31G**/BSSE) calculations on various biological hydrogen-bonded systems. It was demonstrated that RM1BH model outperforms the PM3 and RM1 models in the calculations of the binding energies of biological hydrogen-bonded systems by very close agreement with the values of both high-level calculations and experiments. These results provide insight into the ideas, methods, and views of semiempirical modifications to investigate the weak interactions of biological systems.

scholarly journals Conformational analysis and intramolecular interactions in monosubstituted phenylboranes and phenylboronic acids

2013 ◽  
Vol 9 ◽  
pp. 1127-1134 ◽  
Author(s):  
Josué M Silla ◽  
Rodrigo A Cormanich ◽  
Roberto Rittner ◽  
Matheus P Freitas
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonding ◽  
Conformational Analysis ◽  
Conformational Equilibrium ◽  
Intramolecular Hydrogen Bonding ◽  
Intramolecular Interactions ◽  
Coupling Constant ◽  
Intramolecular Hydrogen ◽  
Phenylboronic Acids ◽  
Electron Donation

A 1 TS J F,H(O) coupling pathway, dictated by a hydrogen bond, in some 2-fluorobenzoic acids has been observed, while such an interaction does not occur in 2-fluorophenol. Thus, this work reports the conformational analysis of 2-fluorophenylboronic acid (1), in order to evaluate a possible intramolecular OH∙∙∙F hydrogen bond in comparison to an nF→pB interaction, which mimics the quantum nF→σ*OH hydrogen bond that would be expected in 2-fluorophenol. 2-Fluorophenylborane (3), which does not experience hydrogen bonding, was used to verify whether nF→pB interaction governs the conformational equilibrium in 1 due to a predominant OH∙∙∙F hydrogen bond or to other effects. A series of 2-X-phenylboranes (X = Cl, Br, NH2, PH2, OH and SH) were further computationally analyzed to search for electron donors to boron, capable of influencing the conformational equilibrium. Overall, the intramolecular OH∙∙∙F hydrogen bond in 1 is quite stabilizing and dictates the 1 h J F,H(O) coupling constant. Moreover, electron donation to the empty p orbital of boron (for noncoplanar BH2 moiety relative to the phenyl ring) is also significantly stabilizing for the NH2 and PH2 derivatives, but not enough to make the corresponding conformers appreciably populated, because of steric effects and the loss of πCC→pB resonance. Thus, the results found earlier for 2-fluorophenol about the lack of intramolecular hydrogen bonding are now corroborated.

(Acetylacetonato-κ2O,O′)[1-(4-bromophenyl-κC2)-3-methylimidazol-2-ylidene-κC2]platinum(II)

2012 ◽  
Vol 68 (8) ◽  
pp. m203-m205 ◽  
Author(s):  
Mario Tenne ◽  
Yvonne Unger ◽  
Thomas Strassner
Keyword(s):  
Hydrogen Bonding ◽  
Solid State ◽  
Intermolecular Hydrogen Bonding ◽  
Coordination Environment ◽  
Π Interactions ◽  
New Class ◽  
Square Planar ◽  
Parallel Fashion

The title platinum(II) complex, [Pt(C10H8BrN2)(C5H7O2)], has a bidentate cyclometallated phenylimidazolylidene ligand and an acetylacetonate spectator ligand, which form a distorted square-planar coordination environment around the PtIIcentre. In the solid state, the molecules are oriented in a parallel fashion by intermolecular hydrogen bonding and π–π and C—H...π interactions, while close Pt...Pt contacts are not observed. The structure is only the second example for this new class of compounds.

Specific features of supramolecular organisation and hydrogen bonding in proline cocrystals: a case study of fenamates and diclofenac

CrystEngComm ◽  
2018 ◽  
Vol 20 (43) ◽  
pp. 6970-6981 ◽  
Author(s):  
Artem O. Surov ◽  
Alexander P. Voronin ◽  
Mikhail V. Vener ◽  
Andrei V. Churakov ◽  
German L. Perlovich
Keyword(s):  
Hydrogen Bonding ◽  
Amino Acid ◽  
Naturally Occurring ◽  
Supramolecular Organisation

New zwitterionic cocrystals of fenamate drugs and diclofenac with the naturally occurring amino acid l-proline have been obtained and thoroughly characterised by a variety of experimental and theoretical techniques.

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