Co-Catalyzed Metal-Ligand Cooperative Approach for N-alkylation of Amines and Synthesis of Quinolines via Dehydrogenative Alcohol Functionalization

Herein we report a cobalt-catalyzed sustainable approach for C−N cross-coupling reaction between amines and alcohols. Using a well-defined Co-catalyst 1 a bearing 2-(phenyldiazenyl)-1,10-phenanthroline ligand, various N-alkylated amines were synthesized in good yields. 1 a efficiently alkylates diamines producing N, N′-dialkylated amines in good yields and showed excellent chemoselectivity when oleyl alcohol and β-citronellol, containing internal carbon-carbon double bond were used as alkylating agents. 1 a is equally compatible with synthesizing N-heterocycles via dehydrogenative coupling of amines and alcohols. 1H-Indole was synthesized via an intramolecular dehydrogenative N-alkylation reaction, and various substituted quinolines were synthesized by coupling of 2-aminobenzyl alcohol and secondary alcohols. A few control reactions and spectroscopic experiments were conducted to illuminate the plausible reaction mechanism, indicating that the 1 a -catalyzed N-alkylation proceeds through the borrowing hydrogen pathway. The coordinated arylazo ligand participates actively throughout the reaction; the hydrogen eliminated during dehydrogenation of alcohols was set aside in the ligand backbone and subsequently gets transferred in the reductive amination step to imine intermediates yielding N-alkylated amines. On the other hand, 1 a -catalyzed quinoline synthesis proceeds through dehydrogenation followed by successive C−C and C−N coupling steps forming H₂O₂ as a by-product under air.     

Efficient Synthesis of 2-Methylene-3phosphorylalkanoates: Phosphorylation of Baylis–Hillman Bromides via an S N 2-S N 2′ Strategy

A novel synthesis of 2-methylene-3-phosphorylalkanoates under mild conditions is described. Thus, Balyis–Hillman bromides react with secondary phosphine oxides or H-phosphonites in the presence of DABCO via an S _N 2-S _N 2′ protocol to produce the target compounds in good yields.     

A Flexible,Extremely Sterically Demanding Triazenide Ligand: Synthesis and Coordination Chemistry

Seeking to further the investigation of extremely sterically congested main group metals, the synthesis of a new oligoaryl triazene (Dipp*₂N₃H) is reported. This was accessed by diazotization of Dipp*NH₂ to access both Dipp*I and Dipp*N₃ in high yield and with scalable preparations. These compounds are used as precursors to Dipp*₂N₃H, via a magnesium aryl, due to the difficulties in obtaining pure triazene via an aryl‐lithium species. Deprotonation of the triazene with both potassium and thallium tert‐butoxides gives the respective metal triazenides in high yield. The solid‐state structures of these complexes have been determined and three high hapticity metal arene‐π interactions, which sterically shield the metal centers, were observed in each case; spectroscopic C_2v symmetry suggests these interactions are fluxional in solution. The variability of these interactions in the solid state as well as the changes in calculated steric demand of the ligand between metals point to an adaptive, flexible coordination mode.     

Synthesis and Structure of N,N-Dimethyldithiocarbamates of Tetraphenylantimony and Tetra-p-tolylantimony

Tetraphenylantimony N,N-dimethyldithiocarbamate (I) and tetra-p-tolylantimony N,N-dimethyldithiocarbamate (II) were synthesized via the reaction of tetraarylantimony chloride Ar₄SbCl (Ar = C₆H₅ or C₆H₄Me-4) with sodium N,N-dimethyldithiocarbamate in water. According to the X-ray diffraction data, the tetraarylantimony N,N-dimethyldithiocarbamate molecules have a distorted octahedral configuration. The Sb–S bond lengths are equal to 2.7158(5) Å, 2.7440(5) Å and 2.761(2) Å, 2.8002(2) Å for I and II, respectively.     

Catalyst-Controlled Dual Reactivity of Sulfonimidamides: Synthesis of Propargylamines and N-Propargyl Sulfonimidamides

Sulfonimidamides (SIAs) are acting both as surrogate amines and nucleophiles depending on the reaction conditions to access propargylamines and N-propargyl SIAs, respectively. The amine part of SIAs has been cleaved in an InCl₃-catalyzed three-component A³ coupling reaction with aldehyde and acetylene to yield propargylamine. Moreover, N-propargyl SIAs were obtained via the direct-imination of propargyl alcohols in the presence of BF₃⋅OEt₂.     

Unprecedented micro-sprout morphology of an ionic palladium(II) complex

The reaction of (tmeda)Pd(ClO₄)₂ (tmeda = N,N,N′,N′-tetramethylethylenediamine) with L (L = bis(4-(4-pyridylcarboxyl)phenyl)methane) affords the ionic cyclodimeric palladium(II) complex [(tmeda)Pd(L)]₂(ClO₄)₄. The complex forms an unprecedented micro-sprout morphology via slow evaporation of acetone in a dilute concentration mixture of acetone and water without any template or additive. In contrast, the palladium(II) complex in a concentrated mixture forms uniform submicrospheres. The formation-process of the micro-sprout morphology has been explained in terms of a stepwise concentration effect. Furthermore, surface modifications and properties of the micro-sprouts via a typical anion exchange or sonication have been studied.     

Assessment of amination reactions via nucleophilic aromatic substitution using conventional and eco-friendly energies

The efficiency of conventional heating energy source compared with Infrared (IR), Ultrasound (US), Microwave and the simultaneous combination US–IR eco-friendly approaches for preparation of new N-(5-R¹ _-amino-2-nitrophenyl)acetamides and 5-R¹-amino-2-nitroaniline by Nucleophilic Aromatic Substitution (S_NAr) via addition–elimination reactions on the halogens F, Cl, Br, I, employing amines as nucleophiles were explored. Moreover, phenyldiazenyl derivatives in good yields by an oxidative one-pot S_NAr-based amination reaction from an unusual oxidation of 2-phenylhydrazinyl derivatives in DMSO was prepared.     

Novel N‐methylbenzothiazolium salts as hardeners for epoxy and acrylate monomers

Novel N‐methylbenzothiazolium salts [N‐methyl‐2‐benzylthiobenzothiazolium, N‐methyl‐2‐(4‐nitrobenzylthio)benzothiazolium, N‐methyl‐2‐(1‐ethoxycarbonylethylthio)benzothiazolium, and N‐methyl‐2‐methylthiobenzothiazolium hexafluoroantimonates] were synthesized by the reaction of the corresponding 2‐substituted benzothiazole with dimethylsulfate, followed by anion exchange with KSbF₆. These benzothiazolium salts cationically polymerized an epoxy monomer by photoirradiation. They also polymerized an acrylate monomer via a photoradical process. The use of aromatic compounds such as 2‐ethyl‐9,10‐dimethoxyanthracene as photosensitizers was effective in enhancing the polymerization. These benzothiazolium salts also served as thermal cationic initiators. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3828–3837, 2003     

UV‐triggered CO2‐responsive behavior of nanofibers and their controlled drug release properties

A novel nanofibrous mat featuring an ultraviolet (UV)‐induced CO₂‐responsive behavior was fabricated via electrospinning and used as a controlled drug release system. First, a random copolymer for electrospinning, poly(N,N‐diethylaminoethyl acrylamide‐co‐N‐benzylacrylamide‐co‐N,N‐dimethyl‐N‐(2‐nitrobenzyl)‐ethaneamine acrylamide‐co‐4‐acryloyloxy benzophenone) [P(DEEA‐co‐BA‐co‐DMNOBA‐co‐ABP)], was prepared based on pentafluorophenyl esters via an “active ester‐amine” chemistry reaction. Subsequently, doxorubicin hydrochloride (DOX)‐loaded P(DEEA‐co‐BA‐co‐DMNOBA‐co‐ABP) nanofibers were fabricated, yielding a new drug‐loaded nanofibrous mat as a potential wound dressing. These DOX‐loaded nanofibers can respond to UV irradiation and CO₂ stimulation. Interestingly, without UV irradiation, the fabricated nanofibers cannot exhibit any responsiveness. Therefore, the majority of the DOX was steadily stored in the nanofibers, even in the presence of CO₂. However, upon UV irradiation, the CO₂‐responsive behavior of the nanofibers was activated and the prepared nanofibers swelled slightly, resulting in the release of around 42% DOX from the nanofibers. Upon further purging with CO₂, the release amount of DOX from the nanofibers could reach up to approximately 85%, followed by the morphological transition from a nanofibrous mat to a porous hydrogel film. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1580–1586     

Preparation of a zwitterionic trichloroplatinum(II) complex with an alkylbipyridinum ligand and its reaction in dmso-<Emphasis Type="BoldItalic">d</Emphasis><Subscript>6</Subscript> solution

A zwitterionic trichloroplatinum(II) complex PtCl₃(4,4′-bpy-N-ⁿBu) (1) was prepared by an aqueous reaction of [4,4′-bpy-N-ⁿBu]Cl with K₂PtCl₄, and was characterized by ¹H-n.m.r. and IR spectroscopy as well as elemental analysis. Dissolving (1) into dmso-d ₆ at 25 °C yields a mixture of the complexes, cis-PtCl₂(4,4′-bpy-N-ⁿBu)(dmso-d ₆) (2-cis), trans-PtCl₂(4,4′-bpy-N-ⁿBu)(dmso-d ₆) (2-trans), [4,4′-bpy-N-ⁿBu]Cl and PtCl₂(dmso-d ₆)₂. Ratio of the products in the dmso-d ₆ solution changed depending on the temperature and the total concentration of the complexes. These compounds are in equilibrium via isomerization reaction between (2-cis) and (2-trans) and via displacement reaction of the alkylbipyridinium ligand of (2-cis) and (2-trans) with dmso-d ₆ to form [4,4′-bpy-N-ⁿBu]Cl and PtCl₂(dmso-d ₆)₂.     

含季铵盐的芳酰腙配体的铜(Ⅱ)配合物的合成和表征:体外DNA键合和核酸酶活性

制备了2个新的含有N,N,N-三甲基丙烷-1-铵基团和N,N,N-三甲基戊烷-1-铵基团的苯乙酮-（4-羟基苯腙）配体：（E）-3-（4-（1-（2-（4-hydroxybenzoyl）hydrazono）ethyl）phenoxy）-N,N,N-trimethylpropan-1-ammonium perchlorate（H₂L¹）和（E）-3-（4-（1-（2-（4-hy-droxybenzoyl）hydrazono）ethyl）phenoxy）-N,N,N-trimethylpentane-1-ammonium perchlorate（H₂L²）。以这2个配体分别合成了2个新的铜配合物：[Cu（HL¹）₂]和[Cu（HL²）₂],研究了这些配体和配合物的DNA结合和切割活性,还研究了DNA切割的机理以及化合物浓度对DNA切割反应的影响。紫外-可见光谱结果表明,所有化合物均优先通过主沟结合模式与DNA结合,在甲基绿（主要的沟结合剂）的存在下切割DNA的活性受到抑制的结果也支持这一结论。电泳研究的结果则表明,化合物在存在或不存在氧化剂（H₂O₂）的情况下均对质粒DNA表现出显著的切割活性,活性主要取决于化合物的浓度。化合物通过水解途径裂解pBR322DNA,在存在不同自由基清除剂情况下的DNA裂解实验也支持这一结论。     

1,4-Aryl migration under copper(I) atom transfer conditions

Reaction of N-alkyl-N-(trichloroacetyl)arylsulfonamides with CuCl/amines leads to N-alkyl-N-(dichloroacetyl)-arylsulfonamides via reduction or N-alkyl-aryldichloroacetamides via 1,4-aryl migration with loss of SO₂. The ratio of reduction to aryl migration is dependent upon the temperature and the ligand utilised. Along with amide bond hydrolysis these reactions may compete when carrying out slow atom transfer radical cyclisation reactions using sulfonamides.     

Electroenzymatic Nitrogen Fixation Using a MoFe Protein System Immobilized in an Organic Redox Polymer

We report an organic redox‐polymer‐based electroenzymatic nitrogen fixation system using a metal‐free redox polymer, namely neutral‐red‐modified poly(glycidyl methacrylate‐co‐methylmethacrylate‐co‐poly(ethyleneglycol)methacrylate) with a low redox potential of ?0.58 V vs. SCE. The stable and efficient electric wiring of nitrogenase within the redox polymer matrix enables mediated bioelectrocatalysis of N₃^?, NO₂^? and N₂ to NH₃ catalyzed by the MoFe protein via the polymer‐bound redox moieties distributed in the polymer matrix in the absence of the Fe protein. Bulk bioelectrosynthetic experiments produced 209±30 nmol NH₃ nmol MoFe^?1 h^?1 from N₂ reduction. ¹⁵N₂ labeling experiments and NMR analysis were performed to confirm biosynthetic N₂ reduction to NH₃.     

A practical access to new pyrrolizine carboxylates via KHMDS-catalyzed carbocyclizations

Easy and effective preparation of new 1H-pyrrolizine carboxylates was achieved with high efficiency via KHMDS-induced carbocyclization of N-alkynyl proline carboxylates under substantially mild conditions. Meanwhile, some trans-diiodoallylic N-proline carboxylates were obtained from N-propargyl proline carboxylates using molecular I₂ with or without KHMDS. This method is quite feasible in terms of practical and quick access to the pyrrolizines and their derivatives over the formation of carbanions.     

Synthesis,characterization, electrochromic properties,and electrochromic device application of a novel star polymer consisting of thiophene end‐capped poly(ε‐caprolactone) arms emanating from a hexafunctional cyclotriphosphazene core

Hexa‐armed and thiophene (Thi) end‐capped poly(ε‐caprolactone) star polymer (N₃P₃‐(PCL‐Thi)₆), containing cyclotriphosphazene core, was prepared in a four‐step reaction sequence. Ring‐opening polymerization (ROP) and “click chemistry” techniques were employed in the first and final steps, respectively. Hexa‐armed PCL star polymer (N₃P₃‐(PCL‐OH)₆) was successfully synthesized via ROP of ε‐caprolactone (ε‐CL) by using hekzakis(p‐(hydroxymethyl)phenoxy) cyclotriphosphazene as the multisite initiator and tin(II) 2‐ethylhexanoate (Sn(Oct₂)) as the catalyst in bulk at 115 °C. Further modifications of the N₃P₃‐(PCL‐OH)₆ were accomplished by derivatization of the hydroxyl‐functional chain ends. The obtained N₃P₃‐(PCL‐OH)₆ was then reacted with 2‐bromo‐2‐methylpropanoyl bromide, and this led to a star polymer with bromide end groups, N₃P₃‐(PCL‐Br)₆. In the third step, N₃P₃‐(PCL‐Br)₆ was azidified with sodium azide (NaN₃) in DMF affording N₃P₃‐(PCL‐N₃)₆. Conversion of the azide chain end groups into Thi was quantitatively accomplished via the “click reaction” between N₃P₃‐(PCL‐N₃)₆ and prop‐2‐yn‐1‐yl 3‐thienyl acetate in the final step. Subsequently, the star polymer with six Thi chain ends (N₃P₃‐(PCL‐Thi)₆) was employed in electrochemical copolymerization with both pyrrole and Thi. Electrochromic properties and electrochromic device application of N₃P₃‐(PCL‐Thi)₆/PThi were also investigated. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3668–3682, 2010     

Synthesis,characterization and antibacterial activity of indium(III) complexes with adamantane-ring containing Schiff bases

Indium(III) chloride tetrahydrate and Schiff-base ligands derived from adamantaneamine and 3-/4-methoxysalicylaldehyde gave two complexes, C₂₂H₃₂Cl₃InN₂O₃ (1) and C₃₆H₄₄C_l3InN₂O₄ (2), respectively. The complexes were characterized by IR, ¹H NMR, elemental analysis, molar conductance, thermal analysis, and single-crystal X-ray diffraction. Complex 1 crystallizes in the monoclinic system, P2₁/n space group with the asymmetric unit consisting of one indium(III), one N-(3-methoxysalicylidene)-aminoadamantane (L¹), three chlorides and one N,N-dimethylformamide molecule. The indium is six-coordinate with reversed triangular-prism geometry via three oxygens and three chlorides. Complex 2 crystallizes in the triclinic system, P 1 space group; the asymmetric unit consists of one indium(III), two N-(4methoxysalicylidene)-aminoadamantane (L²), and three chlorides. The indium is five-coordinate with distorted trigonal-bipyramidal geometry via two oxygens and three chlorides. Antibacterial activities of the complexes have been investigated against Escherichia coli and Staphylococcus aureus.     

New Insights in Frustrated Lewis Pair Chemistry with Azides

The geminal frustrated Lewis pair (FLP) tBu₂PCH₂BPh₂ ( 1 ) reacts with phenyl-, mesityl-, and tert-butyl azide affording, respectively, six, five, and four-membered rings as isolable products. DFT calculations revealed that the formation of all products proceeds via the six-membered ring structure, which is thermally stable with an N-phenyl group, but rearranges when sterically more encumbered Mes−N₃ and tBu−N₃ are used. The reaction of 1 with Me₃Si−N₃ is believed to follow the same course, yet subsequent N₂ elimination occurs to afford a four-membered heterocycle ( 5 ), which can be considered as a formal FLP-trimethylsilylnitrene adduct. Compound 5 reacts with hydrochloric acid or tetramethylammonium fluoride and showed frustrated Lewis pair reactivity towards phenylisocyanate.     

Physicochemical Properties of Complexes of Zinc Iodide with Pyridine N-Oxides

Polycrystalline 1 : 2 complexes of ZnI₂ with N-oxides of pyridine, picoline, and 2,6-lutidine were studied by IR spectroscopy, dielectrometry, and conductometry. An equilibrium between three solid phases was observed. These phases are characterized by different enthalpies of formation of intermolecular bonds and different mechanism of electronic effect transmission via these bonds. Gas-like thermal molecular motion in one of the phases of the 2,6-lutidine N-oxide complex was observed. Reversible chemical reactions on the surface of the crystalline 3-picoline N-oxide complex are initiated on exposure to an alternating electric field. Two complexes, similarly to the ZnCl₂ complexes, are ionized in the cumulative mode on fast heating from 18-19 to 26-45°C. Partial activation energies of electrical conductivity of different ions were determined for a number of complexes and inorganic salts.     

Synthesis of amphiphilic and thermoresponsive ABC miktoarm star terpolymer via a combination of consecutive click reactions and atom transfer radical polymerization

Well‐defined amphiphilic and thermoresponsive ABC miktoarm star terpolymer consisting of poly(ethylene glycol), poly(tert‐butyl methacrylate), and poly(N‐isopropylacrylamide) arms, PEG(‐b‐PtBMA)‐b‐PNIPAM, was synthesized via a combination of consecutive click reactions and atom transfer radical polymerization (ATRP). Click reaction of monoalkynyl‐terminated PEG with a trifunctional core molecule bis(2‐azidoethyl)amine, (N₃)₂? NH, afforded difunctional PEG possessing an azido and a secondary amine moiety at the chain end, PEG‐NH? N₃. Next, the amidation of PEG‐NH? N₃ with 2‐chloropropionyl chloride led to PEG‐based ATRP macroinitiator, PEG(? N₃)? Cl. The subsequent ATRP of N‐isopropylacrylamide (NIPAM) using PEG(? N₃)? Cl as the macroinitiator led to PEG(? N₃)‐b‐PNIPAM bearing an azido moiety at the diblock junction point. Finally, well‐defined ABC miktoarm star terpolymer, PEG(‐b‐PtBMA)‐b‐PNIPAM, was prepared via the click reaction of PEG(? N₃)‐b‐PNIPAM with monoalkynyl‐terminated PtBMA. In aqueous solution, the obtained ABC miktoarm star terpolymer self‐assembles into micelles consisting of PtBMA cores and hybrid PEG/PNIPAM coronas, which are characterized by dynamic and static laser light scattering, and transmission electron microscopy. On heating above the phase transition temperature of PNIPAM in the hybrid corona, micelles initially formed at lower temperatures undergo further structural rearrangement and fuse into much larger aggregates solely stabilized by PEG coronas. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4001–4013, 2009     

Understanding the Deactivation Pathways of Iridium(III) Pyridine-Carboxiamide Catalysts for Formic Acid Dehydrogenation

The degradation pathways of highly active [Cp*Ir(κ²-N,N-R-pica)Cl] catalysts (pica=picolinamidate; 1 R=H, 2 R=Me) for formic acid (FA) dehydrogenation were investigated by NMR spectroscopy and DFT calculations. Under acidic conditions (1 equiv. of HNO₃), 2 undergoes partial protonation of the amide moiety, inducing rapid κ²-N,N to κ²-N,O ligand isomerization. Consistently, DFT modeling on the simpler complex 1 showed that the κ²-N,N key intermediate of FA dehydrogenation ( I_NH ), bearing a N-protonated pica, can easily transform into the κ²-N,O analogue ( I_NH2 ; ΔG^≠≈11 kcal mol⁻¹, ΔG ≈−5 kcal mol⁻¹). Intramolecular hydrogen liberation from I_NH2 is predicted to be rather prohibitive (ΔG^≠≈26 kcal mol⁻¹, ΔG≈23 kcal mol⁻¹), indicating that FA dehydrogenation should involve mostly κ²-N,N intermediates, at least at relatively high pH. Under FA dehydrogenation conditions, 2 was progressively consumed, and the vast majority of the Ir centers (58 %) were eventually found in the form of Cp*-complexes with a pyridine-amine ligand. This likely derived from hydrogenation of the pyridine-carboxiamide via a hemiaminal intermediate, which could also be detected. Clear evidence for ligand hydrogenation being the main degradation pathway also for 1 was obtained, as further confirmed by spectroscopic and catalytic tests on the independently synthesized degradation product 1 c . DFT calculations confirmed that this side reaction is kinetically and thermodynamically accessible.