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The sulfur-carbon electrode, used as a cathode, appears to be an excellent source of nucleophiles which are good sulfuration reagents towards alkenes not substituted by leaving groups.However, the electrochemical reactions are often complex.It should be worth outlining that reaction leads to a vicarious substitution apparently specific of this kind of electrode.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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A reverse hydrogenolysis process has been developed for two-site coupling of 2-hydroxy-1,4-naphthoquinones with olefins to produce naphtha[2,3-b]furan-4,9-diones and hydrogen (H2). The reaction is catalyzed by commercially available Pd/C without oxidants and hydrogen acceptors, thereby providing an intrinsically waste-free approach for the synthesis of functionalized and potentially biologically relevant naphtha[2,3-b]furan-4,9-diones.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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A set of bioinspired carbamoyl CNP pincer complexes are reported that are relevant to [Fe]-hydrogenase (Hmd). The dicarbonyl species [(CNHNNHPR2)Fe(CO)2I] [R = Ph, 1; R = iPr, 2] undergoes ligand deprotonation, resulting in the dearomatized complexes of formulas [(CNHNN=PR2)Fe(CO)2] (5 and 6). The crystal structure and 1H{31P} NMR spectroscopy of the iodide-bound dearomatized species [Na(18-crown-6)][(CNHNN=PPh2)Fe(CO)2I] (7) showed that the deprotonated moiety was the phosphoramine N(H) linkage. Separately, the monocarbonyl complexes [(CNHNNHPR2)Fe(CO)(MeCN)2](BF4) (8 and 9) synthesized, as well as deprotonated and dearomatized in similar fashion. Reactivity studies revealed that the parent dicarbonyl complexes require more forceful conditions for H2 activation, compared with the monocarbonyl complexes. The ligand backbone was not found to participate in H2 activation and H2 ? hydride transfer to an organic substrate was not observed in either case. Density functional theory calculations revealed that the higher reactivity of the monocarbonyl complex in H2 splitting could be attributed to its higher affinity for H2. This behavior is attributed to two key points related to the requisite dI(Fe) ? sigma*(H2) back-bonding interaction in a conventional M-H2 Kubas interaction: (i) generally, the weaker pidonor capacity of the dicarbonyls, and (ii) specifically, the detrimental effect of a strongly piacidic CO ligand (versus weakly piacidic MeCN ligand) trans to the H2 activation site. The higher reactivity of the monocarbonyl complex is also evidenced by the catalytic transfer hydrogenation by monocarbonyl 8, whereas dicarbonyl 1 was ineffective. Overall, the results suggest that Nature uses the dicarbonyl motif in [Fe]-hydrogenase to diminish the interaction between the Fe center and dihydrogen, thereby preventing premature H2 activation prior to substrate (H4MPT+) binding and any resulting nonspecific hydride transfer reactivity.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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A set of bench-stable ruthenium complexes with new N,N,N-tridentate coordinating pincer-type pyridyl-bis(pyridylideneamide) ligands was synthesized in excellent yields, with the pyridylidene amide in meta or in para position (m-PYA and p-PYA, respectively). While complex [Ru(p-PYA)(MeCN)3]2+ is catalytically silent in transfer hydrogenation, its meta isomer [Ru(m-PYA)(MeCN)3]2+ shows considerable activity with turnover frequencies at 50% conversion TOF50 = 100 h-1. Spectroscopic, electrochemical, and crystallographic analyses suggest considerably stronger donor properties of the zwitterionic m-PYA ligand compared to the partially pi-acidic p-PYA analogue, imparted by valence isomerization. Further catalyst optimization was achieved by exchanging the ancillary MeCN ligands with imines (4-picoline), amines (ethylenediamine), and phosphines (PPh3, dppm, dppe). The most active catalyst was comprised of the m-PYA pincer ligand and PPh3, complex [Ru(m-PYA)(PPh3)(MeCN)2]2+, which reached a TOF50 of 430 h-1 under aerobic conditions and up to 4000 h-1 in the absence of oxygen. The presence of oxygen reversibly deactivates the catalytically active species, which compromises activity, but not longevity of the catalyst. Ligand exchange kinetic studies by NMR spectroscopy indicate that the strong trans effect of the phosphine is critical for high catalyst activity. Diaryl, aryl-alkyl, and dialkyl ketones were hydrogenated with high conversion, and alpha,beta-unsaturated ketones produced selectively the saturated ketone as the only product due to exclusive C=C bond hydrogenation, a distinctly different selectivity from most other transfer hydrogenation catalysts.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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2,4,7-Triaryl-5H-3,4-dihydroimidazo<1,2-b>-1,2,4-triazepines were obtained on the basis of 4-phenyl-1,2-diaminoimidazole and chalcones.Their IR, UV, PMR, and mass spectra are discussed.It is shown that the more basic 1-NH2 group of the starting diamine participates in the formation of the azomethine bond of the seven-membered heteroring.The seven-membered ring has a “quasi-boat” form in which the 2- and 4-aromatic substituents occupy equatorial positions.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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A practical and highly enantioselective nonenzymatic kinetic resolution of racemic beta-hydroxy carbonyl (aldol) compounds through enantioselective dehydration process was developed using a cation-binding Song’s oligoethylene glycol (oligoEG) catalyst with potassium fluoride (KF) as base. A wide range of racemic aldols was resolved with extremely high selectivity factors (s = up to 2393) under mild reaction conditions. This protocol is easily scalable. It provides an alternative approach for the syntheses of diverse biologically and pharmaceutically relevant chiral aldols in enantiomerically pure form. For example, racemic gingerols could participate in this kinetic resolution with superb efficiency (s > 240), affording both enantiomerically pure gingerols and corresponding shogaols simultaneously in a single step. The dramatic effectiveness of such kinetic resolution process can be ascribed to systematic cooperative hydrogen-bonding catalysis in a densely confined supramolecular chiral cage in situ generated from the chiral catalyst, substrate, and KF.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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A reagent system of 1-alkyne, SnCl4, and Bu3N alkynylates aldehydes, acetals,and enones under mild reaction conditions giving acetylenic alcohols, acetylenic ethers, and acetylenic ketones, respectively, in high yields.Alkynyltrichlorotins are shown to be the reactive species for these reactions.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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An efficient, catalytic, diastereo- and enantioselective conjugate addition of N-(diphenylmethylene)glycine tert-butyl ester to beta-aryl substituted enones was realized in the presence of 1 mol% of newly desired dinuclear N-spiro-ammonium salts, affording functionalized alpha-amino acid derivatives in 57-98% yields with high diastereoselectivity (up to 99:1 dr) and enantioselectivity (up to 96.5:3.5 er).

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Thiourea-modified cinchona alkaloids as bifunctional catalysts and a base could catalyze a stepwise [5+1] cyclization of divinyl ketones with nitromethane via double Michael additions, furnishing optically active 4-nitro- cyclohexanones with good yields, excellent diastereoselectivities (>20:1) and high enantiomeric ratios (up to 97:3). The Royal Society of Chemistry.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate

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Herein we utilized, for the first time, sodium 2-iodoxybenzoate as a highly specific oxidant for PhthNH2 to create a highly chemoselective aziridination reagent. This method efficiently effects aziridination of electron-rich, electron-deficient, allylic alcohol and alkenyl bromide C=C bonds in good to excellent yields. Inter and intramolecular chemoselectivity was demonstrated between electron-rich and electron-deficient alkenes by using this efficient and metal free protocol.

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Reference:
Synthesis and Crystal Structure of a Chiral C3-Symmetric Oxygen Tripodal Ligand and Its Applications to Asymmetric Catalysis,
Chiral lanthanide(III) complexes of sulphur–nitrogen–oxygen ligand derived from aminothiourea and sodium D-camphor-β-sulfonate