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41.
Catalytic Enantioselective CH Functionalization of Alcohols by Redox‐Triggered Carbonyl Addition: Borrowing Hydrogen,Returning Carbon
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John M. Ketcham Inji Shin T. Patrick Montgomery Prof. Michael J. Krische 《Angewandte Chemie (International ed. in English)》2014,53(35):9142-9150
The use of alcohols and unsaturated reactants for the redox‐triggered generation of nucleophile–electrophile pairs represents a broad, new approach to carbonyl addition chemistry. Discrete redox manipulations that are often required for the generation of carbonyl electrophiles and premetalated carbon‐centered nucleophiles are thus avoided. Based on this concept, a broad, new family of enantioselective C? C coupling reactions that are catalyzed by iridium or ruthenium complexes have been developed, which are summarized in this Minireview. 相似文献
42.
《Journal of Coordination Chemistry》2012,65(3):171-180
Abstract 2-(2′-Pyridyl)benzimidazole (pybzim = LH) coordinates to iron(II) as a bidentate and forms the tris-ligated complex, [Fe(pybzim)3]2+ as isolated in the solid. Titration of [Fe(pybzim)3]2+ with base demonstrates the successive deprotonation of the imino hydrogens of the coordinated ligands. Protonation constants for the free ligand, pybzim (Iog10 K H = 11.33) and the complex, [Fe(pybzim)3]2+ (log10 K H 1 = 9.58, log10 K H 2 = 8.13 and log10 K H 3 = 6.97) were measured in 30% (v/v) H2O/EtOH. Results show that coordination to iron(II) increases the acidity of the imino hydrogen of the ligand. Spin-crossover behaviour of the complex were studied in different solvents ME, AC, AN, NM, NB, DMF, DMSO and ANL. The complex shows strong spin-crossover behaviour which is solvent dependent. Values of the spin-equilibrium constant (K sc) and the associated thermodynamic parameters (ΔH sc = 18.1–21.3 kJ mol?1 and δS sc = 69.6–84.4JK?1 mol?1) were calculated. An increase of the enthalpy is observed with increasing donor number (DN) of the solvent. 相似文献
43.
Lukas Lohmeyer Dr. Elisabeth Kaifer Prof. Hubert Wadepohl Prof. Hans-Jörg Himmel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(26):5834-5845
New redox-active 1,2,5,6-tetrakis(guanidino)-naphthalene compounds, isolable and storable in the neutral and deep-green dicationic redox states and oxidisable further in two one-electron steps to the tetracations, are reported. Protonation switches on blue fluorescence, with the fluorescence intensity (quantum yield) increasing with the degree of protonation. Reactions with N-halogenosuccinimides or N-halogenophthalimides led to a series of new redox-active halogeno- and succinimido-/phthalimido-substituted derivatives. These highly selective reactions are proposed to proceed via the tri- or tetracationic state as the intermediate. The derivatives are oxidised reversibly at slightly higher potentials than that of the unsubstituted compounds to dications and further to tri- and tetracations. The integration of redox-active ligands in the transition-metal complexes shifts the redox potentials to higher values and also allows reversible oxidation in two potentially separated one-electron steps. 相似文献
44.
Nicholas J. Race Qianjia Yuan Prof. Matthew S. Sigman 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(2):512-515
A palladium-catalyzed enantioselective redox-relay Heck reaction of 2-indole triflates and disubstituted alkenes is reported. This process combines readily available indole triflates with a variety of alkenes to afford a range of indole derivatives bearing a stereocenter adjacent to C2. Enantioselectivity is achieved through use of a simple pyridine-oxazoline ligand. Tuning the electronics of the indole, through judicious choice of N-protecting group, is required to ensure selective β-hydride elimination away from the indole core. Utility of this method is highlighted in a modular formal synthesis of an S1P1 agonist precursor developed by Merck. 相似文献
45.
46.
Igor E. Boldeskul Ivan F. Tsymbal 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1)
Phosphoalkenes (1), (R, RI, and RII = H, Hal, Nalk2) show alternative nucleophilic properties towards HX acids or transition metal salts, and depending upon reagent characteristics form addition products throught one of P=C double bond atoms. Coordination of a ligand to a cation by its π-electron donor is also observed due to quazidegeneration of higher occupied molecular orbital. 相似文献
47.
48.
Dr. Karl Kaupmees Robert Järviste Prof. Dr. Ivo Leito 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(48):17445-17449
The basicity scale of very weak bases has been set up in 1,2‐dichloroethane to give, for the first time, reliable quantitative insights into the basic properties of weak bases in a low‐polarity solvent. The scale contains 30 compounds, including anilines; phosphanes, and carbonyl bases, such as esters and amides, linked by 53 relative basicity measurements. The scale spans more than 12 pKip units, expanding to as low pKip values as possible with our current experimental methodology. 相似文献
49.
Daniel Romero Nieto Mikhail G. Zolotukhin Lioudmila Fomina Serguei Fomine 《Journal of Physical Organic Chemistry》2010,23(9):878-884
Energies of mono‐ and multiprotonation for 1,2,3‐indanetrione and ninhydrin in triflic acid (TFSA) media were estimated at PBE0/aug‐cc‐pvtz//6‐31+G** level of theory. The reactivity of formed intermediates in the reaction of aromatic electrophilic substitution has been studied at the same level of theory. It appears that the basicity of carbonyl groups in 1,2,3‐indanetrione is extremely low due to mutual influences of carbonyl groups. Carbonyl 2 is the least basic but the most reactive in accordance with experiment. Calculations demonstrated that monoprotonated intermediates are the principal reactive species in the reaction of hydroxyalkylation of 1,2,3‐indanetrione in TFSA. A new isomerization mechanism of 2,2‐diaryl‐1,3‐indanediones to 3‐(diarylmethylene)isobenzofuranones in TFSA media has been proposed. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
50.
Four novel derivatives of 1,1′-bi-2-naphthol have been prepared and the structures of these compounds characterised by IR, MS, 1H and 13C NMR spectroscopy and elemental analysis. The enantioselective recognition of these sensors has been studied by fluorescence titration and 1H NMR spectroscopy. The sensors exhibited different chiral recognition abilities towards N-Boc-protected amino acid anions and formed 1:1 complexes between the host and the guest. Sensors exhibit excellent enantioselective fluorescent recognition ability towards the amino acid derivatives. 相似文献