By Kenneth D. Karlin
This sequence offers inorganic chemists and fabrics scientists with a discussion board for severe, authoritative reviews of advances in each region of the self-discipline. quantity fifty nine keeps to file contemporary advances with an important, updated number of contributions through internationally-recognized researchers.
The chapters of this quantity are dedicated to the next subject matters:
• Iron Catalysis in artificial Chemistry
• A New Paradigm for Photodynamic treatment Drug layout: Multifunctional, Supramolecular DNA Photomodification brokers that includes Ru(II)/Os(II) gentle Absorbers Coupled to Pt(II) or Rh(III) Bioactive Sites
• Selective Binding of Zn2+ Complexes to Non-Canonical Thymine or Uracil in DNA or RNA.
• Progress towards the Electrocatalytic construction of Liquid Fuels from Carbon Dioxide
• Monomeric Dinitrosyl Iron Complexes: Synthesis and Reactivity
• Interactions of Nitrosoalkanes/arenes, Nitrosamines, Nitrosothiols, and Alkyl Nitrites with Metals
• Aminopyridine Iron and Manganese Complexes as Molecular Catalysts for not easy Oxidative Transformations
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Extra resources for Progress in Inorganic Chemistry, Vol. 59
The enantioselectivity for this reaction was solely attributed to the orientation of carbene, as well as the oleﬁns. For the catalysts containing macrocycles, selectivity appeared due to the parallel orientation of the CC axis with the MC bond (Scheme 26). Minimized steric interactions between the ester group and the axial proton of the chiral cyclohexyl group were achieved, when the oleﬁn approached from path a. Thus, the observed product had an (R,R) conﬁguration and was IRON CATALYSIS IN SYNTHETIC CHEMISTRY 23 TABLE II Cyclopropanation Using the Halterman Catalyst N Cl N Fe N N 23 Fe–Halterman catalyst Substrate Me trans/cis Br Cl MeO 53% 96:4 58% 93:7 58% 58% 94:6 92:8 obtained as a major trans isomer.
NHMe (13−25%) Ar/ Het-Ar H NHMe Ar/ Het-Ar FeCl3 (5−10%) CyBr, THF TMPMgCl*LiCl, rt, 2−18 h Me Me Me . LiCl = TMPMgCl*LiCl N Me MgCl Scheme 60. Iron-catalyzed deprotonative alkylation of heteroarenes (TMP = 2,2,6,6tetramethylpiperidinyl). 7H2O (1 equiv) cyclen (1 equiv) + 1 equiv 90 equiv K3PO4 (4 equiv), pyrazole (2 equiv) 48 h, 80 °C, air R R = Cl, Br, OMe, CO2Me, NO2, CO2H Scheme 61. Iron-mediated direct arylation of arenes by arylboronic acids (cyclen = 1,4,7,10tetraazacyclododecane). IRON CATALYSIS IN SYNTHETIC CHEMISTRY EWG R Het-Ar [Fe] / K2S2O8 solvent, TFA N B(OH)2 R 49 O 1,4-Quinone [Fe] / K2S2O8 solvent O R Scheme 62.
Even for the 3-(alkyl)cycloalkanonenes, the desired intramolecular rearranged bicyclic product was obtained in moderate-to-good yield (71). In all these cases, Fe (dbm)3 was used as an effective catalyst due to its nonhygroscopic, air-stable nature and easy solubility in THF. In addition, other iron complexes including FeCl2, FeCl3, and Fe(acac)3 were found to catalyze this reaction quite effectively (Scheme 45). , esters, amides, and thioesters) were successfully converted into cyclic ketones (Scheme 46) (72).