Iron complexes aromatic

In a related reaction, isocyanides can be converted to aromatic aldimines by treatment with an iron complex followed by irradiation in benzene solution RNC -I- CftHe PhCH=NR. ... 

In addition to nonheme iron complexes also heme systems are able to catalyze the oxidation of benzene. For example, porphyrin-like phthalocyanine structures were employed to benzene oxidation (see also alkane hydroxylation) [129], Mechanistic investigations of this t3 pe of reactions were carried out amongst others by Nam and coworkers resulting in similar conclusions like in the nonheme case [130], More recently, Sorokin reported a remarkable biological aromatic oxidation, which occurred via formation of benzene oxide and involves an NIH shift. Here, phenol is obtained with a TON of 11 at r.t. with 0.24 mol% of the catalyst. 

One-step hydroxylation of aromatic nucleus with nitrous oxide (N2O) is among recently discovered organic reactions. A high eflSciency of FeZSM-5 zeolites in this reaction relates to a pronounced biomimetic-type activity of iron complexes stabilized in ZSM-5 matrix. N2O decomposition on these complexes produces particular atomic oj gen form (a-oxygen), whose chemistry is similar to that performed by the active oxygen of enzyme monooxygenases. Room temperature oxidation reactions of a-oxygen as well as the data on the kinetic isotope effect and Moessbauer spectroscopy show FeZSM-5 zeolite to be a successfiil biomimetic model. 

More recently, an environmentally benign method using air as oxidant has been developed for the oxidative cyclization of arylamine-substituted tricarbonyl-iron-cyclohexadiene complexes to carbazoles (Scheme 19). Reaction of methyl 4-aminosalicylate 45 with the complex salt 6a affords the iron complex 46, which on oxidation in acidic medium by air provides the tricarbonyliron-complexed 4a,9a-dihydrocarbazole 47. Aromatization with concomitant demetalation by treatment of the crude product with p-chloranil leads to mukonidine 48 [88]. The spectral data of this compound are in agreement with those reported by Wu[22j. 

Tricarbonyliron-coordinated cyclohexadienylium ions 569 were shown to be useful electrophiles for the electrophilic aromatic substitution of functionally diverse electron-rich arylamines 570. This reaction combined with the oxidative cyclization of the arylamine-substituted tricarbonyl(ri -cyclohexadiene)iron complexes 571, leads to a convergent total synthesis of a broad range of carbazole alkaloids. The overall transformation involves consecutive iron-mediated C-C and C-N bond formation followed by aromatization (8,10) (Schemes 5.24 and 5.25). 

Over the past 15 years, we developed three procedures for the iron-mediated carbazole synthesis, which differ in the mode of oxidative cyclization arylamine cyclization, quinone imine cyclization, and oxidative cyclization by air (8,10,557,558). The one-pot transformation of the arylamine-substituted tricarbonyl(ri -cyclohexadiene) iron complexes 571 to the 9H-carbazoles 573 proceeds via a sequence of cyclization, aromatization, and demetalation. This iron-mediated arylamine cyclization has been widely applied to the total synthesis of a broad range of 1-oxygenated, 3-oxygenated, and 3,4-dioxygenated carbazole alkaloids (Scheme 5.24). 

The electrophilic aromatic substitution of 655 with the iron-complexed cation 602 afforded the iron complex 657 in almost quantitative yield. Treatment of 657 with... 

For the total synthesis of mukonidine (54), the required arylamine 656 was obtained quantitatively from commercial 4-aminosalicylic acid (659) using diazomethane (559). However, for large-scale preparation, this transformation was better achieved with sulfuric acid and methanol (81). The reaction of the arylamine 656 with the iron-complex salt 602 provided the iron complex 660 in 87% yield. The high yield of C-C bond formation was ascribed to the high nucleophilicity of the ortho-amino position of the aromatic nucleus arising from the hydroxy group in the 3-position of the arylamine. The iron-mediated arylamine cyclization of the complex... 

Electrophilic aromatic substitution of 3-methoxy-4-methylaniline (655) using the 2-methoxy-substituted iron complex salt 665, followed by oxidative cyclization with concomitant aromatization of the resulting iron complex salt 666, affords 2,7-dimethoxy-3-methylcarbazole (667). Oxidation of the carbazole 667 with DDQ... 

Electrophilic aromatic substitution of 708 with the iron-coordinated cation 602 afforded the iron-complex 714 quantitatively. The iron-mediated quinone imine cyclization of complex 714, by sequential application of two, differently activated, manganese dioxide reagents, provided the iron-coordinated 4b,8a-dihydrocarbazole-3-one 716. Demetalation of the iron complex 716 with concomitant... 

Electrophilic aromatic substitution of the arylamine 780a using the iron-complex salt 602 afforded the iron-complex 785. Oxidative cyclization of complex 785 in toluene at room temperature with very active manganese dioxide afforded carbazomycin A (260) in 25% yield, along with the tricarbonyliron-complexed 4b,8a-dihydro-3H-carbazol-3-one (786) (17% yield). The quinone imine 786 was also converted to carbazomycin A (260) by a sequence of demetalation and O-methylation (Scheme 5.86). The synthesis via the iron-mediated arylamine cyclization provides carbazomycin A (260) in two steps and 21% overall yield based on 602 (607-609) (Scheme 5.86). 

Using a one-pot process of oxidative cyclization in air, the arylamine 780a was transformed to the tricarbonyl(ri -4b,8a-dihydro-9H-carbazole)iron complex 792. Finally, demetalation of 792 and subsequent aromatization gave carbazomycin A (260). This synthesis provided carbazomycin A (260) in three steps and 65% overall yield based on 602 (previous route four steps and 35% yield based on 602) (610) (Scheme 5.88). 

The arylamine 794 required for the improved total synthesis of carbazomycin B (261) was prepared in quantitative yield by hydrogenation of the nitroaryl derivative 793 (see Scheme 5.85). Oxidative coupling of the iron complex salt 602 and the arylamine 794 in air afforded the tricarbonyl(ri -4b,8a-dihydro-9H-carbazole)iron complex (795). Demetalation of 795, followed by aromatization, led to O-acetylcarbazomycin B (796). 

The construction of the carbazole framework was achieved by slightly modifying the reaction conditions previously reported for the racemic synthesis (614). Reaction of the iron complex salt 602 with the fully functionalized arylamine 814 in air provided the tricarbonyliron-coordinated 4b,8a-dihydrocarbazole complex 819 via sequential C-C and C-N bond formation. This one-pot annulation is the result of an electrophilic aromatic substitution and a subsequent iron-mediated oxidative cyclization by air as the oxidizing agent. The aromatization with concomitant demetalation of complex 819 using NBS under basic reaction conditions, led to the carbazole. Using the same reagent under acidic reaction conditions the carbazole was... 

Reaction of the iron complex salt 602 with the arylamine 921 in the presence of air led directly to the tricarbonyl(ri -4b,8a-dihydro-9H-carbazole)iron complex (923) by a one-pot C-C and C-N bond formation. Demetalation of complex 923 and subsequent aromatization by catalytic dehydrogenation afforded 3,4-dimethoxy-l-heptyl-2-methylcarbazole (924), a protected carbazoquinocin C. Finally, ether cleavage of 924 with boron tribromide followed by oxidation in air provided carbazoquinocin C (274) (640) (Scheme 5.120). 

Construction of the carbazole framework was achieved by slightly modifying the reaction conditions previously reported for the racemic synthesis (641,642). The reaction of the (R)-arylamine 928 with the iron complex salt 602 in air provided by concomitant oxidative cyclization the tricarbonyliron-complexed 4b,8a-dihydro-9H-carbazole (931). Demetalation of the complex 931, followed by aromatization and regioselective electrophilic bromination, afforded the 6-bromocarbazole 927, which represents a crucial precursor for the synthesis of the 6-substituted carbazole... 

Electrophilic aromatic substitution of the 4-aminobenzofuran 1103 with the complex salt 602 afforded the iron complex 1109 in quantitative yield. Cyclization of the complex 1109 with concomitant aromatization was achieved by oxidation with an excess of iodine in pyridine at 90 °C in air to afford directly furostifoline (224) (688,689) (Scheme 5.179). 

Four years later, we reported an improved iron-mediated total synthesis of furostifoline (224) (689). This approach features a reverse order of the two cyclization reactions by first forming the carbazole nucleus, then annulation of the furan ring. As a consequence, in this synthesis the intermediate protection of the amino function is not necessary (cf. Schemes 5.178 and 5.179). The electrophilic aromatic substitution at the arylamine 1106 by reaction with the iron complex salt 602 afforded the iron... 

The syntheses of iron isonitrile complexes and the reactions of these complexes are reviewed. Nucleophilic reagents polymerize iron isonitrile complexes, displace the isonitrile ligand from the complex, or are alkylated by the complexes. Nitration, sulfonation, alkylation, and bromina-tion of the aromatic rings in a benzyl isonitrile complex are very rapid and the substituent is introduced mainly in the para position. The cyano group in cyanopentakis(benzyl isonitrile)-iron(ll) bromide exhibits a weak "trans" effect-With formaldehyde in sulfuric acid, benzyl isonitrile complexes yield polymeric compositions. One such composition contains an ethane linkage, suggesting dimerization of the transitory benzyl radicals. Measurements of the conductivities of benzyl isonitrile iron complexes indicate a wide range of A f (1.26 e.v.) and o-o (1023 ohm-1 cm.—1) but no definite relationship between the reactivities of these complexes and their conductivities. 

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