Iron tricarbonyl, reaction with

The reaction of o-diphenylcyclobutadiene (generated in situ by oxidation of its iron tricarbonyl complex) with p-benzoquinone yields A as the exclusive product. With tetracyanoethylene, however, B and C are formed in a 1 7 ratio. Discuss these results, and explain how they relate to the question of the square versus rectangular shape of cyclobutadiene. 

In a series of classic studies, Pettit et al. reported the synthesis of (cyclobutadiene)iron tricarbonyl together with a variety of electrophilic substitution reactions of this aromatic system (Scheme S).25-27... 

One final comment relating to the aromaticity of the cyclobutadiene ligand concerns the orientation effect of substituents towards introduction of a second substituent. To date, the only reaction bearing on this question which has been performed is the acetylation of methylcyclobutadiene -Fe(CO)3 (XVIII), which was prepared by reducing the chloromethyl complex (IX). Acetylation of Complex XVIII produces a mixture of 2-and 3-acetyl-1-methylcyclobutadiene-iron tricarbonyl complexes with the latter isomer (XIX) predominating ( 2 1). This is not the orientation... 

A final example of the use of tartrate-derived crotylboronates in natural product synthesis is illustrated in the formal total synthesis of ikarugamicin (Scheme II-11) [179]. Here, Roush and Wada used the asymmetric crotylboration of meso-(t/" -2,4-hexadien-1,6-dial)iron tricarbonyl 266 with (S,S)-(E)-219 to set three stereocenters in their synthesis of the a,s-indacene unit of ikarugamycin. This key reaction provided 267 in 90% yield and >98% ee. Homoallylic alcohol 267 was converted to the allylic acetate 268, which underwent stereoselective ethylation with EtsAl with retention of stereochemistry. The resulting adduct 269 was subsequently elaborated to as -indacene unit 271 through a 15-step synthetic sequence, including the intramolecular Diels-Alder reaction of 270. 

The reactions of cationic (ii -dienyl)iron-tricarbonyl complexes with nucleophiles have been studied extensively by Birch and Pearson. These complexes are prepared by abstraction of an allylic hydride from riMiene complexes, which are readily available from the reaction of 1,3- or 1,4-dienes with Fe fCO),. The parent pentadienyl complex reacts with a variety of nucleophiles exclusively at the termineil carbon, and this reaction generates a new T -diene complex (Equation 11.50). ... 

The initial stage involves the formation of a highly reactive anion Fe(CO)4 , which interacts with isolated double bonds, followed by double bond isomerization and the formation of n-complexes with the iron tricarbonyl residues. The final product is composed of the ri" -(butadienyl)irontricarbonyl units with both trans-trans- and cis-trans-tetramethylene groups. Since the iron tricarbonyl complexes with two noncon-jugated double bonds are unstable, no complexes between two polymer chains are formed. The reaction of iron carbonyls with low-molecular-weight nonconjugated dienes is accompanied by the double bond migration. 

Anionic (77 -allyl)iron tricarbonyl complexes are easily prepared by the hydride reduction of (butadiene)iron tricarbonyl or (l-phenylbutadiene)iron tricarbonyl complexes with Li[BHEt3] in THF. Tricarbonyl(r7" -l,3-diene)-iron(O) complexes undergo addition reactions with reactive carbanions, such as LiCHPh2, to form anionic tricarbonyl(77 7 -but-3-en-l-yl)iron(0) complexes. 

Reactions of azadienes and dienamides, carrying chiral substituents, are repotted295 to react with [Fe2(CO)9] to afford (T -diene) iron tricarbonyl complexes with good to excellent diasteroselectivity, depending on the nature of the chiral auxiliary employed. Complete selectivity was observed for the dienamide prepared from (5)-2-(diphenylhydroxymethyl)pyrrolidine and sorbic acid, leading to a chiral non-racemic diene complex, the stereochemistry of which was determined by single crystal X-ray methods. 

Recent work by several groups has shown that the dienyl-Fe(CO)3 exists as a stable group present in several related cationic species. Thus Dauben and Bertelli (27) have prepared cycloheptadienyl-iron tricarbonyl fluoroborate (LXXII) from cycloheptadiene-Fe(CO)3 (XXXIV) and triphenylmethyl fluoroborate. The inherent stability of the dienyl-Fe(CO)3 grouping is again seen in the reaction of cycloheptatriene-iron tricarbonyl (XXXIII) with the triphenylmethyl cation. Hydride abstraction to give the cycloheptatrienyl-Fe(CO)3 cation does not occur but rather the triphenylmethyl cation adds to the free olefinic bond to produce the cation (LXXIII)... 

Even though the electron density of the diene system in tricarbonyl(T -diene)iron complexes is reduced due to 7t-donation to the iron center, reactions with various electrophiles are still possible. Thus, Friedel-Crafts alkylation of (diene)iron complexes with alkoxychloromethanes gives selectively cis- or tra s-(alkoxypenta-2,4-diene)iron complexes depending on the work-up conditions (Scheme 4—110). ... 

A convenient synthesis of a cubane system, in which the cyclobutadiene transfer reaction plays a key role, was reported by Pettit et al. (Scheme 11). By the oxidative decomposition of cyclobutadiene-iron tricarbonyl 56 with Ce + ion in the presence of a dienophile, a molecule of cyclobutadiene can be transferred from the iron to the dienophile. Decomposition of 56 in the presence of 2,5-dibromobenzoquinone 57 yielded the Diels-Alder adduct 58 with e do-configuration. Irradiation of 58 in benzene with a high-pressure Hg lamp afforded the bishomocubane derivative 59, which gave cubane-1,3-dicarboxylic acid 60 (80%) by treatment of 59 with aqueous KOH at 100°C. 

Other Reactions. Due to the highly reactive conjugated double bonds, butadiene can undergo many reactions with transition metals to form organometaHic complexes. For instance, iron pentacarbonyl reacts with butadiene to produce the tricarbonyl iron complex (10) (226). This and many other organometaHic complexes have been covered (227). 

The reactivity sequence furan > tellurophene > selenophene > thiophene is thus the same for all three reactions and is in the reverse order of the aromaticities of the ring systems assessed by a number of different criteria. The relative rate for the trifluoroacetylation of pyrrole is 5.3 x lo . It is interesting to note that AT-methylpyrrole is approximately twice as reactive to trifluoroacetylation as pyrrole itself. The enhanced reactivity of pyrrole compared with the other monocyclic systems is also demonstrated by the relative rates of bromination of the 2-methoxycarbonyl derivatives, which gave the reactivity sequence pyrrole>furan > selenophene > thiophene, and by the rate data on the reaction of the iron tricarbonyl-complexed carbocation [C6H7Fe(CO)3] (35) with a further selection of heteroaromatic substrates (Scheme 5). The comparative rates of reaction from this substitution were 2-methylindole == AT-methylindole>indole > pyrrole > furan > thiophene (73CC540). 

Diels-Alder reactions, 4, 842 flash vapour phase pyrolysis, 4, 846 reactions with 6-dimethylaminofuKenov, 4, 844 reactions with JV,n-diphenylnitrone, 4, 841 reactions with mesitonitrile oxide, 4, 841 structure, 4, 715, 725 synthesis, 4, 725, 767-769, 930 theoretical methods, 4, 3 tricarbonyl iron complexes, 4, 847 dipole moments, 4, 716 n-directing effect, 4, 44 2,5-disubstituted synthesis, 4, 116-117 from l,3-dithiolylium-4-olates, 6, 826 electrocyclization, 4, 748-750 electron bombardment, 4, 739 electronic deformation, 4, 722-723 electronic structure, 4, 715 electrophilic substitution, 4, 43, 44, 717-719, 751 directing effects, 4, 752-753 fluorescence spectra, 4, 735-736 fluorinated derivatives, 4, 679 H NMR, 4, 731 Friedel-Crafts acylation, 4, 777 with fused six-membered heterocyclic rings, 4, 973-1036 fused small rings structure, 4, 720-721 gas phase UV spectrum, 4, 734 H NMR, 4, 7, 728-731, 939 solvent effects, 4, 730 substituent constants, 4, 731 halo... 

Benzocyclobutene, when generated by oxidation of its iron tricarbonyl complex, can function as the dipolarophile in 1,3-dipolar cycloaddition reactions with arylnitrile oxides (Scheme 113).177 Unfortunately the synthetic versatility of this type of process is limited because of the unreactivity of other 1,3-dipolar species such as phenyl azide, benzonitrile N-phenylimide, and a-(p-tolyl)benzylidenamine N-oxide.177... 

The oxidative cyclization of chiral 2-pyrrolidino-l-ethanol derivatives is shown in the reaction of 251 with trimethyl-amine iV-oxide and a substoichiometric amount of cyclohexadiene iron tricarbonyl to produce the corresponding oxazolopyrrolidine ring 252. The mechanism of this reaction is unknown. Both amine oxide and iron complex are essential for the reaction (Equation 39) <2005TL3407>. 

The iodine oxidative closure of iron tricarbonyl complex 299 (R = H and Me), itself prepared by the reaction of an arylamine with the tricarbonyl-(cyclohexadienyl)iron cation, may have potential as a method. ... 

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