Electrophilic reactions iron carbonyl complexes

In addition to benzene and naphthalene derivatives, heteroaromatic compounds such as ferrocene[232, furan, thiophene, seienophene[233,234], and cyclobutadiene iron carbonyl complex[235] react with alkenes to give vinyl heterocycles. The ease of the reaction of styrene with substituted benzenes to give stilbene derivatives 260 increases in the order benzene < naphthalene < ferrocene < furan. The effect of substituents in this reaction is similar to that in the electrophilic aromatic substitution reactions[236]. 

Treatment of the potentially electrophilic Z-xfi-unsaturated iron-acyl complexes, such as 1, with alkyllithium species or lithium amides generates extended enolate species such as 2 products arising from 1,2- or 1,4-addition to the enone functionality are rarely observed. Subsequent reaction of 2 with electrophiles results in regiocontrolled stereoselective alkylation at the a-position to provide j8,y-unsaturated products 3. The origin of this selective y-deproto-nation is suggested to be precoordination of the base to the acyl carbonyl oxygen (see structures A), followed by proton abstraction while the enone moiety exists in the s-cis conformation23536. 

Reaction of Z-a./j-unsaturated iron-acyl complexes with bases under conditions similar to those above results in exclusive 1,4-addition, rather than deprotonation, to form the extended enolate species. However, it has been demonstrated that in the presence of the highly donating solvent hexamethylphosphoramide, y-deprotonation of the -complex 6 occurs. Subsequent reaction with electrophiles provides a-alkylated products such as 736 this procedure, demonstrated only in this case, in principle allows access to the a-alkylatcd products from both Z- and it-isomers of a,/j-unsaturated iron-acyl complexes. The hexamethylphosphoramide presumably coordinates to the base and thus prevents precoordination of the base to the acyl carbonyl oxygen, which has been suggested to direct the regioselective 1,4-addition of nucleophiles to -complexes as shown (see Section 1.1.1.3.4.1.2.). These results are also consistent with preference for the cisoid conformations depicted. 

The reactions of a,a -dibromoketones with iron carbonyls generate oxyallyliron complexes (75). These undergo cycloaddition with cyclopentadiene and furan, but with thiophene only products of electrophilic attack are obtained (78JA1765). Thus the oxyallyliron complex (75 R = Me R = H) reacts with thiophene to produce (76) in 37% yield. 

Dienes form very stable complexes with a variety of metal caibonyls, particularly Fe(CO)s, and the neutral V-diene metal carbonyl complexes are quite resistant to normal reactions of dienes (e.g. hydrogenation, Diels-Alder). However, they are subject to nucleophilic attack by a variety of nonstabilized carbanions. Treatment of -cyclohexadiene iron tricarbonyl with nonstabilized carbanions, followed by protonolysis of the resulting complex, produced isomeric mixtures of alkylated cyclohexenes (Scheme 15).24 With acyclic dienes, this alkylation was shown to be reversible, with kinetic alkylation occurring at an internal position of the complexed dienes but rearranging to the terminal position under thermodynamic conditions (Scheme 16).2S By trapping the kinetic product with an electrophile, overall carbo-... 

Reactions of acyclic derivatives with carbon electrophiles have also been examined.33,34 An illustrative reaction involving methylation of the unsubstituted complex [MnCr 4-butadiene)(CO)3], (19), is shown in Scheme 16. Again, the reaction is presumed to occur via a methylmanganese species (20) and after methyl migration the unsaturated metal center is stabilized by formation of a Mn—H—C bridge (isomers 21a and 21b). Deprotonation of equilibrating (21a and 21b) yields the [Mn(l-methylbutadiene)(CO>3]-complex (22), which has exclusively trans stereochemistry.34 This sequence represents alkylation of the terminal carbon of butadiene and complements the iron carbonyl chemistry, where terminal acylation has been achieved as described above. Unpublished results indicate that a second methylation of (22) occurs... 

Water also attacks the electrophilic a carbon of the ruthenium vi-nylidene complex 80. The reaction does not yield the ruthenium acyl complex, however, as is found for the reaction with the similar iron vinylidene complex [(i75-C5H5)(CO)2Fe=C=CHPh]+ (56), but rather 91 is the only isolated product (78). The mechanism for this transformation most reasonably involves rapid loss of H+ from the initially formed hydroxycarbene to generate an intermediate acyl complex (90). Reversible loss of triphenyl-phosphine relieves steric strain at the congested ruthenium center, and eventual irreversible migration of the benzyl fragment to the metal leads to formation of the more stable carbonyl complex (91) [Eq. (86)]. 

A noteworthy work on complexes of this type has been on the oxyallyl complexes (171) and their related dimers (172). Despite the fact that only electrophilic substitution is observed in the reactions of these complexes and their derived (oxyallyl)Fe(CO)4 cations, these compounds, or structurally very similar ones, have been proposed as intermediates in iron carbonyl mediated [4 + 3] cycloaddition reactions of a ,a -dibromoketones and dienes. " ... 

Cyclobutadiene-iron tricarbonyl is prepared through reaction of S,4-dichlorocydolmtene and diiron enneacarbonyl. In an analogous manner, one can prepare 1,2-diphenyl- 1,2,3,4-tetramethyl- and benzocyclobutadiene-iron tri-carbonyl complexes. Cyclobutadiene-iron tricarbonyl is aromatic" in the sense that it undergoes facile attack by electrophilic reagents to produce monosubstituted cydo-butadiene-iron tricarbonyl complexes. Functional groups in the substituents display many of their normal chemical reactions which can be used to prepare further types of substituted cyclobutadiene-iron tricarbonyl complexes. 

Cyclooctatetraene, as a ligand in transition-metal complexes (especially iron carbonyls), reacts with electrophiles to form t -bicylo[5.1. Ojoctadienyl complexes such as 7. Reviews concerning early examples of this reaction type are available. 

Allyl)iron(III) complexes have been implicated in the enzymatic lipoxygenation of polyunsaturated fatty acids. In the proposed model, concerted allylic deprotonation and electrophilic addition see Electrophilic Reaction) of Fe gives an iron allyl species, which undergoes Fe-C bond insertion by O2. In model studies, reaction of allyltributyltin compounds with FeBrs, followed by exposure to oxygen, gives oxidation to the carbonyl compounds (26) through presumed intermediates (27). 

Similar to the reaction course of the allylic substitution, which involves formation of tr-allyl moieties followed by subsequent nucleophilic addition across the Jt-bond, the mononitrosyl iron(—II) complex was expected to be active in transesterifications involving activation of carbonyl group and nucleophilic addition to the electrophilic carbon atom [100]. This assumption could be verified by experimental tests. Under neutral conditions without addition of a ligand co-catalyst, the iron complex 31 exhibited high activity in the transesterification of vinyl acetate. Good to excellent yields were obtained affording a new ester bond, as depicted in Scheme 39. 

Complexation of alkenes to iron carbonyl fragments increases the electrophilicity of the alkene, owing to the electron-withdrawing ability of the carbonyl ligands. The anion of dimethyl malonate will attack the iron tetracarbonyl complex of methyl acrylate 6.295 (Scheme 6.113). " The resulting anion 6.296 is obviously related to the intermediates involved in the reactions of Collman s reagent (Section 4.5.1). Thus, carbonylation and addition of an alkyl halide results in acylation. 

Iron-acyl enolates such as 1, 2, and 3 react readily with electrophiles such as alkyl halides and carbonyl compounds (see Houben-Weyl, Vol. 13/9a p418). The reactions of these enolatc species with alkyl halides and similar electrophiles are discussed in Section D.1.1.1.3.4.1.3. To date, only the simple enolates prepared by a-deprotonation of acetyl and propanoyl complexes have been reacted with ketones or aldehydes. 

Electrophilic aromatic substitution of 5-hydroxy-2,4-dimethoxy-3-methylaniline by reaction with the iron complex salts affords the corresponding aryl-substituted tricarbonyliron-cyclohexadiene complexes. O-Acetylation followed by iron-mediated arylamine cydization with concomitant aromatization provides the substituted carbazole derivatives. Oxidation using cerium(IV) ammonium nitrate (CAN) leads to the carbazole-l,4-quinones. Addition of methyllithium at low temperature occurs preferentially at C-1, representing the more reactive carbonyl group, and thus provides in only five steps carbazomycin G (46 % overall yield) and carbazomycin H (7 % overall yield). 

Figure 12 shows a generally accepted reaction sequence for these enzymes. O2 can bind trans to any of the facial triad residues forming an adduct that may be described as an iron(III)-superoxide complex as shown in Figure 12d. This superoxide then attacks the electrophilic carbonyl carbon of 2-OG to form iron(IV)-peroxo adduct Figure 12e, which in turn undergoes C-C bond cleavage and subsequent O bond...

The Simmons-Smith reaction is an efficient and powerful method for synthesizing cyclopropanes from alkenes [43]. Allylic alcohols are reactive and widely used as substrates, whereas a,j8-unsaturated carbonyl compounds are unreactive. In 1988, Ambler and Davies [44] reported the electrophilic addition of methylene to a,/3-unsaturated acyl ligands attached to the chiral-at-metal iron complex. The reaction of the racemic iron complex 60 with diethylzinc and diiodomethane in the presence of ZnCl2 afforded the c/s-cyclopropane derivatives 61a and 61b in 93 % yield in 24 1 ratio (Sch. 24). 

---