Tricarbonyl iron complexes carbonylation

Carboxylic acids, a-bromination of 55, 31 CARBOXYLIC ACID CHLORIDES, ketones from, 55, 122 CARBYLAMINE REACTION, 55, 96 Ceric ammonium nitrate [Ammonium hexa mtrocerate(IV)[, 55, 43 Chlorine, 55, 33, 35, 63 CHROMIUM TRIOXIDE-PYRIDINE COMPLEX, preparation in situ, 55, 84 Cinnamomtnle, a-phenyl- [2-Propeneni-tnle 2,3-diphenyl-], 55, 92 Copper(l) iodide, 55, 105, 123, 124 Copper thiophenoxide [Benzenethiol, copper(I) salt], 55, 123 CYCLIZATION, free radical, 55, 57 CYCLOBUTADIENE, 55, 43 Cyclobutadieneiron tricarbonyl [Iron, tn-carbonyl(r)4-l,3-cyclo-butadiene)-], 55,43... 

P. Vogel s group studied exhaustively the 5,6,7,8-tetramethylidenebicyclo[2.2.2]octane system and its metal carbonyl complexes. The preparation and CD spectra of tricarbonyl-iron complexes (144-147) were reported333. The chirality of complexes 144 and 146 is due uniquely to the coordination of Fe(CO)3 moieties. The signs of the Cotton effects for (+)-144 and (+)-146 obey the octant rule, as the endo-Ft(CO)j, of 144 and 146 fall in a positive octant, while the second exo-Fe(CO)3 (syn to the carbonyl) lies almost on the XY nodal plane, and thus its contribution is expected to be small. The deuterium-substituted free tetraenone 148, however, showed an anti-octant behavior. The CD spectra of 144 and 146 are strongly temperature and solvent dependent. 

Bicyclo[4.1.1] or [3.2.1]octenones and cyclopropanes have resulted from decomplexation of the iron tricarbonyl group from the alkyl-allyliron tricarbonyl complex, using oxidative (i.e., GO atmosphere) or carbonylative methods for the bicyclooctenones and ceric ammonium nitrate (GAN) for the cyclopropanes. Photolysis of analogous tricarbonyl iron complexes leads to monoolefmic hydrocarbons or aldehydes. The kinetics of GO substitution in reactions of 77 -cyclopropenyl complexes of iron is also reported. " A number of comprehensive reviews have appeared since 1992, illustrating the chemistry of ry -allyliron complexes. 

A [5+1] carbonylative cycloaddition of chromium Fischer carbene complexes having /ra j,/ra 5-dienyl substituents at the carbene carbon atom with nonacarbonyldiiron gives ri -2-alkoxycyclohexa-2,4-dienone(tricarbonyl)iron complexes and 2-alkoxyphenols (Scheme 4-13). Without the addition of the carbonyliron complex, this reaction works only for substrates that have a cw-disposition at the a,P-double bond. The ri -2-alkoxycyclohexa-2,4-dienone(tricarbonyl)iron complexes can be converted to the corresponding phenols by treatment with base or by stirring with silica gel in the presence of air. 

Iron carbonyls have been used in stoichiometric and catalytic amounts for a variety of transformations in organic synthesis. For example, the isomerization of 1,4-dienes to 1,3-dienes by formation of tricarbonyl(ri4-l,3-diene)iron complexes and subsequent oxidative demetallation has been applied to the synthesis of 12-prostaglandin PGC2 [10], The photochemically induced double bond isomerization of allyl alcohols to aldehydes [11] and allylamines to enamines [12,13] can be carried out with catalytic amounts of iron carbonyls (see Section 1.4.3). 

My co-worker H. Beutner (95) was able to isolate from a nitrite-containing carbonylferrate solution, in trace amounts only, a binuclear nitrogen-atom-bridged iron carbonyl compound. This complex is now obtained in good yield by UV irradiation of the reaction solution and was identified mass spectrometrically as di-/x-amino-bis(tricarbonyl)iron, (OC)3Fe(NH2)2Fe (C0)3. The group... 

Previous syntheses of tricarbonyl( /-diene)iron complexes have relied mainly on the reaction of Fe(CO)s, Fc3(CO)i2, or Fc2(CO)9 with the free diene. The use of the first two carbonyls suffers from the prolonged reflux times and/or ultraviolet irradiation necessary to obtain reaction and the consequent low yields and mixtures of complexes obtained with heat- and ultraviolet-sensitive dienes. The latter reagent, although utilized at lower temperatures, may react with polyenes (n > 3) to give mixtures containing, in addition to the expected product, binuclear derivatives containing a metal—metal bond.2... 

The complex functions as a convenient source of the tricarbonyliron moiety by displacement of the unsaturated ketone. For example, reaction with 1,3-cycloheptadiene results in a 78% yield of (//-l,3-cycloheptadiene)tricar-bonyliron. More importantly, it may be used in syntheses of tricarbonyl-(diene)iron complexes where the iron carbonyls are not satisfactory. Several complexes of sensitive heptafulvenes have been prepared in this way, and the reagent has been used in the synthesis of tricarbonyliron complexes of several steroids. 

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. 

Bis(phosphine) derivatives of pentacarbonyliron are starting materials for the synthesis of several organometallic iron complexes. " Iron carbonyl phosphine complexes have attracted attention because of their relevance to photochemical catalysis of olefin hydrosilation. Though Fe(CO)3(PR3)2 complexes are used widely in organotransition metal chemistry, an efficient preparation of these compounds has not been reported. Clifford and Mukherjee describe two methods for the synthesis of tricarbonyl-bis(triphenyphosphine)iron(0). They report that direct reaction between Fe3(CO)j2 and triphenylphosphine in THF solvent gives a mixture of Fe(CO)3[P(C6Hs)3]2 (27%) and Fe(CO)4[P(C5H5)3] (34%). The second... 

Tricarbonyliron complexes of conjugated trienes react with diazoalkanes at the free (uncom-plexed) double bond. In the synthesis of dimethyl 2-formylcyclopropane-l, 1-dicarboxylate (48), the ceric ion served the double function of catalyzing the deazetization and removing the tricarbonyl iron protecting group. When the optically active iron carbonyl complex was used, the addition of diazomethane gave selectively one diastereomer and this was used to make optically active dimethyl 2-formylcyclopropane-l,1-dicarboxylate (>90% ee). A similar route was employed to make the optically active formyl cyclopropanes 49, precursors to optically active cis- and tran.v-chrysanthemic acids. 

In contrast, the reaction of 1,2,3-triphenylcyclopropenylium bromide (33) with tricarbonyl-nitrosylferrate ion afforded the (cycloprop-2-enyl)carbonyl-iron complex 34. ... 

Little meaningful physical data on these complexes has appeared yet. The study of their reactivity is complicated by the effects of the substituents on the cyclobutadiene ring and the other ligands present. Until more information is available on the properties of the recently prepared unsubstituted cyclobutadieneiron tricarbonyl (XVIII) 38) and similar molecules, it is hard to be certain which properties are due to the presence of a cyclobutadiene group. Thus while cyclobutadieneiron tricarbonyl (XVIII) is easily oxidized by ferric chloride in ethanol (as are other diene-iron tri-carbonyl complexes, albeit to different types of product), tetraphenyl-cyclobutadieneiron tricarbonyl (XIII) is very resistant to this reagent, and indeed to most others, presumably mainly due to the steric hindrance of the phenyls. 

The largest group of diene complexes which have been investigated are iron carbonyl compounds. When 1,3-butadiene reacts with Fe lCO), the initial product is a labile f/ -complex, which readily loses carbon monoxide to yield (f/ -C4Hg)Fe(CO)3. Butadiene(tricarbonyl)iron is a yellow, essentially air stable complex, m.p. 19 "C. It was first prepared by Reihlen in 1930 by heating FeiCO), with butadiene in a tube under pressure, but this was an isolated discovery which did not arouse much interest at the time. On account of the ease of preparation and handling of these diene complexes, however, an enormous amount of work has been done in this area since the late 1950s. Only modest precautions are required to protect solutions from oxidation and some operations can be carried out even in air. 

Bia.2 b,3i -pjjg synthesis of Routiennocin employed iron tricarbonyl chemistry for the synthesis of the spiroketal unit. In this sequence the allylic epoxide 39 is converted to a mixture of allyl iron complexes 40 and 41 which is not separated but carbonylated together to give lactone 42 as a 9 1 (a 3 3"y) mixture (Scheme 4.14) this mixture is subsequently reduced to the saturated lactone 43. ... 

The reactions of various iron carbonyl complexes, such as Fe(GO)4(NMe3), with allene compounds under photo-lytic conditions, yield chelated 77 -allyliron complexes. Two brief reviews discussing the chemistry and application to organic synthesis of these (7r-allyl)tricarbonyl iron lactone complexes have appeared recently. Reaction of the iron lactone complexes with trimethyloxonium tetrafluoroborate yields the carbene complex 23 in good yields. Treatment of the cationic carbene complex with triphenylphosphine results in substitution at the terminal end of the allyl ligand of the trimethylenemethane complex 24. 

The olefin-iron carbonyl complexes were first introduced by two entirely different synthetic methods. In 1930 Reihlen and co-workers (I) obtained butadiene-iron tricarbonyl by a reaction of butadiene with iron penta-carbonyl and in 1953 Reppe and Vetter (2) reported organoiron compounds, since shown to be diene-iron carbonyl complexes, following reaction of acetylene with iron carbonyls. 

A side-chain carbonyl group in an T -allyl(tricarbonyl)iron lactone complex can be stereoselectively reduced with diisobutyl aluminum hydride. This constitutes an... 

Cyclopentadiene iron tricarbonyl has been prepared and decomposes thermally to the binuclear carbonyl [a -C5H5Fe(CO)2]2 [26o]. The binuclear iron complex may further react with cyclopentadiene or thermally decompose ( 200°) [27, 28] to give ferrocene. Monosubstituted ferrocenes may be prepared by the former reaction [27]. Chromium hexacarbonyl and cyclopentadiene at 280-350° react to give chromocene [29] the reaction is reversible since treatment of chromocene with carbon monoxide under pressure affords chromium hexacarbonyl, together with intermediate products such as [jr-CpCr(CO)3]2, [jr-Cp2Cr][3r-CpCr(CO)3] and, when hydrogen is also present, the cyclopentenyl complex jr-CsH5CrC5H7(CO)2, 4.1, is formed [30, 31, 32]. 

The tetra-cA-cycIononatetracne 241 is unstable and easily rearranges at 23 °C (t /2 50 min) to the isomeric d.v-8,9-dihydroindcne 242 (equation 77)89. It is interesting, however, that the iron(III) tricarbonyl complex of tetraene 241 is stable for many days at room temperature and isomerizes to the Fe-complex of 242 only upon heating in octane at 101 °C89. The principle of stabilization of the reactive multiple bonds with metal carbonyl complexes is well-known in modem organic synthesis (e.g. see the acylation of enynes90). 

In 1989, Thomas reported3 the novel synthesis of tricarbonyl(774-vinylke-tene)iron(O) complexes (221) from the corresponding 774-vinylketones (222). Nucleophilic attack by methyllithium on a carbonyl ligand is thought to produce the anionic complex 223, which then carbonylates to give the rf-... 

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