Iron-catalyzed carbonylations

An iron-catalyzed carbonylation reaction of alkynes 120 forming succinimides 121 by the aid of Fe(CO)5 78 or [Fe3(CO)i2] 119 has been reported by Beller et al. (Scheme 31) [94]. This reaction seems interesting as iron-carbonyl complexes are kinetically relatively inert. As a model system 3-hexyne was reacted with excess ammonia under 20 bar CO pressure. Employing a higher pressure leads to... 

Scheme 31 Catalytic cycle for the iron-catalyzed carbonylation proposed by Seller et al. [94]...

Iron-catalyzed carbonylations, 34 124-125 Fe(CO)5/amine catalysts, 34 124 homologation of methanol, 34 124 proposed mechanism for, 34 125 Iron complexes... 

Scheme 1.27 Iron-catalyzed carbonylative synthesis of amides and esters.

Oriyama and coworkers reported an iron-catalyzed reductive etherification of carbonyl compounds with triethylsilane and alkoxytriaUcylsilane [149, 150] and alcohols (Scheme 48) [151]. 

Scheme 48 Iron-catalyzed reductive etherification of carbonyl compounds...

Although some methods for reductive etherifications of carbonyl compounds have been reported [152-162], the iron-catalyzed version possesses several advantages (1) fairly short reaction times are needed, (2) not only trimethylsilyl ether but also triethylsilyl and butyldimethylsilyl ethers and alcohols are adaptable, and (3) a broad substrate scope. 

Scheme 33 Iron-catalyzed reductive carbonylation reported by Reppe [108]...

Additionally, various intra- and intermolecular iron-catalyzed Barbier-type reactions of organosamarium com-pounds and carbonyl electrophiles have been reported by Molander and co-workers. 

Durandetti et al. have described iron-catalyzed electrochemical allylation of carbonyl compounds with allylic acetates (Equation (27)).333 In the case of aldehydes, slow addition of the corresponding aldehyde is required in order to avoid pinacol formation. With crotyl acetate (R3 = Me), the reaction proved to be highly regioselective, providing almost exclusively branched homoallylic alcohols 150. 

There are a number of amine-catalyzed carbonylation reactions which are catalyzed by cobalt carbonyl and iron carbonyl. It seems to me that these are insertion reactions of metal amides, where carbon monoxide is inserted and then some kind of a reduction or subsequent reaction gives the observed products, urea derivatives or carbamates in alcohols. We do not know the structure of the iron compound it is probably similar to the cobalt species shown. 

This chapter will be divided into sections according to the electrophiles aldehydes and ketones, imines and iminium salts, carboxylic acid derivatives and finally a,P-unsaturated carbonyl compounds, which undergo conjugate additions. Further subdivision will be made according to the nature of the nucleophile, i.e. 0-, N-, S-, P- or C-nucleophiles. Finally, multicomponent heterocyclic syntheses will be mentioned, if they consist at least of one iron-catalyzed addition step to a carbonyl compound. 

The iron-catalyzed [3 + 2]-cycloaddition (Huisgen reaction) of nitriles and carbonyl compounds as reported by Itoh et al. is one of the rare examples reported where an iron reagent can be utilized for the synthesis of 1,2,4-oxadiazoles (Scheme 9.35) [93]. In this reaction, methyl ketones are nitrated at the a-position by Fe(N03)3 to generate an a-nitro ketone. This intermediate rearranges to an acyl cyanate, which reacts further with the nitrile to give the heterocyclic product 48 in good to excellent yields (R1 = Ph, R2 = CH3 95% yield). 

Along with several other Lewis acids, FeCl3 was also tested by Hsung and coworkers in the formal [3 + 3]-cycloaddition of enolized 1,3-diketones with a,(3-unsaturated carbonyl compounds (Scheme 9.39) [97]. The iron-catalyzed reaction gave the desired bicyclic compound 52 in good yields better results were obtained utilizing BF3OEt2 or In(OTf)3 as Lewis acid. 

Scheme 9.45 Carbonylative iron-catalyzed ring expansion of epoxides.

New catalysts have helped increase the conversion and yields. The older, high-pressure processes used zinc-chromium catalysts, but the low-pressure units use highly active copper catalysts. Liquid-entrained micrometer-sized catalysts have been developed that can convert as much as 25 percent per pass. Contact of the synthesis gases with hot iron catalyzes competing reactions and also forms volatile iron carbonyl that fouls the copper catalyst. Some reactors are lined with copper. 

Nadal and colleagues recently reported a Ni-catalyzed carbonylative Pauson-Khand-like [2+2+1] cycloaddition of allyl halides and alkynes in the presence of carbon monoxide and iron as the stoichiometric reducing agent [148]. The reaction was proposed to occur via reductively generated Ni(I)-radical like species free radicals were, however, considered unlikely. 

Cobalt-, Manganese- and Iron-catalyzed Cross-coupling Reactions 9.4.2.1 Carbonylations and acylations... 

Olefins are usually carbonylated in the presence of metal carbonyls, such as nickel, cobalt, and iron carbonyls under homogeneous conditions, and the mechanism of these carbonylations has been established in several cases. On the other hand, isolation or formation of true palladium carbonyl has not been reported. Since palladium is an efficient and versatile catalyst for various types of the carbonylation mentioned above, the mechanisms of the carbonylation of olefin-palladium chloride complexes and of metallic palladium catalyzed carbonylations seem to be worth investigating. 

Satoh T, Kokubo K, Miura M et al (1994) Effect of copper and iron cocatalysts on the palladium-catalyzed carbonylation reaction of iodobenzene. Organometallics 13 4431 1436... 

Several other examples of intramolecular ruthenium-, copper-, rhodium- and iron-catalyzed cyclizations via carbometalation with polyhalocarbons are known, with a range of stereoselectivities25 4 49. Similarly, palladium-catalyzed intramolecular ene-halogenocyclization" of unsaturated a-iodo carbonyl compounds, using Pd(dppe)2, has been applied to heterocyclic synthesis26 29. 

Aside from the thermal and photochemical activation of Fe(CO)5 and related iron carbonyl compounds, the field of iron catalyzed hydrogenation lay mostly dormant for decades. As outhned in the previous section, comprehensive follow-up papers on Fe(CO)5 chemistry had appeared but few new metal-ligand platforms for cata-... 

Although nickel-catalyzed carbonylative Pauson-Khand cycloadditions have not been broadly developed, related doubly carbonylative cycloadditions involving allyl halides have been demonstrated as an entry to functionalized cyclopentenones. In recent catalytic versions, iron powder was used as the terminal reductant and dehalogenating agent (Scheme 3-38). [Caution Ni(CO)4, which could potentially be liberated in this reaction, is a highly toxic gas.]... 

Transition-metal-catalyzed carbonylation reactions have shown impressive progress during past few decades especially, the use of ruthenium, rhodium, and palladium as catalysts is widespread. More recently, iron and copper catalysts have also been attracting the attention of synthetic chemists because of their low cost and environmentally benign properties. 

Iron-, Copper-, Nickel-, and Cobalt-Catalyzed Carbonylative Domino Reactions... 

Even though Ni(CO)4 is called liquid death, this nickel catalyst has been applied in carbonylation reactions [52]. The group of Ricart reported a nickel-catalyzed carbonylative cycloaddition of alkynes and aUyl hahdes to cyclopentanes. The desired products were obtained in high yields and with controlled stereoselectivity. Iron was used as a reductant. An extension of the reaction to new substrates led to the conclusion that, although the steric and electronic effects of the alkyne substituents are generally irrelevant in relation to the adducts and their yields, those of the allylic counterpart may have a significant influence on the outcome of the reaction. However, the presence of the amine moiety in the alkyne completely inhibited the reaction. The feasibility of a multicentered reaction was verified with a triacetylene, in which up to 12 bonds were created simultaneously and in good yield (Scheme 1.30). 

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