Chiusoli reaction

Moreto and coworkers have made improvements to the Chiusoli reaction, the Ni(CO)4-mediated carbonylation cyclization of allyl halides and alkynes, by conducting it in methanol403. It has subsequently been applied in the synthesis of methylenomycin B, in an intramolecular sense to provide bicyclo[3.3.0]octenones, and in intermolecular cases to form both fused bicyclic cyclopentenones and spirocyclopentenones (equations 203 and 204)403-405. 

G. P. Chiusoli Catalysis of some insertion reactions by nickel complexes, pp, 169-199 (31). 

Another clear example of an acetylene insertion reaction was reported by Chiusoli (15). He observed that allylic halides react catalytically with nickel carbonyl in alcoholic solution, in the presence of CO and acetylene, to form esters of cis-2,5-hexadienoic acid. The intermediate in this reaction is very probably a 7r-allylnickel carbonyl halide, X, which then undergoes acetylene insertion followed by CO insertion and alcoholysis or acyl halide elimination (35). Acetylene is obviously a considerably better inserting group than CO in this reaction since with acetylene and CO, the hexadienoate is the only product, whereas, with only CO, the 3-butenoate ester is formed (15). [See Reaction 59]. 

The principal investigators in this field (Chiusoli and co-workers) have recently reviewed their contribution (39), and we will here only outline the course of reaction and discuss the most recent developments. 

The reactions described above are not limited to acetylene but appear to be general for monosubstituted acetylenes (54), the allylic group adding predominantly to the unsubstituted carbon atom. Reactions using substituted allyl halides indicate that the acetylene molecule attaches itself to the least-substituted terminal carbon atom of the allyl group. The interested reader is referred to the review by Chiusoli and Cassar (39) for the exact product distribution in these cases. 

Additions of aromatic C-H bond to olefins and acetylenes result in the formation of aryl-alkyl and aryl-alkenyl bonds. This type of addition reaction is not applicable to aryl-aryl bond formation. Catellani and Chiusoli [52] reported the first example of this type of arylation in 1985. To date, several arylation reactions of aromatic rings have been developed. In almost all cases, C-H bond cleavage proceeds through electrophilic substitution with transition-metal complexes [53]. 

P. M. Maitlis, and A. Haynes, Carbonylation Reactions of Alcohols and Esters, in Metal-catalysis in Industrial Organic Processes (Eds. G. P. Chiusoli, and P. M. Maitlis, RSC Publishing, Cambridge, 2006, Chap. 4.2). 

Another rapidly progressing field is that of multistep reactions which occur in ordered sequences chemo-, regio- and stereo-selectively on a transition metal species. To this end, it is necessary to delay release of the desired product until the whole series of steps has been completed competitive terminations (such as hydride elimination) must be prevented or must only occur at low rates compared to the main sequence. An example, reported by Chiusoli in the late 50s, is offered by the nickel-catalyzed synthesis of methyl 2,5-heptadienoate from 2-butenyl chloride, acetylene, CO and methanol. The reaction is chemo-, regio- and stereo-selective the four molecules react in the order shown in Equation A3.4 (chemoselectivity) the butenyl group attacks the terminal allylic carbon rather than the internal one (regioselectivity) and acetylene insertion leads to a Z double bond (stereoselectivity). 

G. P. Chiusoli and L. Cassar Angew. Chem. 79,177 (1967) Angew. Chem. Int. Ed. Engl. 6, 124 (1967) Nickel-catalysed reactions of allyl halides and related compounds 10 (55) ... 

In such situations, even the insertion into aryl C—H bonds can occur, e.g., in the coupling of aryl halides 135-X with norbornene (53). Thus, upon reaction of iodo- or bromoarenes 135-X with norbornene (53) (in the presence of [Pd(PPh3)4], KOrBu, and anisole at 110°C), Catellani and Chiusoli obtained the norbomane-annelated 9,10-dihydrophenanthrenes 136 and 137 (Scheme 3-36) [43, 187]. However, under different reaction conditions (Pd(OAc)2, K2CO3, Bu4NBr, DMF, 80 °C) the norbomane-annelated 4-aryl-9,10-dihydrophenanthrenes 138 were formed almost exclusively, apparently from three molecules of 135-Br and one molecule of norbornene (53) [188], The diversion from these two reactions is likely to occur only after the first three identical steps. ortho-C—H activation must occur twice in the formation of 138. 

The insertion reactions may occur more than once. Successive insertions can make quite complex organic compounds. For example, successive olefin insertion takes place in the polymerization reaction. The factors which differentiate oligomerization and polymerization are not clear. That is, the factors which determine whether one step or successive insertions will occur constitute an interesting but difficult problem. Selective and successive insertion reactions were observed by Chiusoli, Pottaccio, and Cassar in the reaction of allyl chlor-... 

A somewhat different example of /6-carbon elimination was observed by Catel-lani and Chiusoli in 1983 [14]. Reaction of two molecules of norbomene (79) with bromobenzene gave rise to 83. Stepwise carbopalladations of norbomene generate 80 and 81. Then /6-carbon elimination yields the alkylpalladium 82 and /6-H elimination affords 83. As described in Chapter 3.8.1, the deinsertion of norbomene from 84 to generate norbomene (79) and arylpalladium 85 is an example of /6-carbon elimination. 

M. Catellani and G. P. Chiusoli, J. Organomet. Chem., 1983, 250, 509-515. The Termination Step in Palladium-Catalyzed Insertion Reactions. 

R. Noyori, M. Uchiyama, H. Kato, S. Wakabayashi, and Y. Hayakawa, Pure Appl. Chem., 1990, 62, 613-622. Organometallic Methodologies for Nucleic Acid Synthesis. M. Catellani, G. P. Chiusoli, and M. Costa, Pure Appl. Chem., 1990, 62, 623-630. Some Palladium-Catalyzed Carbon-Carbon Bond Formation Reactions. 

Reactions of nickel carbonyl with allylic halides have been studied by Chiusoli (16). At 100° and 50 atm of carbon monoxide in the presence of... 

A number of terpenoid compounds have been synthesized by the reaction of n-allylnickel(I) halides with allyl bromides. Geranyl acetate (XCI) and farnesyl acetate (XCII) have been obtained from the nickel complex (XC) and appropriate allylic halides (Guerrieri and Chiusoli, 1969). The reaction of the complex (XCIII) and the bromides (XCIV) forms geranyl ether or ester... 

Methyl farnesoate (CIII) has been synthesized stereoselectively by the coupling of the geranyl nickel compound (Cl) (L = acetonitrile) with the allylic bromide (CII) (Chiusoli, 1971 Guerrieri et al., 1974). The stereochemistry of the reaction of 7t-allyl complexes of type CIV with allyl chloride depends markedly on the nature of the solvents. Media of low polarity and low coordinating power favor the formation of the cis isomer (CV), whereas in... 

The formation of phenols, which is a side reaction in the formation of doubly unsaturated acids from allyl halides, acetylene and carbon monoxide, as described by Chiusoli, may also be explained by the above scheme. 

Systems for which suggestions of intermediate Pd(IV) species formed by aryl halide oxidative addition have been proposed include reactions such as that of Scheme 9 developed by Catellani, Chiusoli and and de Meijere... 

In essence, these domino-coupling reactions form cyclohexadiene fragments from three two-carbon fragments. The 1 2 coupling of norbomene and iodobenzene discovered by Catellani and Chiusoli can also be adopted to couple norbomene with /3-bro-mostyrene.f hi an attempt to apply this Pd-catalyzed [2+2 + 2] assembly for an alternative and more productive access to Hopf s trifoliaphane, a 1 2 mixture of [2.2]paracyclophan-l-ene and l-bromo[2.2]paracyclophan-l-ene was tfeated with palladium acetate under Jeffery conditions. The main product was the hydrocarbon consisting of three [2.2]paracyclophane units linked by a common bicyclo[3.3.0]octene unit (Scheme Apparently, the key intermediate formed via a palladacycle preferen-... 

Bartolo, G., Salerno, G., Costa, M. and Chiusoli, G.P. (2004) Recent advances in the synthesis of carbonyl compounds by palladium-catalyzed oxidative carbonylation reactions of unsaturated substrates. Current Organic Chemistry, 8, 919-946. 

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