Nickel‐Catalysed Reactions of Allyl Halides and Related Compounds

Abstract

Allyl compounds react with carbon monoxide, or with carbon monoxide and acetylene, in the presence of tetracarbonylnickel as catalyst. These catalysts are involvedalso in coupling reactions and addition reactions of activated olefins and ketones. Reactions of this type can be used for the preparation of unsaturated aliphatic acids, esters, nitriles, hydrocarbons, alicyclic ketones, keto acids, keto esters, diketones, lactones, phenols, and other compounds. The reactions proceed via n-allylnickel complexes. In earlier publications L1 -21 we described two reactions for the preparation of unsaturated acids or esters by "carbonylation" with tetracarbonylnickel as the catalyst: Reaction (a) gives b,y-unsaturated compounds, while reaction (b) yields compounds with double bonds in both the a,@ and B,E positions, the K,@ substituents being cis to each other. Reaction (a) is carried out at room temperature and at 2-3 atm pressure. The reaction is suppressed at higher pressures unless the temperature is also raised, whereas lower pressures favor dimerization of the allyl groups. Generally the yields do not exceed 50%. Reaction (b) is best carried out at room temperature and at atmospheric pressure (yield up to 80 %). In both cases, the start of the reaction is characterized by a strong reddish coloration of the reaction mixture, which changes to green toward the end of the reaction. If the compound is a secondary halide that can rearrange to a primary halide, it reacts in the primary form; e.g. CH3-CHCl-CH=CH;, reacts as CH3-CH=CH-CH2C1 [ usual mild conditions (0-50 "C), but rearrange first to give secondary halides. Preparation of Unsaturated Acids and Esters fromWhen inert solvents (e.g. ethers or aromatic hydrocarbons) are used, the products are acyl halides [2a, 353. Reactions (a) and (b) are best carried out in dilute solution in the presence of an excess of tetracarbonylnickel (more than 1 mole per mole of allyl compound). Table 1 shows some methyl esters obtained via equation (b). No attempt was made to determine the optimum conditions for their syntheses. Reaction (b) may also yield by-products, such as acrylic acids or esters, from acetylene and carbon monoxide; however, the formation of these products can be suppressed by neutralization of the hydrogen chloride liberated. 3-Chloro-1-propyne (propargyl chloride) reacts with carbon monoxide, water, and tetracarbonylnickel to give 2,3-butadienoic acid and itaconic acid. The similarity between this and the reaction of allyl chloride is, however, purely formal. RCH=CH-COOCH3 R"-= CHz=CH-CHz-CH~-CH=CH-CHZ-CH2= C(CH3)CHz-CH3-CH = CH-CH(CH3)-CH~-C(CH~)=CH-CHZ-CH,-(CH2)2-CH=CH-CH2-CH~-(CH~)~-CH=CH-CHZ-CH,-(CH2)6-CH= CH-CHz-CH~-(CH~)I~-CH=CH-CHZ-CH~-C(CH~)~-CHZ-CH=CH-CHZ-H~COCO-CH=CH-CHZ-H~COCO-CHZ-CH=CH-CH~ HsCOCO-CH= CH-CH~-CHECH-CH~-H~COCO-CH=C(CH~)-CHZ-H~C-COO-CH~-CH=CH-CHZ-NC-CHz-CH=CH-CHz- 2-Cyclopenten-1-yl 2-Cyclohexen-1-yl GHs-CH=CH-CHz-H,COCO-CH=CH-CH2-CH=CH-CHZ-CH~-CH= CH-CHz-is a by-product in water/acetone).These reactions are carried out in the presence ...

The mechanism of transition metal catalyzed carbonylation of allyl halides: A theoretical investigation

“…However, since alternative techniques that avoid the direct manipulation of the toxic Ni(CO) 4 have been quite recently proposed, the use of nickel complexes has known a renewed interest. Moreto and co-workers [22,23] have applied a new synthetic approach to the Ni-mediated cyclocarbonylation of allyl halides and alkynes, a reaction reported some time ago by Chiusoli [17][18][19]. These authors have shown that, if pallyl nickel complexes (the hypothesized key-species of the process) are previously prepared (following a procedure suggested by Mackenzie et al [27]), cyclopentanones can be efficiently and selectively obtained without any handling of nickel carbonyl.…”

“…A number of papers, where different transition metal complexes are used as catalysts in the carbonylation of allyl halides, have appeared in the literature [5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20]. This process can be catalyzed by nickel tetracarbonyl Ni(CO) 4 [6,[15][16][17][18][19][20][21][22][23] and it was first reported by Chiusoli [6][7][8][9][10][11][12][13][14][15].…”

“…This process can be catalyzed by nickel tetracarbonyl Ni(CO) 4 [6,[15][16][17][18][19][20][21][22][23] and it was first reported by Chiusoli [6][7][8][9][10][11][12][13][14][15]. Room temperature and atmospheric or low (2-3 atm) CO pressures [17] can be used to carry out this reaction, but large amount of nickel tetra-carbonyl is required. The products are acyl halides in the presence of inert solvents, such as ethers or aromatic compounds.…”

A theoretical investigation of the oxidation states of palladium complexes and their role in the carbonylation reaction

“…A special case is represented by the carbonylation of allyl halides. For this reaction several papers proposing different transition metal complexes as catalysts, have appeared [21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36]. Nickel tetracarbonyl Ni(CO) 4 [22,31,37] was proposed for the first time by Chiusoli [22,31].…”

“…However, even if this reaction can be carried out at room temperature and under atmospheric or low CO pressures (2-3 atm.) [33], a large amount of nickel tetra-carbonyl is required.…”