Monoxide alkyl migration

Independent experiments show that the alkyl alkyne undergoes alkyl migration to carbon monoxide at — 100°C where the acyl can be trapped with phosphine, phosphite, or free carbon monoxide. Although the alkyl alkyne is converted to the acyl derivative by scavenging CO under the photolytic reaction conditions, these same alkyl derivatives can be isolated following thermal disproportionation of the acyl for a few minutes in refluxing toluene. Evidently thermal loss of CO from CpW(CO)-(HC=CH)[C(0)Me] promotes alkyl migration from the acyl back to the... 

Unlike the hydrogenation catalysts, most iridium catalysts studied for hydroformylation chemistry are not particularly active and are usually much less active than their rhodium counterparts see Carbonylation Processes by Homogeneous Catalysis). However, this lower activity was useful in utihzing iridium complexes to study separate steps in the hydroformylation mechanism. Using iridium complexes, several steps important in the hydroformylation cycle such as alkyl migration to carbon monoxide were studied. Another carbonylation reaction in which iridum catalysis appears to be conunercially viable is in the carbonylation of methanol. ... 

By the nature of its molecular mechanism, the carbonyl-insertion reaction represents a typical reaction mode of o alkyltransition metal complexes. Formation of the new C—C cr-bond takes place during a 1,2-alkyl-migration step, transforming an alkylmetal carbonyl moiety [cts-M(CO)R] into an acylmetal unit (M—COR) (89). In general, (s-cir-diene)-zirconocene complexes 5 appear to exhibit a substantial alkylmetal character (90). Therefore, it is not too surprising that some members of this class of compounds [in contrast to most other dienetransition metal complexes (97)] react with carbon monoxide with C—C bond formation (45). However, as demonstrated by X-ray structural data for 5 (Tables V... 

Reaction of [Mn(R)(CO)j] with neutral nucleophiles is by far the most widely studied type of reaction for [Mn(R)(CO)s] compounds. The reaction usually involves addition of the neutral neucleophile, L, and is accompanied by CO insertion/alkyl migration to form an acyl species [Eq. (29)]. L is usually a tertiary phosphine (PR3), an alkylated amine (RNH2), or free carbon monoxide. Besides being a carbon-carbon bond forming reaction of fundamental importance, alkyl migration reactions of transition metal alkyl species have direct relevance to catalysis, especially for the 0X0 or hydroformylation process (2), the Monsanto acetic acid synthesis (2), and the synthesis of ethylene glycol (94). 

When octahedral alkylpentacarbonyl derivatives of manganese(I) undergo carbon monoxide insertion assisted by a nucleophile L different from carbon monoxide (L = tertiary phosphines, amines, CO, etc.), the cis product is initially formed this observation, however, is not sufficient to permit one to distinguish between the alkyl migration mechanism [reaction (a)] and the insertion of a precoordinated carbonyl group into the manganese-carbon bond [reaction (e)]. In both cases mutually cis positions are involved. 

Carbon monoxide insertion into the copper-alkyl bond is indirectly shown by reaction of CO with dibutylcuprate(I), an anionic dialkyl derivative of dicoordinated copper(I). The product of the reaction, dibutylketone, may be rationalized by assuming carbon monoxide coordination to the anionic copper complex, followed by alkyl migration to the unstable anionic complex Cu[C(0)Bu](Bu) , with subsequent reductive elimination to the observed organic product. 

The insertion reaction is thus best considered as an alkyl migration to a coordinated carbon monoxide ligand in a m-position, and the migration probably proceeds through a three-center transition state ... 

The Monsanto acetic acid process produces acetic acid from methanol and CO gas under fairly mild conditions (I80 C, 30-40 atm). The process utilizes a square planar Rh(l) catalyst. As shown in Figure 19.33, the first step in the catalytic mechanism is the OA of methyl iodide to form an 18-electron compound. In the second step, CO insertion (alkyl migration) occurs, resulting in a 16-electron species. Carbon monoxide adds to the vacant coordination site to r enerate a saturated compound, which then undergoes RE of CH3COI to regenerate the catalyst. The CH3COI product is further processed by reaction with water to make acetic acid and HI. The latter... 

Schriver s group has shown that even in the absence of free carbon monoxide, the Lewis acids such as AlBr3 induce an alkyl migration in various complexes such as [MnMe(CO)s], [Mn(CH2Ph)(CO)5], [CpFeMe(CO)2l, and [CpMoMe(CO)3] to give products of the type in structure 2. 

Preparation.—Variations continue to appear on the theme of alcohol production by hydroboration-oxidation of olefins. 5-Methoxydialkylboranes react with olefins in the presence of lithium aluminium hydride to afford a new route to trialkylboranes and thence, by carbonylation-oxidation, to trialkylcarbinols. Carbonylation with carbon monoxide is avoided in a new procedure in the presence of an excess of trifluoroacetic anhydride, trialkyl cyanoborates undergo a triple alkyl migration from boron to carbon to give, on oxidation, high yields of trialkylcarbinols (Scheme 126). Tri-... 

Carbon Monoxide.—Some examples of carbon monoxide insertion (alkyl migrations) have been mentioned in the discussion of carbonylation and hydroformylation reactions in the previous chapter (Part IV, Chapter 3, Section 10). The remaining reports will be treated here in Periodic Table order. 

The reaction is sensitive to the presence of water, which inhibits the migration of the third alkyl group and leads to dialkyl ketones (see Chapter 12, Section II). The convenience of the hydroboration reaction combined with the use of carbon monoxide at atmospheric pressure provides the most accessible route to many trialkylcarbinols. 

As mentioned in the preceding section, the presence of water during the reaction of trialkylboranes with carbon monoxide inhibits the migration of the third alkyl group and leads to production of dialkyl ketones (i). This fact can be employed to advantage for the preparation of dialkyl ketones as shown in the scheme. 

Coupling of organostannanes with halides in a carbon monoxide atmosphere leads to ketones by incorporation of a carbonylation step.249 The catalytic cycle is similar to that involved in the coupling of alkyl or aryl halides. These reactions involve Reactions involving a migration of one of the organic substituents to the carbonyl carbon, followed by... 

The key steps in the reaction are addition of hydridorhodium to the double bond of the alkene and migration of the alkyl group to the complexed carbon monoxide. Hydrogenolysis then leads to the aldehyde. 

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